- Instytut Chemii i Techniki Jądrowej

Transcription

ANNUAL REPORT
2006
INSTITUTE
OF NUCLEAR CHEMISTRY
AND TECHNOLOGY
EDITORS
Prof. Jacek Michalik, Ph.D., D.Sc.
Wiktor Smułek, Ph.D.
Ewa Godlewska-Para, M.Sc.
PRINTING
Sylwester Wojtas
© Copyright by the Institute of Nuclear Chemistry and Technology, Warszawa 2007
All rights reserved
CONTENTS
GENERAL INFORMATION
MANAGEMENT OF THE INSTITUTE
9
11
MANAGING STAFF OF THE INSTITUTE
11
HEADS OF THE INCT DEPARTMENTS
11
SCIENTIFIC COUNCIL (2003-2007)
11
SCIENTIFIC STAFF
14
PROFESSORS
14
ASSOCIATE PROFESSORS
14
SENIOR SCIENTISTS (Ph.D.)
14
RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES
17
REACTIONS OF SUPEROXIDE RADICAL ANION WITH METHIONINE-ENKEPHALIN
AND ITS TERT-BUTOXYCARBONYL DERIVATIVE. PULSE AND GAMMA RADIOLYSIS STUDIES
O. Mozziconacci, J. Mirkowski, K. Bobrowski, Ch. Houée-Levin
19
REACTIONS OF HYDROGEN ATOM WITH METHIONINE-ENKEPHALIN AND RELATED
PEPTIDES. PULSE RADIOLYSIS STUDY
O. Mozziconacci, K. Bobrowski, C. Ferreri, Ch. Chatgilialoglu
21
PULSE RADIOLYSIS GENERATION OF THE RADICAL ANION DERIVED
FROM 2,3-DIHYDRO-OXOISOAPORPHINE IN ORGANIC SOLVENTS
K. Bobrowski, G. Kciuk, E. Sobarzo-Sanchez, J.R. De la Fuente
22
PULSE RADIOLYSIS STUDY OF THE INTERMEDIATES FORMED IN IONIC LIQUIDS. NATURE
OF INTERMEDIATES IN PULSE IRRADIATED p-TERPHENYL SOLUTION IN THE IONIC LIQUID
METHYLTRIBUTYLAMMONIUM BIS[(TRIFLUOROMETHYL)SULFONYL]IMIDE
J. Grodkowski, R. Kocia, J. Mirkowski
23
STEREOELECTRONIC CONTROL OVER THE MECHANISM OF SINGLET OXYGEN-INDUCED
DECARBOXYLATION IN ALKYLTHIOCARBOXYLIC ACIDS
M. Celuch, M. Enache, D. Pogocki
25
OXIDATION OF THIOETHERS BY ORGANIC COMPLEXES OF COPPER
M. Celuch, K. Serdiuk, J. Sadło, M. Enache, D. Pogocki
27
ORGANOSILVER RADICALS IN ZEOLITES
J. Turek, J. Sadło, J. Michalik
28
EPR STUDY ON RADIATION-INDUCED RADICAL DISTRIBUTION IN MASSIVE BONE GRAFTS
J. Sadło, J. Michalik, G. Strzelczak, A. Dziedzic-Gocławska , A. Kamiński
30
RADIATION CHEMISTS VIEW ON PANSPERMIA HYPOTHESIS
Z.P. Zagórski
31
MODIFIED BENTONITE FILLERS IN POLYMER COMPOSITES
Z. Zimek, G. Przybytniak, A. Nowicki, K. Mirkowski
33
POLY(SILOXANEURETHANE) UREAS BASED ON ALIPHATIC AND AROMATIC DIISOCYANATES
MODIFIED BY IONIZING RADIATION
E.M. Kornacka, G. Przybytniak, J. Kozakiewicz, J. Przybylski
36
RADIATION EFFECTS IN POLYPROPYLENE/POLYSTYRENE BLENDS
W. Głuszewski, Z.P. Zagórski
39
APPLICATION OF GAS CHROMATOGRAPHY TO STUDY POSTIRRADIATION PROCESSES
OF POLYMER OXIDATION
W. Głuszewski, Z.P. Zagórski
41
CHEMICAL-RADIATION DEGRADATION OF NATURAL POLYSACCHARIDES (CHITOSAN)
A.G. Chmielewski, W. Migdał, U. Gryczka, W. Starosta
42
DSC STUDIES OF GAMMA IRRADIATION EFFECT ON INTERACTION OF POTATO STARCH
WITH THE SELECTED FATTY ACIDS AND THEIR SODIUM SALTS
K. Cieśla, H. Rahier
44
SURFACE TENSION STUDIES OF BINDING CETYLTRIMETHYLAMMONIUM BROMIDE
TO GAMMA IRRADIATED AND NON-IRRADIATED POTATO AMYLOPECTIN
K. Cieśla, H. Lundqvist, A.-C. Eliasson
47
GAMMA IRRADIATION INFLUENCE ON STRUCTURE OF POTATO STARCH GELS STUDIED
BY SEM
K. Cieśla, B. Sartowska, E. Królak, W. Głuszewski
49
RADIOLYTIC DEGRADATION OF FUNGICIDE CARBENDAZIM BY GAMMA RADIATION
FOR ENVIRONMENTAL PROTECTION
A. Bojanowska-Czajka, P. Drzewicz, Z. Zimek, B. Szostek, H. Nichipor, M. Trojanowicz
52
COMPARISON OF PPSL AND TL METHODS FOR THE DETECTION OF IRRADIATED FOOD
AND FOOD COMPONENTS
G.P. Guzik, W. Stachowicz
56
DEVELOPMENT AND ACCREDITATION OF EPR METHOD FOR DETECTION OF IRRADIATED
FOOD CONTAINING SUGAR
K. Lehner, W. Stachowicz
58
DETECTION OF IRRADIATION IN HERBAL PHARMACEUTICALS WITH THE USE
OF THERMOLUMINESCENCE AND ELECTRON PARAMAGNETIC RESONANCE SPECTROMETRY
M. Laubsztejn, K. Malec-Czechowska, G. Strzelczak, W. Stachowicz
60
ACTIVITY OF THE LABORATORY FOR DETECTION OF IRRADIATED FOOD IN 2006
W. Stachowicz, K. Malec-Czechowska, K. Lehner, G.P. Guzik, M. Laubsztejn
63
RADIOCHEMISTRY, STABLE ISOTOPES,
NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY
65
103
Ru/103mRh GENERATOR
B. Bartoś, E. Kowalska, A. Bilewicz, G. Skarnemark
ZOLEDRONIC ACID LABELED WITH 47Sc AND
M. Neves, I. Antunes, A. Majkowska, A. Bilewicz
211
67
177
Lu FOR BONE PAIN THERAPY
67
211
Rh[16aneS4] At AND Ir[16aneS4] At COMPLEXES AS PRECURSORS FOR ASTATINE
RADIOPHARMACEUTICALS
M. Pruszyński, A. Bilewicz, M.R. Zalutsky
69
FORMATION KINETICS AND STABILITY OF SOME TRI- AND TETRAAZA DERIVATIVE
COMPLEXES OF SCANDIUM
A. Majkowska, A. Bilewicz
70
IN VITRO STABILITY OF TRICARBONYLTECHNETIUM(I) COMPLEXES
WITH N-METHYL-2-PYRIDINECARBOAMIDE AND N-METHYL-2-PYRIDINECARBOTHIOAMIDE
– HISTIDINE CHALLENGE
M. Łyczko, J. Narbutt
99m
ION EXCHANGE STUDIES ON THE ORGANOMETALLIC AQUA-ION fac-[
IN ACIDIC AQUEOUS SOLUTIONS
Z. Samczyński, M. Łyczko, R. Dybczyński, J. Narbutt
Tc(CO)3(H2O3]
71
+
73
SYNERGISTIC EFFECT OF NEUTRAL BIDENTATE N-HETEROCYCLIC LIGANDS
ON THE SEPARATION OF Am(III) FROM Eu(III) BY SOLVENT EXTRACTION
WITH TETRADENTATE 6,6’-BIS-(DIETHYL-1,2,4-TRIAZIN-3-YL)-2,2’-BIPYRIDINE
J. Narbutt, J. Krejzler
75
ESTIMATION OF CYTOSTATIC AND ANTIMICROBIAL ACTIVITY OF PLATINUM(II) COMPLEXES
WITH THIOUREA DERIVATIVES
E. Anuszewska, B. Gruber, H. Kruszewska, L. Fuks, N. Sadlej-Sosnowska
77
TRANSITION METAL SORPTION BY ALGINATE BIOSORBENT
D. Filipiuk, L. Fuks, M. Majdan
79
GALLIUM AND INDIUM ISOTOPE EFFECTS IN THE DOWEX 1-X8/HCl SYSTEM
I. Herdzik, W. Dembiński , W. Skwara, E. Bulska, A. Wysocka
81
PROFICIENCY TESTING SCHEME PLANTS 6 – DETERMINATION OF As, Cd, Cu, Hg, Pb, Se and Zn
IN DRY MUSHROOM POWDER (Suillus bovinus)
H. Polkowska-Motrenko, E. Chajduk, J. Dudek, M. Sadowska-Bratek, M. Sypuła
82
NEW POLISH CERTIFIED REFERENCE MATERIALS FOR INORGANIC TRACER ANALYSIS:
CORN FLOUR (INCT-CF-3) AND SOYA BEAN FLOUR (INCT-SBF-4)
H. Polkowska-Motrenko, R. Dybczyński, E. Chajduk, B. Danko, K. Kulisa, Z. Samczyński, M. Sypuła, Z. Szopa
85
DETERMINATION OF CADMIUM, LEAD AND COPPER IN FOOD PRODUCTS
AND ENVIRONMENTAL SAMPLES BY ATOMIC ABSORPTION SPECTROMETRY
AFTER SEPARATION BY SOLID PHASE EXTRACTION
J. Chwastowska, W. Skwara, E. Sterlińska, J. Dudek, L. Pszonicki
89
CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE
LIGANDS. PART LIX. THE CRYSTAL AND MOLECULAR STRUCTURE OF A ZINC(II) COMPLEX
WITH PYRIDAZINE-3,6-DICARBOXYLATE AND WATER LIGANDS
M. Gryz, W. Starosta, J. Leciejewicz
91
LIGANDS. PART LX. THE CRYSTAL AND MOLECULAR STRUCTURES OF MAGNESIUM(II)
AND ZINC(II) COMPLEXES WITH IMIDAZOLE-4-CARBOXYLATE AND WATER LIGANDS
92
LIGANDS. PART LXI. THE CRYSTAL AND MOLECULAR STRUCTURE OF A MANGANESE(II)
COMPLEX WITH PYRAZOLE-3,5-DICARBOXYLATE AND WATER LIGANDS
T. Premkumar, S. Govindarajan, W. Starosta, J. Leciejewicz
93
LIGANDS. PART LXII. THE CRYSTAL STRUCTURE AND MOLECULAR DYNAMICS
OF 2-AMINOPYRIDINE-3-CARBOXYLIC ACID
A. Pawlukojć, W. Starosta, J. Leciejewicz, I. Natkaniec, D. Nowak
94
LIGANDS. PART LXIII. THE CRYSTAL AND MOLECULAR STRUCTURE OF A CALCIUM(II)
COMPLEX WITH PYRAZINE-2,3,5,6-TETRACARBOXYLATE AND WATER LIGANDS
W. Starosta, J. Leciejewicz
94
LIGANDS. PART LXIV. THE CRYSTAL AND MOLECULAR STRUCTURE OF A ZINC(II) COMPLEX
WITH PYRAZOLE-4-CARBOXYLATE AND WATER LIGANDS
96
RADIOBIOLOGY
IRON CHELATORS INHIBIT DNIC FORMATION TO THE SAME EXTENT, INDEPENDENTLY
OF PERMEABILITY
K. Brzóska, H. Lewandowska, S. Męczyńska, B. Sochanowicz, J. Sadło, M. Kruszewski
97
99
GHRELIN, A LIGAND FOR THE GROWTH HORMONE SECRETAGOGUE RECEPTOR, INCREASES
DNA BREAKAGE IN X-IRRADIATED PIGLET BLOOD MONONUCLEAR CELLS
M. Kruszewski, T. Iwaneńko, J. Woliński, M. Wojewódzka
100
GHRELIN INCREASES HYDROGEN PEROXIDE-INDUCED DNA BREAKAGE IN PIGLET BLOOD
MONONUCLEAR CELLS
T. Bartłomiejczyk, T. Iwaneńko, M. Wojewódzka, J. Woliński, R. Zabielski, M. Kruszewski
101
THE EFFECT OF LEPTIN ON DNA BREAKAGE INDUCED BY GENOTOXIC AGENTS IN HUMAN
PERIPHERAL BLOOD MONONUCLEAR CELLS
M. Kruszewski, T. Iwaneńko, M. Wojewódzka, J. Woliński, R. Zabielski
102
CABAS – A FREELY AVAILABLE PC PROGRAM FOR FITTING CALIBRATION CURVES
IN CHROMOSOME ABERRATION DOSIMETRY
J. Deperas, M. Szłuińska, M. Deperas-Kaminska, A. Edwards, D. Lloyd, C. Lindholm, H. Romm, L. Roy, R. Moss,
J. Morand, A. Wójcik
103
THE TEMPERATURE EFFECT ON THE FREQUENCY OF RADIATION-INDUCED MICRONUCLEI
IN HUMAN PERIPHERAL BLOOD LYMPHOCYTES IS ABOLISHED BY DMSO
K. Brzozowska, A. Wójcik
104
VARIABLE RADIOSENSITIVITY OF CHROMOSOMES 2, 8 AND 14 IN HUMAN PERIPHERAL
BLOOD LYMPHOCYTES EXPOSED TO 480 MeV/n 12C-IONS
M. Deperas-Kaminska, G.N. Timoshenko, E.A. Krasavin, A. Wójcik
105
EFFICIENT DOUBLE STRAND BREAK REJONING AND SURVIVAL IN X-IRRADIATED HUMAN
GLIOMA M059 CELLS ARE DEPENDENT ON EGF RECEPTOR KINASE ACTIVITY
I. Grądzka, B. Sochanowicz, I. Szumiel
106
DECREASED PERSISTANCE OF γH2AX FOCI IN X-IRRADIATED xrs6 CELLS TREATED
WITH SIRTUIN INHIBITOR
M. Wojewódzka, M. Kruszewski, I. Szumiel
107
TWO p53 BINDING PROTEINS ARE PRESENT IN LY-R (REPAIR COMPETENT) AND LY-S (REPAIR
DEFICIENT) CELLS IN DIFFERENT PROPORTIONS
B. Sochanowicz, I. Szumiel
108
PREMATURE CHROMOSOME CONDENSATION IN BIOLOGICAL DOSIMETRY AFTER HIGH DOSE
GAMMA IRRADIATION
S. Sommer, I. Buraczewska, A. Wójcik
109
NUCLEAR TECHNOLOGIES AND METHODS
111
PROCESS ENGINEERING
113
METHOD FOR COLLECTION OF NITRATE FROM WATER SAMPLES AND DETERMINATION
OF NITROGEN AND OXYGEN ISOTOPE COMPOSITION
M. Derda, S.M. Cuna, R. Wierzchnicki
113
THE KINETICS OF TRANS-DICHLOROETHYLENE DECOMPOSITION IN AIR
UNDER ELECTRON-BEAM IRRADIATION
Y. Sun, A.G. Chmielewski, S. Bułka, Z. Zimek, H. Nichipor
114
ELECTRON BEAM OF VOCs TREATMENT EMITTED FROM OIL COMBUSTION PROCESS
A. Ostapczuk, J. Licki, A.G. Chmielewski
115
ELECTRON BEAM TREATMENT OF FLUE GAS FROM FUEL OIL COMBUSTION
A.G. Chmielewski, A. Pawelec, B. Tymiński, Z. Zimek, J. Licki, A.A. Basfar
117
DOSIMETRY FOR COMBUSTION FLUE GAS TREATMENT WITH ELECTRON BEAM
K. Mehta, S. Bułka
118
CATALYTIC CRACKING OF POLYOLEFINE WASTES IN A LARGE LABORATORY INSTALLATION
B. Tymiński, K. Zwoliński, R. Jurczyk
119
ECONOMICAL COMPARISON OF ABSORPTION AND MEMBRANE METHODS APPLIED
FOR THE ENRICHMENT OF METHANE IN BIOGAS
M. Harasimowicz, G. Zakrzewska-Trznadel, W. Ziółkowska, A.G. Chmielewski
120
STUDY OF BOUNDARY-LAYER PHENOMENA IN MEMBRANE PROCESSES
G. Zakrzewska-Trznadel, A. Miśkiewicz, M. Harasimowicz, E. Dłuska, S. Wroński, A. Jaworska, C. Cojocaru
121
A STUDY OF STABLE ISOTOPE COMPOSITION IN MILK
R. Wierzchnicki, M. Derda
123
3
INTERLABORATORY TESTS OF H MEASUREMENTS IN WATER SAMPLES
W. Sołtyk, J. Walendziak, J. Palige
124
MODELLING FOR GROUNDWATER FLOW IN THE OPENCAST BEŁCHATÓW AREA
R. Zimnicki
124
TRACER AND CFD INVESTIGATIONS OF SEDIMENTATION PROCESSES IN RECTANGULAR
SETTLER
J. Palige, A. Dobrowolski, S. Ptaszek, A.G. Chmielewski
125
NATIVE AND TRANSPLANTED Pleurozium schreberi (Brid.) Mitt. AS BIOINDICATOR
OF NITROGEN DEPOSITION IN A HEAVY INDUSTRY AREA OF UPPER SILESIA
G. Kosior, A. Samecka-Cymerman, A.G. Chmielewski, R. Wierzchnicki, M. Derda, A.J. Kempers
126
MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS
128
IDENTIFICATION OF LEAD WHITE OF THE 15th CENTURY GDAŃSK PANEL PAINTINGS
BY MEANS OF INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS
E. Pańczyk, J. Olszewska-Świetlik, L. Waliś
128
ELEMENTAL COMPOSITION AND PARTICLES MORPHOLOGY OF LEAD WHITE PIGMENTS
B. Sartowska, E. Pańczyk, L. Waliś
130
ULTRAVIOLET BLUE FLUORESCENCE OF CENTRAL EUROPEAN BAROQUE GLASS
(FURTHER RESULTS)
J. Kunicki-Goldfinger, J. Kierzek, P. Dzierżanowski
134
LATE 17th CENTURY GLASS VESSELS FROM EILAND – TECHNOLOGICAL APPROACH
J. Kunicki-Goldfinger, M. Mádl, P. Dzierżanowski
136
WATER SOLUBLE SILICA BIOCIDES CONTAINING QUATERNARY AMMONIUM SALTS
A. Łukasiewicz, D.K. Chmielewska, L. Waliś
141
THE ROLE OF CARBON, CHROMIUM AND NITROGEN IN AUSTENITIZATION OF UNALLOYED
AND ALLOYED STEELS BY INTENSE PLASMA PULSES
J. Piekoszewski, L. Dąbrowski, B. Sartowska, L. Waliś, M. Kopcewicz, J. Kalinowska, M. Barlak, J. Stanisławski,
Z. Werner, A. Barcz
141
THERMAL STABILITY OF THE PHASES FORMED IN THE NEAR SURFACE LAYERS OF CARBON
STEEL BY NITROGEN PULSED PLASMA TREATMENT
B. Sartowska, J. Piekoszewski, L. Waliś, J. Stanisławski, L. Nowicki, R. Ratajczak, M. Kopcewicz
142
ELECTRON-BEAM IRRADIATION OF PVDF MEMBRANES AS A METHOD FOR OBTAINING
BRITTLE FRACTURES FOR SEM OBSERVATIONS
B. Sartowska, O. Orelovitch, A. Nowicki
144
SELECTED PROPERTIES OF POLYPYRROLE NANOSTRUCTURES DEPOSITED
IN TRACK-ETCHED MEMBRANE TEMPLATES
M. Buczkowski, W. Starosta, B. Sartowska, D. Wawszczak
145
SOL-GEL-DERIVED HYDROXYAPATITE AND ITS APPLICATION TO SORPTION OF HEAVY
METALS
A. Deptuła, J. Chwastowska, W. Łada, T. Olczak, D. Wawszczak, E. Sterlińska, B. Sartowska, M. Brykała,
K.C. Goretta
147
PHYSICAL AND CHEMICAL PROPERTIES OF YTTERBIUM DOPED KY(WO4)2 NANOCRYSTALS
A. Deptuła, M.T. Borowiec, V.P. Dyakonov, W. Łada, T. Olczak, D. Wawszczak, P. Aleshkevych, W. Domuchowski,
T. Zayarnyuk, M. Barański, H. Szymczak, M. Brykała
151
SAXS STUDY OF XERO- AND AERO-GELS FORMED FROM MONOSACCHARIDE GELATORS
H. Grigoriew, D.K. Chmielewska
153
NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS
222
MEASUREMENT OF Rn AND
B. Machaj, P. Urbański, J. Bartak
220
156
Rn WITH SINGLE SCINTILLATION CELL
156
DOSIMETRIC GATE DSP-15
E. Świstowski, J. Mirowicz, P. Urbański, J. Pieńkos
158
GAMMA THIN LAYER CHROMATOGRAPHY ANALYZER SC-05
E. Świstowski, B. Machaj, E. Kowalska, J. Pieńkos, E. Gniazdowska
159
INVESTIGATION OF DUST POLLUTION IN ASSEMBLING HALL OF TV SETS
J. Pieńkos, P. Urbański
160
COMMERCIAL APPLICATION OF ELECTRON BEAM ACCELERATORS AT R&D AND SERVICE
CENTER
A.G. Chmielewski, W. Migdał, Z. Zimek, I. Kałuska, S. Bułka
161
ELECTRON GUN FOR 10 MeV, 10 kW ELECTRON ACCELERATOR
Z. Dźwigalski, Z. Zimek
163
THE INCT PUBLICATIONS IN 2006
165
ARTICLES
165
BOOKS
173
CHAPTERS IN BOOKS
173
THE INCT REPORTS
174
CONFERENCE PROCEEDINGS
175
CONFERENCE ABSTRACTS
176
SUPPLEMENT LIST OF THE INCT PUBLICATIONS IN 2005
185
NUKLEONIKA
186
INTERVIEWS IN 2006
191
THE INCT PATENTS AND PATENT APPLICATIONS IN 2006
192
PATENTS
192
PATENT APPLICATIONS
192
CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2006
193
Ph.D./D.Sc. THESES IN 2006
198
Ph.D. THESES
198
D.Sc. THESES
198
EDUCATION
199
Ph.D. PROGRAMME IN CHEMISTRY
199
TRAINING OF STUDENTS
199
RESEARCH PROJECTS AND CONTRACTS
201
RESEARCH PROJECTS GRANTED BY THE MINISTRY OF SCIENCE
AND HIGHER EDUCATION IN 2006 AND IN CONTINUATION
201
RESEARCH PROJECTS ORDERED BY THE MINISTRY OF SCIENCE
AND HIGHER EDUCATION IN 2006
202
IAEA RESEARCH CONTRACTS IN 2006
202
IAEA TECHNICAL CONTRACTS IN 2006
202
EUROPEAN COMMISSION RESEARCH PROJECTS IN 2006
202
OTHER FOREIGN CONTRACTS IN 2006
203
LIST OF VISITORS TO THE INCT IN 2006
204
THE INCT SEMINARS IN 2006
206
LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2006
207
LECTURES
207
SEMINARS
209
AWARDS IN 2006
211
INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 212
INDEX OF THE AUTHORS
224
GENERAL INFORMATION
9
GENERAL INFORMATION
The Institute of Nuclear Chemistry and Technology (INCT) is one of the successors of
the Institute of Nuclear Research (INR) which was established in 1955. The latter
Institute, once the biggest Institute in Poland, has exerted a great influence on the
scientific and intelectual life in this country. The INCT came into being as one of the
independent units established after the dissolution of the INR in 1983.
At present, the Institute research activity is focused on:
• radiation chemistry and technology,
• radiochemistry and coordination chemistry,
• radiobiology,
• application of nuclear methods in material and process engineering,
• design of instruments based on nuclear techniques,
• trace analysis and radioanalytical techniques,
• environmental research.
In the above fields we offer research programmes for Ph.D. students.
At this moment, with its nine electron accelerators in operation and with the staff
experienced in the field of electron beam (EB) applications, the Institute is one of the
most advanced centres of radiation research and EB processing. The accelerators are
installed in the following Institute units:
• pilot plant for radiation sterilization of medical devices and transplants,
• pilot plant for radiation modification of polymers,
• experimental pilot plant for food irradiation,
• pilot plant for removal of SO2 and NOx from flue gases,
• pulse radiolysis laboratory, in which the nanosecond set-up was put into operation
in 2001. A new 10 MeV accelerator was constructed in the INCT for this purpose.
Based on the technology elaborated in our Institute, an industrial installation for
electron beam flue gas treatment has been implemented at the EPS “Pomorzany” (Dolna
Odra PS Group). This is the second full scale industrial EB installation for SO2 and
NOx removal all over the world.
***
In 2006, the INCT scientists published 81 papers in scientific journals registered in
the Philadelphia list, among them 49 papers in journals with an impact factor (IF)
higher than 1.0. The INCT research workers are also the authors of one book and 7
chapters in scientific books published in 2006.
In 2006, the Ministry of Science and Higher Education (MSHE) granted 5 research
projects. Altogether the INCT is carrying out 23 MSHE research projects including 3
ordered projects and 1 implementation project, and 6 research projects supported financially by the European Commission.
Annual rewards of the INCT Director-General for the best publications in 2006
were granted to the following research teams:
• First degree group award to Leon Pszonicki, Jadwiga Chwastowska, Witold Skwara
and Elżbieta Sterlińska for two publications in “Talanta” presenting methods for
the determination of platinum, palladium and chromium in trace quantities in environmental samples and speciation analysis of Cr(VI) in the presence of Cr(III).
10
GENERAL INFORMATION
• Second degree group award to Marcin Kruszewski, Hanna Lewandowska, Teresa
Bartłomiejczyk, Teresa Iwaneńko and Barbara Sochanowicz for publications
in the journals “Biochemical and Biophysical Research Communications”, “Journal
of Biological Chemistry” and “Acta Biochimica Polonica” devoted to studies of relations between the metabolism of iron on a cell level and DNA oxidative damage.
• Third degree group award to Sławomir Siekierski and Kinga Frąckiewicz for the
essential contribution to the work on basic studies of secondary periodicity of elements of the block p (group 13) published in “European Journal of Inorganic Chemistry”.
In 2006, the INCT scientific community was especially active in organizing scientific conferences. In total, in 2006, five international meetings have been organized:
• Regional Training Course “Application of Monte Carlo modeling methods for
dosimetry calculation in radiation processing” in the frame of the IAEA Technical
Cooperation Project RER/8/010 “Quality control methods and procedures for radiation technology” (3-7 April 2006, Warszawa);
• The Workshop “Dosimetry for radiation application in technologies for environmental pollution control” in the frame of the Marie Curie Host Fellowships for the
EU Transfer of Knowledge “Advanced methods for environment research and control (AMERAC)” (5 April 2006, Warszawa);
• The Workshop “Methods of enviromental research” in the frame of the Marie Curie
Host Fellowships for the EU Transfer of Knowledge “Advanced methods for environment research and control (AMERAC)” (10 August 2006, Warszawa);
• Symposium on Chemistry and Radiation Techniques: Challenge and Possibilities –
Jubilee of the 80th Anniversary of Prof. Zbigniew P. Zagórski, Ph.D., D.Sc. (17
October 2006, Warszawa);
• IV Conference on Problems of Waste Disposal (27 November 2006, Warszawa).
The international journal for nuclear research – NUKLEONIKA, published by
the INCT, was mentioned in the SCI Journal Citation List.
11
MANAGING STAFF OF THE INSTITUTE
Director
Assoc. Prof. Lech Waliś, Ph.D.
Deputy Director for Research and Development
Prof. Jacek Michalik, Ph.D., D.Sc.
Deputy Director for Maintenance and Marketing
Roman Janusz, M.Sc.
Accountant General
Małgorzata Otmianowska-Filus, M.Sc.
HEADS OF THE INCT DEPARTMENTS
•
•
•
•
•
Department of Nuclear Methods of Materials
Engineering
Wojciech Starosta, Ph.D.
Department of Radioisotope Instruments
and Methods
Prof. Piotr Urbański, Ph.D., D.Sc.
Department of Radiochemistry
Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.
Department of Nuclear Methods of Process
Engineering
Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.
Department of Radiation Chemistry
and Technology
Zbigniew Zimek, Ph.D.
•
•
•
•
•
Department of Analytical Chemistry
Prof. Rajmund Dybczyński, Ph.D., D.Sc.
Department of Radiobiology and Health
Protection
Prof. Irena Szumiel, Ph.D., D.Sc.
Experimental Plant for Food Irradiation
Assoc. Prof. Wojciech Migdał, Ph.D., D.Sc.
Laboratory for Detection of Irradiated Food
Wacław Stachowicz, Ph.D.
Laboratory for Measurements of Technological
Doses
Zofia Stuglik, Ph.D.
SCIENTIFIC COUNCIL (2003-2007)
1. Prof. Grzegorz Bartosz, Ph.D., D.Sc.
University of Łódź
• biochemistry
2. Assoc. Prof. Aleksander Bilewicz, Ph.D., D.Sc.
Institute of Nuclear Chemistry and Technology
• radiochemistry, inorganic chemistry
3. Prof. Krzysztof Bobrowski, Ph.D., D.Sc.
(Chairman)
• radiation chemistry, photochemistry, biophysics
4. Sylwester Bułka, M.Sc.
• electronics
5. Prof. Witold Charewicz, Ph.D., D.Sc.
Wrocław University of Technology
• inorganic chemistry, hydrometallurgy
12
6. Prof. Stanisław Chibowski, Ph.D., D.Sc.
Maria Curie-Skłodowska University
• radiochemistry, physical chemistry
21. Prof. Józef Mayer, Ph.D., D.Sc.
Technical University of Łódź
• physical and radiation chemistry
7. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.
• chemical and process engineering, nuclear chemical engineering, isotope chemistry
22. Prof. Jacek Michalik, Ph.D., D.Sc.
• radiation chemistry, surface chemistry, radical
chemistry
8. Prof. Jadwiga Chwastowska, Ph.D., D.Sc.
• analytical chemistry
23. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.
• radiochemistry, coordination chemistry
9. Prof. Rajmund Dybczyński, Ph.D., D.Sc.
24. Jan Paweł Pieńkos, Eng.
10. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc.
(Vice-chairman)
Warsaw University of Technology
• chemical technology
11. Prof. Leon Gradoń, Ph.D., D.Sc.
Warsaw University of Technology
chemical and process engineering
•
12. Assoc. Prof. Edward Iller, Ph.D., D.Sc.
Radioisotope Centre POLATOM
• chemical and process engineering, physical
chemistry
13. Assoc. Prof. Marek Janiak, Ph.D., D.Sc.
Military Institute of Hygiene and Epidemiology
• radiobiology
14. Iwona Kałuska, M.Sc.
• radiation chemistry
15. Assoc. Prof. Marcin Kruszewski, Ph.D., D.Sc.
• radiobiology
16. Prof. Marek Lankosz, Ph.D., D.Sc.
AGH University of Science and Technology
physics, radioanalytical methods
•
• electronics
25. Prof. Leon Pszonicki, Ph.D., D.Sc.
26. Prof. Sławomir Siekierski, Ph.D.
• physical chemistry, inorganic chemistry
27. Prof. Sławomir Sterliński, Ph.D., D.Sc.
Central Laboratory for Radiological Protection
• physics, nuclear technical physics
28. Prof. Irena Szumiel, Ph.D., D.Sc.
• cellular radiobiology
29. Prof. Jerzy Szydłowski, Ph.D., D.Sc.
Warsaw University
• physical chemistry, radiochemistry
30. Prof. Jan Tacikowski, Ph.D.
Institute of Precision Mechanics
• physical metallurgy and heat treatment of metals
31. Prof. Marek Trojanowicz, Ph.D., D.Sc.
17. Prof. Janusz Lipkowski, Ph.D., D.Sc.
Institute of Physical Chemistry, Polish Academy
of Sciences
• physicochemical methods of analysis
32. Prof. Piotr Urbański, Ph.D., D.Sc.
(Vice-chairman)
• radiometric methods, industrial measurement
equipment, metrology
18. Zygmunt Łuczyński, Ph.D.
Institute of Electronic Materials Technology
• chemistry
33. Assoc. Prof. Lech Waliś, Ph.D.
• material science, material engineering
19. Prof. Andrzej Łukasiewicz, Ph.D., D.Sc.
• material science
34. Prof. Andrzej Wójcik, Ph.D., D.Sc.
(Vice-chairman)
• cytogentics
20. Prof. Bronisław Marciniak, Ph.D., D.Sc.
Adam Mickiewicz University
• physical chemistry
35. Prof. Zbigniew Zagórski, Ph.D., D.Sc.
•
physical chemistry, radiation chemistry, electrochemistry
13
•
electronics, accelerator techniques, radiation
processing
36. Zbigniew Zimek, Ph.D.
HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (2003-2007)
1. Prof. Antoni Dancewicz, Ph.D., D.Sc.
• biochemistry, radiobiology
14
SCIENTIFIC STAFF
SCIENTIFIC STAFF
PROFESSORS
1. Bobrowski Krzysztof
9. Piekoszewski Jerzy
radiation chemistry, photochemistry, biophysics
2. Chmielewski Andrzej G.
solid state physics
10. Pszonicki Leon
chemical and process engineering, nuclear chemical engineering, isotope chemistry
3. Chwastowska Jadwiga
analytical chemistry
11. Siekierski Sławomir
physical chemistry, inorganic chemistry
12. Szumiel Irena
4. Dybczyński Rajmund
cellular radiobiology
13. Trojanowicz Marek
5. Leciejewicz Janusz
crystallography, solid state physics, material science
6. Łukasiewicz Andrzej
14. Urbański Piotr
radiometric methods, industrial measurement
equipment, metrology
material science
7. Michalik Jacek
15. Wójcik Andrzej
radiation chemistry, surface chemistry, radical chemistry
8. Ostyk-Narbutt Jerzy
radiochemistry, coordination chemistry
cytogenetics
16. Zagórski Zbigniew
physical chemistry, radiation chemistry, electrochemistry
ASSOCIATE PROFESSORS
1. Bilewicz Aleksander
6. Pogocki Dariusz
radiochemistry, inorganic chemistry
2. Grigoriew Helena
radiation chemistry, pulse radiolysis
7. Przybytniak Grażyna
solid state physics, diffraction research of non-crystalline matter
radiation chemistry
8. Waliś Lech
3. Grodkowski Jan
material science, material engineering
radiation chemistry
9. Zakrzewska-Trznadel Grażyna
4. Kruszewski Marcin
process and chemical engineering
radiobiology
10. Żółtowski Tadeusz
5. Migdał Wojciech
chemistry, science of commodies
nuclear physics
SENIOR SCIENTISTS (Ph.D.)
1. Bartłomiejczyk Teresa
biology
2. Borkowski Marian
chemistry
3. Buczkowski Marek
physics
4. Cieśla Krystyna
physical chemistry
SCIENTIFIC STAFF
5. Danilczuk Marek
chemistry
6. Danko Bożena
7. Dembiński Wojciech
chemistry
8. Deptuła Andrzej
chemistry
9. Derda Małgorzata
chemistry
10. Dobrowolski Andrzej
chemistry
11. Dudek Jakub
chemistry
12. Dźwigalski Zygmunt
high voltage electronics, electron injectors, gas
lasers
13. Frąckiewicz Kinga
chemistry
14. Fuks Leon
chemistry
15. Gniazdowska Ewa
chemistry
16. Grądzka Iwona
biology
17. Harasimowicz Marian
technical nuclear physics, theory of elementary
particles
18. Kierzek Joachim
physics
19. Kornacka Ewa
15
27. Owczarczyk Andrzej
chemistry
28. Palige Jacek
metallurgy
29. Panta Przemysław
nuclear chemistry
30. Pawelec Andrzej
chemical engineering
31. Pawlukojć Andrzej
physics
32. Polkowska-Motrenko Halina
33. Rafalski Andrzej
radiation chemistry
34. Sadło Jarosław
chemistry
35. Samczyński Zbigniew
36. Skwara Witold
37. Sochanowicz Barbara
biology
38. Sommer Sylwester
radiobiology, cytogenetics
39. Stachowicz Wacław
radiation chemistry, EPR spectroscopy
40. Starosta Wojciech
chemistry
41. Strzelczak Grażyna
radiation chemistry
chemistry
20. Krejzler Jadwiga
chemistry
21. Kunicki-Goldfinger Jerzy
conservator/restorer of art
22. Lewandowska-Siwkiewicz Hanna
chemistry
23. Machaj Bronisław
radiometry
24. Mikołajczuk Agnieszka
chemistry
25. Mirkowski Jacek
nuclear and medical electronics
26. Nowicki Andrzej
organic chemistry and technology, high-temperature technology
42. Stuglik Zofia
radiation chemistry
43. Sun Yongxia
chemistry
44. Szpilowski Stanisław
chemistry
45. Szreder Tomasz
chemistry
46. Tymiński Bogdan
chemistry
47. Warchoł Stanisław
solid state physics
48. Wąsowicz Tomasz
radiation chemistry, surface chemistry, radical chemistry
16
SCIENTIFIC STAFF
49. Wierzchnicki Ryszard
chemical engineering
50. Wiśniowski Paweł
radiation chemistry, photochemistry, biophysics
51. Wojewódzka Maria
radiobiology
52. Zielińska Barbara
chemistry
53. Zimek Zbigniew
electronics, accelerator techniques, radiation processing
RADIATION CHEMISTRY
AND PHYSICS,
RADIATION TECHNOLOGIES
19
REACTIONS OF SUPEROXIDE RADICAL ANION
WITH METHIONINE-ENKEPHALIN
AND ITS TERT-BUTOXYCARBONYL DERIVATIVE.
PULSE AND GAMMA RADIOLYSIS STUDIES
Olivier Mozziconacci, Jacek Mirkowski, Krzysztof Bobrowski, Chantal Houée-Levin1/
1/
Université Paris-Sud, Orsay, France
The pentapeptide methionine-enkephalin (Met-enk)
(Chart 1) is a natural opiate that inhibits signals of
pain. Many studies have demonstrated the connection between the interactions of the opiate and reactive oxygen species (ROS) with cell injuries [1].
The aromatic amino acid residues are especially
good targets for oxidation by ROS during oxidative stress. In particular tyrosine can be converted
into a dimer or into dihydroxyphenylalanine (DOPA)
in enkephalins [2,3]. This interesting free-radical
chemistry occurs widely in biological systems but
it is still a largely unexplored area of research. The
addition of superoxide radical anion (O2 –) to a tyrosyl radical (TyrO ) leads to a hydroperoxide, which
gets cyclized by the Michael addition of the amine
onto the ring [4]. The stability of the hydroperoxide depends on the neighboring function [5]. However, the occurrence of this mechanism on peptides
or proteins has never been directly demonstrated.
In this report we report evidence for this mechanism on a natural peptide, Met-enk. Moreover, we
show that, when the amine function is blocked by
the tert-butoxycarbonyl group – t-Boc-Met-enk
(Chart 1), tyrosine is restored by O2 –.
The transient absorption spectrum of Met-enk
recorded 55 μs after the pulse in N2O-saturated
solution containing azide ions, revealed two absorption bands with maxima in the visible region
at 390 and 405 nm (Fig.1, curve a). This absorption is assigned to TyrO radicals which were formed upon oxidation of the tyrosine residue (TyrOH)
in Met-enk by N3 radicals:
·
·
·
·
·
Fig.1. Absorption spectra obtained after oxidation of
Met-enk (c) and t-Boc-Met-enk (z) by N3 radicals
in N2O-saturated aqueous solutions containing 0.1
mM of peptides and 50 mM of N3– taken 55 μs after
the pulse.
·
·
·
TyrOH + N3 → TyrO + H+ + N3–
Similar transient absorption spectrum with the
two absorption bands at 390 and 405 nm and again
assigned to TyrO radicals was observed in the same
conditions in solution containing t-Boc-Met-enk
(Fig.1, curve b).
Like in N2O-saturated solutions, the transient
absorption spectra recorded 55 μs after the pulse
observed in O2-saturated solutions containing
Met-enk and t-Boc-Met-enk were assigned to TyrO
radicals.
However, in O2-saturated solutions containing
Met-enk and t-Boc-Met-enk a new absorption
band at 360-380 nm appeared at the millisecond
time scale (Fig.2). This band was attributed to the
product of the reaction of O2 – with TyrO . However, the kinetic traces leading to this spectrum
were different (Fig.2, insets). In solution containing t-Boc-Met-enk, the decay at 405 nm reached a
pseudo-plateau around 1 ms after the pulse.
Two peaks were observed in HPLC chromatograms after gamma-irradiation in N2O-saturated
solutions containing Met-enk. The first peak corresponds to the native Met-enk. The second peak
increased with the dose (Fig.3A). It was the most
intense peak when fluorescence detection (exc. 284
nm, em. 425 nm) was applied. Additionally, a third
peak appeared which also increased with the dose
and was fluorescent with the same characteristics
(Fig.3B). Both peaks were attributed to dimers of
Met-enk linked by bityrosine, the most intense as the
3,3’-bityrosine. UV-VIS spectrum of the irradiated
Met-enk solution was characteristic of bityrosine.
·
·
·
Chart 1.
·
20
On the other hand, HPLC chromatograms after
irradiation of O2-saturated solution containing
t-Boc-Met-enk showed only one peak (Fig.4B)
which had the same retention time as the native
peptide (Fig.4A) and its density remained very close
to that in non-irradiated solution. This indicates
that irradiation of Boc-Met-enk in aerobic conditions does not lead to oxidation products since the
amount of non-modified peptide was unchanged.
All observations described above showed that
blocking the amine function by the tert-butoxycarbonyl group does not affect the reaction pathway of TyrO radicals in anaerobic conditions.
·
Fig.2. Absorption spectrum obtained after oxidation of
t-Boc-Met-enk (z) by N3 radicals in O2-saturated
aqueous solutions containing 0.1 mM of the peptide
and 5 mM of N3– taken 1 ms after the pulse. Insets:
The time profiles recorded at λ=405 nm in O2-saturated aqueous solutions containing 5 mM of N3– and
0.1 mM of Met-enk (left) or t-Boc-Met-enk (right).
·
In O2-saturated solution containing Met-enk,
the peak that corresponds to 3,3’-bityrosine was
visible only by its very weak fluorescence. This indicates a small yield of 3,3’-bityrosine formation
in Met-enk dimer. On the other hand, another
new peak with elution time shorter than the native
Met-enk was observed. Compared to N2O-saturated
solution, the shape of the UV-VIS spectrum was
different. The bands at 290 and 315 nm were much
weaker, with two intense absorption bands located
at 275 and 285 nm. This indicates a lower amount
of Met-enk dimers with bityrosine and formation
of a new stable product.
In N2O-saturated solution containing t-Boc-Met-enk, the stable product pattern was similar
to that observed in N2O-saturated solution containing Met-enk (vide supra).
Fig.4. HPLC chromatograms recorded in (A) non-irradiated, (B) irradiated with 84 Gy O2-saturated aqueous solutions containing 0.25 mM of t-Boc-Met-enk
and 50 mM of N3–. Detection by UV-Vis absorption
at 274 nm.
In spite of the fact that the first step of oxidation of Met-enk and t-Boc-Met-enk by N3 in aerobic conditions is the same, there are different mechanisms for the secondary reactions occurring in
Met-enk and t-Boc-Met-enk in the presence of
oxygen compared to its absence.
These differences can be rationalized in the following way. In both peptides the addition of O2 – to
the aromatic ring of TyrO occurs resulting in their
respective peroxide anion enones which further
protonate forming the hydroperoxide enones. In
Met-enk the hydroperoxide enone undergoes the
Michael-addition-type reaction leading to the cyclized compound which further hydrolyses forming
stable compound. Its formation might be indicated
by a new peak observed in the HPLC chromatogram
of irradiated O2-saturated solutions of Met-enk,
but not in t-Boc-Met-enk ones. Since the amine
functionality is not available in t-Boc-Met-enk, the
respective hydroperoxide enone cannot undergo
Michael-addition-type reaction. Moreover, it was
observed [5] that efficient conversion to the respective hydroperoxides occurs only in peptides contain-
·
·
Fig.3. HPLC chromatograms recorded in irradiated with
84 Gy N2O-saturated aqueous solution containing 0.25
mM of Met-enk and 50 mM of N3–. Detection by: (A)
UV-VIS absorption at 274 nm and (B) fluorescence
(exc. 284 nm, em. 425 nm).
·
ing a free amino group in tyrosine itself. Therefore,
in t-Boc-Met-enk one has to consider reaction pathway involving hydroperoxide anion, which might
undergo oxygen elimination with simultaneous
formation of phenoxide-type anions followed by
their instantaneous protonation (regeneration of
t-Boc-Met-enk). Blocking the terminal amine had
thus a key role in the protection of tyrosine. This
finding might be exploited in the search for new
pain inhibitors.
Work was supported by the EC Marie Curie
Research Training Network SULFRAD under contract No. HPRN-CT-2002-000184.
21
References
[1]. Fontana M., Mosca L., Rosei M.A.: Biochem.
Pharmacol., 61, 1253-1257 (2001).
[2]. Rosei M.A., Mosca L., De Marco C.: Biochim.
Biophys. Acta, 1243, 71-77 (1995).
[3]. Rosei M., Blarzino C., Coccia R., Foppoli C., Mosca
L., Cini C.: Int. J. Biochem. Cell Biol., 30, 457-463
(1998).
[4]. Jin F., Leitich J., Sonntag von C.: J. Chem. Soc., Perkin
Trans., 1583-1588 (1993).
[5]. Winterbourn C.C., Parsons-Mair H.N., Gebicki S.,
Gebicki J.M., Davies M.J.: Biochem. J., 381, 241-248
(2004).
REACTIONS OF HYDROGEN ATOM
WITH METHIONINE-ENKEPHALIN AND RELATED PEPTIDES.
PULSE RADIOLYSIS STUDY
Olivier Mozziconacci, Krzysztof Bobrowski, Carla Ferreri1/, Chryssostomos Chatgilialoglu1/
1/
Institute for Organic Synthesis and Photoreactivity (ISOF), National Research Council (CNR),
Bologna, Italy
·
The role of hydrogen atoms (H ) in biology has
not yet been completely assessed. It has been suggested that their involvement is not only based on
the effect of ionizing radiation in water systems
since H can be generated efficiently by the reaction of electrons with dihydrogen phosphate anion (H2PO4–) present in the biological environment
[1]. Therefore, a peptide and/or protein damage
due to the H attack has to be considered in great
detail in order to establish its contribution to the
context of radical stress to biomolecules [2]. The
selectivity shown by the involvement of methionine
(Met) residues could be conveniently evaluated in
short amino acid sequences, which also allow
gathering further data on the H reactivity. As a
model peptide, we considered Met-enkephalin, a
neuropeptide composed by five amino acid residues (Tyr-Gly-Gly-Phe-Met; Tyr – tyrosine, Gly –
glycine, Phe – phenylalanine), its leucine analogue
(Leu instead of Met), and few selected peptides
containing Met. The presence of aromatic residues
(Tyr and Phe) and a sulfur-containing amino acid
(Met), together with the possibility of comparing
analogous sequences without Met, represents an
ideal case to study any selectivity of reducing species
towards the sulfur-containing amino acid and/or
the participation of other reactive sites in the ovearll
molecular reactivity. Here, we report pulse radiolysis study of Met- and Leu-enkephalins applying
reaction conditions where the H are the relevant
reactive species, which affect the Met residues.
The optical absorption spectra obtained from
the pulse irradiation of argon-purged aqueous solutions of Met- or Leu-enkphalin (0.1 mM) and
tert-butanol – t-BuOH (0.5 M) at pH 1.5 are shown
in Figs.1 and 2, respectively. Under these conditions, the hydroxyl radicals ( OH) are scavenged
–
by t-BuOH and eaq
are efficiently converted to H .
In order to evaluate the relative reactivity of the
two enkephalins towards H and the site of the attack, pulse radiolysis experiments were performed
·
·
·
·
·
·
·
Fig.1. Resolution of the spectral components in the transient absorption spectrum following the H atom reaction with Met-enkephalin (0.1 mM) in argon-saturated aqueous solutions containing t-BuOH (0.5 M)
at pH 1.5 taken 10 μs after the pulse.
·
in order to obtain spectra of isolated radicals derived from Tyr, Phe, and Met. Experiments were
performed with a tripeptide Tyr-Gly-Gly, and two
dipeptides, Phe-Leu and Gly-Met under identical
conditions as for enkephalins. These peptides were
selected in order to mimic an appropriate fragment
of either Leu-enkephalin or Met-enkephalin and
also the position with respect to the N- and/or
C-terminal functions of the most vulnerable amino
acids (Tyr, Phe and Met) towards the H attack.
The transient spectra obtained from these peptides
were then used as possible components in the resolution of the transient spectra following reaction
of H with Leu- and Met-enkephalins. After resolution of the spectrum for Met-enkephalin (Fig.1),
the G×ε values for Tyr-Gly-Gly and Phe-Leu are
1.8×10 –4 and 1.5×10 –4 dm3 J–1cm–1, respectively.
Analogously, after resolution of the Leu-enkepha-
·
·
22
·
reduced the amount of H by 55% from further
reaction with the Tyr and Phe residues. Moreover,
the pulse radiolysis experiments indicated that
about 50% of H attack the thioether moiety of
Met moiety presumably via a sulfuranyl radical
(>S -OH) [3,4] with formation of CH3SH and/or
CH3S radicals. By using a peptide-liposome model,
the cis-trans isomerization of phospholipids has
been detected highlighting the role of trans lipid
as marker of this radical damage [5].
Work was supported by the EC Marie Curie
Research Training Network SULFRAD under contract No. HPRN-CT-2002-000184.
·
·
·
References
Fig.2. Resolution of the spectral components in the transient absorption spectrum following the H atom reaction with Leu-enkephalin (0.1 mM) in argon-saturated aqueous solutions containing t-BuOH (0.5 M)
at pH 1.5 taken 10 μs after the pulse.
·
lin spectrum (Fig.2), the G×ε values for Tyr-Gly-Gly
and Phe-Leu are 4.0×10–4 and 2.5×10–4 dm3J–1cm–1,
respectively. Therefore, substitution of Leu by Met
[1]. Ferreri C., Manco I., Faraone-Minella M.R., Torregiani A., Tamba M., Manara S., Chatgilialoglu C.:
ChemBioChem., 7, 1738-1744 (2006).
[2]. Lipinski B.: Br. J. Nutr., 87, 93-94 (2002).
[3]. Ferreri C., Manco I., Faraone-Minella M.R., Torregiani A., Tamba M., Manara S., Chatgilialoglu C.:
ChemBioChem., 5, 1710-1712 (2004).
[4]. Wiśniowski P., Bobrowski K., Carmichael I., Hug G.L.:
J. Am. Chem. Soc., 126, 14468-14474 (2004).
[5]. Mozziconacci O., Bobrowski K., Ferreri C., Chatgilialoglu C.: Chem. Eur. J., (2007), in press (available on
the website).
PULSE RADIOLYSIS GENERATION OF THE RADICAL ANION
DERIVED FROM 2,3-DIHYDRO-OXOISOAPORPHINE
IN ORGANIC SOLVENTS
Krzysztof Bobrowski, Gabriel Kciuk, Eduardo Sobarzo-Sanchez1/, Julio R. De la Fuente2/
1/
University of Santiago de Compostela (USC), Spain
2/
Universidad de Chile, Santiago de Chile, Chile
Oxoisoaporphines are a family of oxoisoquinoline-derived alkaloids that have been isolated from
Menispermaceae as the sole known natural source
[1]. Formation of radical anions (A –) and neutral
hydrogenated radicals (A-NH ) from the triplet
manifold (3A) was postulated during photoreduction of 2,3-dihydro-oxoisoaporphine dye (A) by
amines [2]. Quantum mechanical semi-empirical
PM3 and ZINDO/S calculations reproduce adequately experimentally observed absorption spectra of the excited triplet (3A) and of neutral hydrogenated radicals (A-NH ) with maxima located at
450 and 390 nm, respectively [2]. However, the
calculated absorption maximum (λmax~600 nm) of
the isolated 2,3-dihydro-oxoisoaporphine radical
anion (A –) did not match the experimentally observed transient absorption spectrum with maximum located at λmax~490 nm. Therefore, the latter
spectrum was assigned to the radical ion-pair between the radical anion of 2,3-dihydro-oxoisoaporphine and the radical cation of the respective amine.
This assignment was further confirmed by Molecular Mechanics and ZINDO/S calculations [2].
Many previous studies have revealed that radical ions can be easily generated by pulse radiolysis
in a number of non-polar, polar-nonprotic, and
polar-polar protic solvents. Therefore, one may, by
choice of solvent and saturating gas, excercise some
·
·
·
·
control over the nature of the radical ionic species
formed in secondary reactions in irradiated solutions, and thus generate both radical anions and
cations or preferentially one of them. We have initiated this study in order to obtain a knowledge
about the spectral properties of radical ions derived from oxoisoaporphines. The present work is
of interest in shedding some light on spectral properties of the radical anion derived from 2,3-dihydro-oxoisoaporphine. Both acetonitrile and
acetone are known for pulse radiolytic generation
of cation as well anion radicals precursors. In these
two solvents, both radical ions and only the radical cation are formed under N2 and O2 saturation,
respectively [3,4].
The optical absorption spectra obtained from
the pulse irradiation of argon-purged acetonitrile
solutions of 2,3-dihydro-oxoisoaporphine (0.1
mM) are shown in Fig.1.
The transient spectrum recorded 0.2 μs after
electron pulse show two maxima at 450 and 605
nm, respectively (Fig.1, curve a). They become suppressed upon O2 saturation (Fig.1, curve c), suggesting that they might be associated with the 2,3-dihydro-oxoisoaporphine radical anion (A –). The
location of the maximum at longer wavelength is
in excellent agreement with that calculated for isolated 2,3-dihydro-oxoisoaporphine radical anion
·
·
(A –). Therefore, the 605-nm band was unequivocally assigned to the radical anion (A –). While,
the radical anion (A –) decays over a microsecond
time scale (t1/2~5 μs) (Fig.1, right inset), a new transient spectrum appears which is characterized by
two absorption maxima located at 420 and 500 nm,
respectively (Fig.1, curve b). Since these two absorption bands are also suppressed in oxygenated
solutions they might be assigned to the secondary
product(s) derived from the radical anion (A –).
This new absorption could be attributed to the neutral N-hydrogen radical of 2,3-dihydro-oxoisoaporphine (A-NH ) formed through protonation of
the radical anion (A –). The decay of neutral N-hydrogen radical (A-NH ) occurs on the hundred of
microseconds time range (Fig.1, left inset).
23
·
·
·
·
·
·
Fig.2. Transient absorption spectra recorded (a) 1 μs and
(b) 40 μs in argon-saturated and (c) 0.2 μs in O2-saturated acetone solutions containing 2,3-dihydro-oxoisoaporphine (0.1 mM) after electron pulse. Inset:
Absorption changes at λ=610 nm vs. time following
pulse irradiation of 2,3-dihydro-oxoisoaporphine
(0.1 mM) in argon-saturated acetone solutions.
tion bands become suppressed upon O2 saturation
(Fig.2, curve c). Again, they can be assigned to the
radical anion (A –). However, at shorter wavelength we cannot rule out the contribution of the
excited triplet state of 2,3-dihydro-oxoisoaporphine (3A) [2]. The decay of radical anion (A –) in
acetone is slightly slower (τ1/2~10 μs) in comparison to acetonitrile (Fig.2, inset). It is evident that
the spectral changes observed on a longer time
scale (Fig.2, curve b) after decay of the radical anion (A –) are similar to those observed in acetonitrile. Therefore, the absorption could be attributed
again to the neutral N-hydrogen radical of 2,3-dihydro-oxoisoaporphine (A-NH ).
·
·
Fig.1. Transient absorption spectra recorded (a) 0.2 μs and
(b) 50 μs in argon-saturated and (c) 0.2 μs in O2-saturated acetonitrile solutions containing 2,3-dihydro-oxoisoaporphine (0.1 mM) after electron pulse. Insets:
Absorption changes at λ=420 nm (left) and λ=605
nm (right) vs. time following pulse irradiation of
2,3-dihydro-oxoisoaporphine (0.1 mM) in argon-saturated acetonitrile solutions.
Acetone is known to give both solute cations and
anions, as well excited states. The optical absorption spectra obtained from the pulse irradiation of
argon-purged acetone solutions of 2,3-dihydro-oxoisoaporphine (0.1 mM) are shown in Fig.2. The transient spectrum recorded 1 μs after electron pulse
show two maxima at 430 and 610 nm, respectively
(Fig.2, curve a). As in acetonitrile, both absorp-
·
·
References
[1]. Sugimoto Y., Babiker H.A.A., Inanaga S., Kato M.,
Isogay A.: Phytochemistry, 52, 1431-1435 (1999).
[2]. De la Fuente J.R., Neira V., Saitz C., Jullian C.,
Sobarzo-Sanchez E.: J. Phys. Chem. A, 109, 5897-5904
(2005).
[3]. Bobrowski K., Das P.K.: J. Phys. Chem., 90, 927-931
(1986).
[4]. Bobrowski K., Das P.K.: J. Phys. Chem., 89, 5733-5738
(1985).
PULSE RADIOLYSIS STUDY OF THE INTERMEDIATES
FORMED IN IONIC LIQUIDS. NATURE OF INTERMEDIATES
IN PULSE IRRADIATED p-TERPHENYL SOLUTION
IN THE IONIC LIQUID METHYLTRIBUTYLAMMONIUM
BIS[(TRIFLUOROMETHYL)SULFONYL]IMIDE
Jan Grodkowski, Rafał Kocia, Jacek Mirkowski
Room temperature ionic liquids (IL) [1-5] are considered non-volatile and non-flammable and serve
as good solvents for various reactions and have been
proposed as solvents for green processing and very
effective media for numerous reactions [3-5]. Promising experiments concerning application of IL in the
nuclear industry brought the question of radiation
chemistry in these media. Up to now, only a limited
number of experiments were directly focused on
radiation stability of IL, the rate constants of several
elementary reactions in IL have been studied by
the pulse radiolysis technique instead [6-12].
24
In this study, the formation of intermediates
derived from p-terphenyl (TP) in the ionic liquid methyltributylammonium bis[(trifluoromethyl)sulfonyl]imide (R4NNTf2) solutions has been studied
by pulse radiolysis. TP was chosen because resulting anionic, cationic and excited intermediates have
absorption spectra in UV/VIS range (Table) [13].
The pulse radiolysis of TP solution in R4NNTf2 gives
subsequently some insight into the nature of primary products of R4NNTf2 radiolysis. The relations
between TP* (excited singlet and triplet states) and
TP – have been already described. TP photocatalytic activity was the other reason to chose this compound for experiments in IL and select the best
conditions for TP – formation. In photochemical
process TP – (often used in CO2 reduction [14,15
and references therein]) is formed mainly from singlet excited states 1TP* by reaction with electron
donor triethylamine (TEA) and in radiolysis directly in reaction with solvated electrons [14,15].
TP* in IL solution can also be formed by energy
transfer from excited radiolysis products of IL and
in direct TP excitation by Èerenkov light.
·
·
·
Table. Position of λmax of absorption spectra of intermediates derived from TP [13].
Fig. Spectrum at 400 ns after subtraction of the initial spectrum (corrected for spectrum of solvated electron),
Ar-saturated 14 mM TP solutions in R4NNTf2 with
3% TEA added, dose – 15 Gy.
·
even under the best conditions for radiolytic TP –
formation (Ar and TEA presence) TP – is always
accompanied by other intermediates, mostly 3TP*.
TEA enhances the yield of TP – due to scavenging
of cation radicals and 1TP*, however it reacts more
slowly with 3TP* [15]. The presence of solvated
electron scavengers cuts the initial spectrum in the
region 400-500 nm to about half value. This indicates that under Ar most of the TP – is formed in
the reaction of TP with solvated electrons and their
precursors, dry electrons. Some of TP – (less than
50%) are produced in the presence of TEA from
1
TP*.
Kinetics of the total absorption decay (in the
range 400-500 nm) is quite complicated and the
best fitting to the experimental results can be
achieved using exponential decay equation with at
least three different constants. Addition of O2 to
the TP solution, besides elimination of solvated
electrons and consequently decreasing the intensity of the spectra, drastically increases the rate of
absorption decay.
The reduction potentials of TP – and CO2 – in
IL are close to each other and the reactions between TP and CO2 and their radical anions in any
directions cannot be seen in pulse radiolysis experiments.
Concluding, the primary radiolysis products of
R4NNTf2 solvent constitute of dry and solvated electrons, cation radicals and excited species. Reduction potential of cationic species it is not high
enough to oxidize Br– or SCN– but allows formation of cation radicals of TP. TP – is produced
mainly in the reaction with dry and solvated electrons and its lifetime is in order of tens of microseconds in the pulse radiolysis experiments.
·
·
·
·
The pulse radiolysis of TP solution in R4NNTf2
has been carried out under Ar, CO2, O2 and N2O
in the presence or absence of TEA. Fast kinetic
measurements have been carried out using 10 ns,
10 MeV electron pulses from a LAE 10 linear electron accelerator [16] delivering a dose up to 20 Gy
per pulse. The details of the computer controlled
measuring system were described before [11,17].
Resulted under Ar intermediate spectra are
formed in two steps, one very fast already completed
during the pulse, and the second lasting hundreds
of nanoseconds depending on TP concentrations.
The second step is eliminated in the presence of
electron acceptors. The initial spectra are related
to the species listed above and also to solvated electrons, except 1TP* which is too short lived to be
observed in nanosecond time scale.
In Figure, there is presented an absorption spectrum corresponding to the second step only. It is
set up from the difference between the spectrum at
400 ns after the electron pulse (end of the second
step) and the initial spectrum (corrected for spectrum of solvated electron) obtained in pulse radiolysis of Ar-saturated 14 mM TP solutions in
R4NNTf2 with 3% TEA added. Very similar spectrum is calculated from the results without added
TEA. The spectra can be ascribed to the TP – because of the similarity to the reported before results in frozen systems [13]. Comparison of the
calculated TP – spectrum with the shape of direct
experimental spectra leads to the conclusion that
·
·
·
·
·
References
[1].
[2].
Welton T.: Chem. Rev., 99, 8, 2071-2083 (1999).
Wasserscheid P., Keim W.: Angew. Chem. Int. Ed.,
39, 21, 3772-3789 (2000).
[3]. Ionic liquids: Industrial application to green chemistry.
Eds. R.D. Rogers, K.R. Seddon. ACS Symp. Ser., 818
(2002).
[4]. Chiappe C., Pierracini D.: J. Phys. Org. Chem. 18,
275-297 (2005).
[5].
[6].
[7].
[8].
[9].
[10].
[11].
[12].
Jain N., Kumar A., Chauchan S., Chauhan S.M.S.:
Tetrahedron, 61, 1015-1060 (2005).
Grodkowski J., Neta P.: J. Phys. Chem. A, 106, 22,
5468-5473 (2002).
9030-9035 (2002).
11130-11134 (2002).
Wishart J.F., Neta P.: J. Phys. Chem. B, 107, 30,
7261-7267 (2003).
Grodkowski J., Neta P., Wishart J.F.: J. Phys. Chem.
A, 107, 46, 9794-9799 (2003).
Grodkowski J., Płusa M., Mirkowski J.: Nukleonika,
50, Suppl.2, s35-s38 (2005).
Wishart J.F., Funston A.M., Szreder T.: Radiation
chemistry of ionic liquids. In: Molten saltz. The
Electrochemical Society, Pennigton, NJ, USA, 2006.
25
[13]. Shida T.: Electronic absorption spectra of radical
ions. Elsevier, Amsterdam 1988, p. 446.
[14]. Grodkowski J.: Radiacyjna i fotochemiczna redukcja
dwutlenku węgla w roztworach katalizowana przez
kompleksy metali przejściowych z wybranymi układami makrocyklicznymi. Instytut Chemii i Techniki
Jądrowej, Warszawa 2004, 56 p. Raporty IChTJ. Seria
A nr 1/2004 (in Polish).
[15]. Fujiwara H., Kitamura T., Wada Y., Yanagida S.,
Kamat P.V.: J. Phys. Chem. A, 103, 4874-4878 (1999).
[16]. Zimek Z., Dźwigalski Z.: Postępy Techniki Jądrowej,
42, 9-17 (1999), in Polish.
[17]. Grodkowski J., Mirkowski J., Płusa M., Getoff N.,
Popov P.: Radiat. Phys. Chem., 69, 379-386 (2004).
STEREOELECTRONIC CONTROL OVER THE MECHANISM
OF SINGLET OXYGEN-INDUCED DECARBOXYLATION
IN ALKYLTHIOCARBOXYLIC ACIDS
Monika Celuch, Mirela Enache1/, Dariusz Pogocki
1/
Institute of Physical Chemistry “I.G. Murgulescu”, Romanian Academy, Bucharest, Romania
Our recent investigations have been devoted to
understanding the irreversible pathways of singlet
oxygen-induced (1O2-induced) oxidation of carboxyl-substituted thioethers. The reaction of 1O2
with thioether sulphur initially leads to the formation of peroxysulphoxide [1,2]:
1
O2 + >S → >S(+)O-O(–)
(1)
being in the equilibrium with superoxide radical
anion (O2 –) and respective sulphur-centered radical cation:
>S(+)O-O(–) = >S + + O2 –
(2)
The major, enzymatically reversible [3], pathway
of persulphoxide decay is the bimolecular reaction
with the second molecule of thioether that leads
to the formation of respective sulphoxide [1,2]:
>S(+)O-O(–) + >S → 2 >S=O
(3)
Our previous experimental observation [4,5] for
the following model thioethers: 2,2’-thiodiethanoic
acid (TDEA), 3,3’-thiodipropionic acid (TDPA),
2-(methylthio)ethanoic acid (MTEA), 3-(carboxymethylthio)propionic acid (CMTPA), 2-(carboxymethylthio)succinic acid (CMTSA), have shown
the presence of the competitive, irreversible process of decarboxylation that can be schematically
represented by below reaction:
R- S +-CH2-CO2– → R-S-CH2 + CO2 (4)
That process could be quite effective for the sulphur-centered radical cations of α-carboxyl-substituted thioethers. Moreover, the nucleophilic catalysis of reaction (2) seems to be crucial for the
competitiveness of the irreversible reaction pathway. In such catalytic process, the weak nucleophile O2 – (pKA(HO2 /O2 –)≈4.8 [6]) is replaced by a
stronger nucleophile like OH– or Cl– anions. The
DFT calculations have predicted the formation of
tetravalent transient – product of OH– (or halogenic
anions) addition to persulphoxide, pointing at the
occurrence of two-step (AN+DN)-type mechanism
of subsequent nucleophilic addition and nucleo-
·
·
·
·
(5)
·
·
· ·
philic dissociation [4,5,7]. The observed influence
of β-carboxylic groups on the efficiency of decarboxylation suggest that β-carboxylate may catalyze
decarboxylation of α-carboxylate in the intramolecular process:
The differences in the decarboxylation yield between the acids (Table) can be rationalized in terms
of the stereoelectronically controlled Wagner-Meerwein rearrangement [8,9] previously observed for
carbocations:
(6)
The upper branch of this mechanism shows the fragmentation pathway that could be easily adopted for
decarboxylation of sulphur-centered radical cations
in alkylthiocarboxylic acids.
(7)
In this mechanism, the electron from the σ bond
(between Cα and carboxylate) is donated to the radical-cation center. The weakening of the bond results
in a subsequent release of carbon dioxide. Therefore, the quite objective measure of the radical-cation propensity to undergo such fragmentation could
be distortion of the donor σ bond toward the electron acceptor site at oxidized thioether sulphur.
26
Table. Alkylthiocarboxylic acids, structures and relative
yields of 1O2-induced decarboxylation.
Fig.2. Relative yield of 1O2-induced decarboxylation in alkylthiocarboxylic acids vs. the ξ angle.
In the DFT quantum chemical calculations [10] we
obtained geometries and electronic structures of
sulphur-centered radical cations derived from each
of the investigated transient species. (The representative example for CMTSA is presented in Fig.1.)
For CMTPA and CMTSA, the sulphur-centered
leaning of σ bond towards the radical-cation centre
that seems to confirm the assumed mechanism.
This work described herein was supported by
the Polish Ministry of Education and Science
(grant No. 3 T09A 066 26). The computations were
performed employing the computer resources of
the Interdisciplinary Centre for Mathematical and
Computational Modelling, Warsaw University
(ICM G24-13).
References
Fig.1. The DFT (B3LYP/6-31G(d)) calculated structure of
sulfur-centered radical cation in CMTSA. The angle
ξ has been chosen as a measure of distortion of the
donor σ bond (Cα-CO2) toward the electron acceptor radical cation.
radical cations being precursor of α-carboxylate decarboxylation could be stabilized by the formation
of three-electron-bonded species with the oxygen
atom of adjacent β-carboxylate group. (The geometries and electronic structures of such species
we have extensively investigated previously [11,12].)
In order to analyze the structures of sulfur-centered radical cations in terms of the Wagner-Meerwein rearrangement mechanism we chose the angle
ξ (Fig.1) as a measure of distortion of the σ bond
toward the radical-cation centre. Indeed, the computational results show a quasi-linear dependence
of relative yield of decarboxylation on ξ (Fig.2).
The decarboxylation yield increases with growing
[1]. Clennan E.L.: Acc. Chem. Res., 34, 875-884 (2001).
[2]. Jensen F., Greer A., Clennan E.L.: J. Am. Chem. Soc.,
120, 4439-4449 (1998).
[3]. Sharov V.S., Ferrington D.A., Squier T.C., Schöneich
C.: FEBS Lett., 455, 247-250 (1999).
[4]. Celuch M., Enache M., Pogocki D.: Singlet oxygen-induced oxidation of alkylthiocarboxylic acids. In:
INCT Annual Report 2005. Institute of Nuclear Chemistry and Technology, Warszawa 2006, pp. 26-28.
[5]. Celuch M., Pogocki D.: Singlet oxygen-induced decarboxylation of carboxyl substituted thioethers. In: INCT
Annual Report 2004. Institute of Nuclear Chemistry
and Technology, Warszawa 2005, pp. 27-29.
[6]. Bartosz,G.: Druga twarz tlenu. Wolne rodniki w przyrodzie. Wydawnictwo Naukowe PWN, Warszawa
2003, pp. 1-447 (in Polish).
[7]. Williams A.: Concerted organic and bio-organic
mechanisms. CRC Press, Boca Raton 2000, pp. 1-286.
[8]. Rauk A.: Orbital interaction theory of organic chemistry. John Wiley & Sons, Inc., New York 2001, pp.
1-343.
[9]. Chanon M., Rajzman M., Chanon F.: Tetrahedron,
46, 6193-6299 (1990).
[10]. Frisch M.J. et al.: Gaussian 03. (Rev. B.03). Gaussian
Inc., Pittsburgh PA 2003.
[11]. Pogocki D., Schöneich C.: J. Org. Chem., 67, 1526-1535
(2002).
[12]. Pogocki D., Serdiuk K., Schöneich C.: J. Phys. Chem.
A, 107, 7032-7042 (2003).
27
OXIDATION OF THIOETERS BY ORGANIC COMPLEXES OF COPPER
Monika Celuch, Katarzyna Serdiuk1/, Jarosław Sadło, Mirela Enache2/, Dariusz Pogocki
1/
2/
Jan Długosz University of Częstochowa, Poland
Institute of Physical Chemistry “I.G. Murgulescu”, Romanian Academy, Bucharest, Romania
The presence of cupric ions is essential for proper
metabolism of many organisms. The best recognized
and appreciated function of cupric ions is their participation in the active centers of numerous enzymes
[1]. On the other hand, the faults in copper homeostasis in humans are frequently related to disorders
with neurological symptoms [2,3]. For example,
copper is bind by β-amyloid peptide (βA), the most
abundant constituent of senile plaques observed in
Alzheimer’s disease (AD) brains [2,3]. The βA-bound
copper can be involved in the cycle of Fenton like
reactions, in which free radicals and other reactive
oxygen species (ROS) presented in pathology of AD
may be formed [4].
In this work, we continue investigation of the
mechanisms that may explain the ability of βA to
reduce copper in reaction:
MetS + βA(CuII) ↔ βA(CuI) + MetS + (1)
Such process seems thermodynamically unfavorable [5], since in normal conditions the difference
between the reduction potentials of βA(CuI/CuII)
(0.5-0.55 V vs. Ag/AgCl) [6] and MetS +/Met
(1.26-1.5 V vs. Ag/AgCl) [7-10], is about ca. 0.7-1.0
V, thus equilibrium (1) should be shifted to the far
left-hand side [5].
However, reaction (1) may occur if coupled with
the other exergonic reaction. One of possible scenario is the removing of MetS + from the equilibrium
by the formation of α-(alkylthio)alkyl radicals
(αS ) in exergonic, general base catalyzed reaction:
MetS + + B → Met(αS) + BH+
(2)
Therefore, in this work we studied, on the model
systems, reactions that may spontaneously lead to
the formation α-(alkylthio)alkyl radicals, potentially
influencing equilibrium (1) and accelerating oxidation of the methionine (Met) residue in peptides.
We examined a molecular system, in which
the complex of CuII with imidazole mimics cupric
site of βA. The fifth fold excess of imidazole (Im)
over Cu2+ guarantee that at least 95% of copper
is in the form of Cu(Im)42+-type complex of known
properties: λmax≈590 nm (ε=53 ±2 M–1cm–1) [11]
and E0(CuII/CuI)≤0.2 V and E0(CuI/Cu0)≤0.6 V vs.
SCE [12]. The methionine residue was mimicked
by organic α-substituted thioethers: 2,2’-thiodiacetic acid (TDEA, HO2C-CH2-S-CH2-CO2H),
and 2-(methylthio)acetic acid amide (MTAA,
CH3-S-CH2-CO2-NH2). In both cases the reduction
of Cu(Im)42+-complexes should be accompanied by
a simultaneous formation of the resonance stabilized α-(alkylthio)alkyl radicals. For TDEA, entropy driven decarboxylation is the main source of
α-(alkylthio)alkyl radicals, whereas for MTAA the
facilitated deprotonation, due to the captodative
effect stabilizing α-(alkylthio)alkyl radicals, will
dominate [13]. Contrary to fast decarboxylation of
TDEA, deprotonation in MTAA should be susceptible to the presence of proton acceptors [14].
·
·
·
·
·
·
Fig.1. The ESR signal changes vs. incubation time in argon-saturated (solid symbols) and oxygen-saturated
(open symbols) solutions containing: 1.5×10–3 M
CuCl2, 7.5×10–3 M Im and 0.75×10–3 M (square) or
3.0×10–3 M (triangle) of MTAA.
The reduction of Cu(Im)42+ by thioethers was
investigated in oxygen- or argon-saturated aqueous solution containing 1.5×10–3 M CuCl2, 7.5×10–3
M Im, and (0.75; 1.5 or 3.0)×10–3 M of thioethers
at neutral pH, incubated at 50oC. The progress of
reaction was monitored using three independent
methods: high performance ion chromatography
exclusion (HPICE) [15] was applied for quantitative
determination of products and substrates. Decay of
CuII was monitored by electron spin resonance
(ESR) spectroscopy (in the redox pair CuII/CuI only
CuII cations are paramagnetic). The formation of
CuI was followed using UV-VIS absorption spec-
Fig.2. The concentration of Cu(BCA)23– complexes vs. incubation time for argon-saturated solutions containing: 3.0×10–3 M of thioether (MTAA – squares, TDEA
– triangles), 1.5×10–3 M CuCl2 and 7.5×10–3 M Im.
troscopy of 2,2’-bicinchoninic acid (BCA) complex
with Cu+ cations (Cu(BCA)23–: λmax≈562 nm, ε≈7700
M–1cm–1) [16].
28
show faster changes for TDEA, which reduces CuII
with more than two times higher efficiency than
MTAA. On the other hand, we obtained the evidence that the process of CuII-complexes reduction,
induced by deprotonating thioether such as MTAA,
could be accelerated in general acid-base catalysis
by phosphate ions (Fig.3). The mechanism shown
in Scheme is a preliminarily attempt to rationalize
current observation for MTAA. It requires, however, additional consideration especially on the
mechanistic details of the conversion of peroxyl
radicals regenerating the mother compounds.
This work described herein was supported by
the Polish Ministry of Education and Science (grant
No. 3 T09A 066 26).
Fig.3. The influence of phosphate ions (H2PO4–/HPO42–) on
the kinetics of CuII reduction by MTAA in argon-saturated solutions containing: 0.75×10–3 M thioether,
1.5×10–3 M CuCl2, 7.5×10–3 M Im and (solid symbols)
0.15×10–3 M phosphate buffer, (open symbols) phosphate free solution.
References
[1].
[2].
[3].
For the all samples containing TDEA, and for
argon-saturated samples containing MTAA we observed the decay of ESR signal. Whereas for oxygen-saturated samples of MTAA the intensity of
ESR signal remained on the same level for more
than 300 h of incubation (see example in Fig.1).
Also, the HPICE measured changes of MTAA
concentration during incubation in oxygen-saturated solutions were insignificant. Similarly, the
formation of Cu(BCA)23– complexes was observed
in the presence of both thioethers in argon-saturated samples (Fig.2). Generally, the significant
differences in kinetics between thioethers were observed. For the same concentrations of TDEA and
MTAA, both the ESR and the UV-VIS experiments
[4].
[5].
[6].
[7].
[8].
[9].
[10].
[11].
[12].
[13].
[14].
[15].
[16].
Scheme.
Holm R.H., Kennepohl P., Solomon E.I.: Chem.
Rev., 96, 2239-2314 (1996).
Strausak D., Mercer J.F., Dieter H.H., Stremmel W.,
Multhaup G.: Brain Res. Bull., 55, 175-185 (2001).
Gaggelli E., Kozłowski H., Valensin D., Valensin G.:
Chem. Rev., 106, 1995-2044 (2006).
Halliwell B., Gutteridge J.M.: Free radicals in biology
and medicine. Oxford University Press, Oxford 1999,
pp. 1-936.
Schöneich C.: Arch. Biochem. Biophys., 397, 370-376
(2002).
Huang X. et al.: J. Biol. Chem., 274, 37111-37116
(1999).
Merényi G., Lind J., Engman L.: J. Phys. Chem., 100,
8875-8881 (1996).
Engman L., Lind J., Merényi G.: J. Phys. Chem., 98,
3174-3182 (1994).
Huie R.E., Clifton C.L., Neta P.: Radiat. Phys. Chem.,
92, 477 (1991).
Sanaullah, Wilson S., Glass R.S.: J. Inorg. Biochem.,
55, 87-99 (1994).
Edsall J.T., Falsenfeld G., Goodman D.S., Guard
F.R.N.: J. Am. Chem. Soc., 76, 3054-3061 (1954).
Li N.C., White J.M., Dood E.: J. Am. Chem. Soc., 76,
6219-6223 (1954).
Wiśniowski P.: Wpływ grup funkcyjnych na inicjowane
radiacyjnie procesy rodnikowe w tioeterach (The influence of functional groups on the radiation initiated
radical processes in thioethers). Ph.D. thesis. Instytut
Chemii i Techniki Jadrowej, Warszawa 2001 (in Polish).
Mönig J., Goslich R., Asmus K.-D.: Ber. Bunsen-Ges.
Phys. Chem., 90, 115-121 (1986).
Weiss J.: Ion chromatography. VCH, Weinheim 1995,
pp. 1-465.
Boyd-Kimball D., Mohmmad A.H., Reed T., Sultana R.,
Butterfield D.A.: Chem. Res. Toxicol., 17, 1743-1749
(2004).
ORGANOSILVER RADICALS IN ZEOLITES
Jerzy Turek, Jarosław Sadło, Jacek Michalik
During radiolysis of solutions containing silver
salts, Ag+ cations are reduced to Ag0 atoms which
initiate silver agglomeration process. The solvent
radicals formed radiolytically compete with Ag0 to
react with Ag+ cations. Just after irradiation at 77
K in frozen solution of methanol containing silver
perchlorate the electron paramagnetic resonance
(EPR) measurements reveal a doublet with silver
hyperfine splitting in the range 60-70 mT representing Ag0 atoms [1]. During thermal annealing, a
doublet with much smaller splitting Aiso(Ag)=13.6
mT appears together with a less intense triplet with
A(Ag)=30.0 mT. Based on the electron spin echo
envelope modulation (ESEEM) result, the doublet
was assigned to an adduct of Ag+ cation and hydroxymethyl radical ( CH2OH) with a one-electron
bond between silver and carbon.
In gamma-irradiated silver zeolites exposed to
methanol vapour the doublet of silver hydroxymethyl radical is also observed, but hyperfine splitting values vary very much for different zeolite structures [2]. The goal of our studies was to define the
nature of bonding between Ag+ cation and small
carbon radicals and to determine the factors that
affect the value of A(Ag) hyperfine splitting for
organosilver radicals.
After dehydration at 200oC, the zeolite samples
have been oxidized with O2 under pressure of 300
Torr for one hour. Next, oxygen was pumped out
and the methanol was adsorbed at room temperature. The samples were gamma-irradiated at 77 K
in a 60Co source. The EPR spectra were measured
using a Bruker ESP-300 spectrometer equipped
with a cryostat operating in the temperature range
100-350 K.
·
Fig. The EPR spectra at 160 K of (a) Ag-ferrierite and (b)
Ag-NaA zeolites exposed to methanol vapour and
gamma-irradiated at 77 K. Ag·C dublets represent
silver hydroxymethyl radicals.
Typical EPR doublets of [Ag·CH2OH]+ adduct
labelled as Ag·C are shown in Fig. for Ag-NaA and
Ag-ferrierite zeolites exposed to methanol. The
hyperfine splitting values for various zeolite structures are presented in Table 1. They differ from
12.0 mT for 4A zeolite to 19.5 mT for ferrierite.
The dependence of Aiso(Ag) constant on the Si/Al
ratio is strong in big cation capacity zeolites and
probably is linear. However, the cation capacity
affects A(Ag) value of [Ag·CH2OH]+ only to a minor degree as was proved by the experiments with
Ag-ZSM-5 zeolites with Si/Al ratio in the range
30 to 200 and MCM-41 zeolites with Si/Al ratio
from 10 to 30. To verify our experimental conclusions concerning the zeolite lattice influence on the
29
Ag·C radical structure, we performed density functional theory (DFT) calculations for a system of Ag+
cation interacting with hydroxymethyl radical. Those
calculations confirmed that the one-electron bond
between silver and carbon is able to stabilize the
[Ag·CH2OH]+ adduct. The formation of the adduct
causes a substantial shift of spin density from carbon
to silver. An EPR doublet cannot originate from
the Ag·O one-electron bond because such configuration gives a very low spin density on silver.
The results of DFT calculations show that the
A(Ag) of [Ag·CH2OH]+ radical depends strongly
on the interaction of Ag+ with the surroundings
especially with electronegative atoms. Theoretical
value of hyperfine splitting of the free silver hydroxymethyl radical is equal to 16.4 mT. If one takes into
consideration the interaction of one methanol
molecule with the metallic centre of [Ag·CH2OH]+
radical, the A(Ag) value calculated by the DFT
method decreases to 14.2 mT which is very close
to the experimental value observed in gamma-irradiated frozen solutions of silver perchloride in
methanol. But when the radical forms a hydrogen
bond A(Ag) this value increases to 216 G.
Comparing DFT results with the data of EPR
experiments, it was proved that in zeolites with big
cation capacity the silver hydroxymethyl radical
interacts with a silicaallumina network by the metallic centre of the radical. The decrease of cation
capacity modifies the radical surroundings changing electronic density distribution. In zeolites with
small cation capacity, the formation of hydrogen
bonds with zeolite network is postulated as a dominating interaction of silver hydroxymethyl radical.
The theoretical calculations showed also a substantial influence of the functional group on the Ag
hyperfine splitting for different adducts with the
Ag·C one-electron bond (Table 2). It depends on
the ability of the functional group to attract or repulse electrons. Electron donor functional groups
Table 2. Theoretical values of A(Ag) for different organosilver radicals.
Table 1. Experimental values of A(Ag) hyperfine splitting
for [Ag·CH2OH]+ in different zeolites.
increase spin density on the Ag nucleus which results with large values of hyperfine splitting ranging from 13 to 20 mT. In contrast, A(Ag) for Ag·C
organosilver radicals with electron acceptor groups
are in the range 5-8.5 mT because they decrease the
spin density on silver.
30
It is worthy of stressing that the functional
groups which decrease or increase A(Ag) splitting
are similar to those which, in a similar way, affect
electron density on π orbitals of benzene ring. Thus,
we can speculate that resonance structures similar
to the structures in the chemistry of aromatic hydrocarbons are responsible for the observed effect.
References
[1]. Symons M.C.R., Janes R., Stevens A.D.: Chem. Phys.
Lett., 160, 386 (1989).
[2]. Michalik J., Sadlo J., van der Pol A., Reijerse E.: Acta
Chem. Scand., 51, 330 (1997).
EPR STUDY ON RADIATION-INDUCED RADICAL DISTRIBUTION
IN MASSIVE BONE GRAFTS
Jarosław Sadło, Jacek Michalik, Grażyna Strzelczak, Anna Dziedzic-Gocławska1/ ,
Artur Kamiński1/
1/
Central Tissue Bank, Medical University of Warsaw, Poland
The bone transplantation method, a useful tool of
orthopedic surgery, requires advanced and fully
controlled methods of sterilization, mainly using
ionizing radiation sources. Radiation can fast provide sufficient energy to sterilize a whole volume
of bone pieces. Small volume grafts – like bone
powder fillers or pieces of compact bone like plates
or poles, have been sterilized in the Institute of Nuclear Chemistry and Technology (INCT) by accelerators for many years.
Recently, tissue banks offer also massive grafts
– the whole fragments of bone. In that case, because
of complicated shape and composition of compact
and spongy bone types, it is necessary to control
the dose distribution as well as the distribution of
radiation-induced radicals. It should be stressed
that dose distribution must not be identical with
radical distribution because of inhomogeneity of
bone structure.
For experiments, the human tibia bones were
used. A massive fragment was cut into thin slices
assembled back into the anatomical shape. Next,
it was one-sided irradiated by a 10 MeV electron
beam (Elektronika, INCT) with a dose of 30 kGy.
A similar fragment was two-sided irradiated with
a dose of 2x20 kGy. The fragment of the same configuration was irradiated by 60Co gamma rays
(Issledovatel, INCT, 30 kGy). Next, all the slices
were cut into about 100 small pieces and then
crushed into powder to avoid anisotropic effects.
Electron paramagnetic resonance (EPR) measurements were carried out using an X-band Bruker
ESP 300 spectrometer. The measured EPR signal,
an anisotropic singlet with g⊥=2.003 and gll=1.997
(Fig.1), origins from mineral part of the bone was
assigned earlier to CO2– radical. The signal is stable
and its intensity increases linearly with absorbed
dose.
The highest difference in the concentration of
CO2– radicals in small pieces of the bone irradiated
in a 60Co source does not exceed 18%. That type of
radiation can easily penetrate the bone fragments
in the whole volume because of high penetrability
of gamma rays. Thus, the radicals concentration
should be similar in the whole cross-section of the
bone. However, the experimental results are different because of inhomogeneity of bone structure and,
in practice, the radical concentration in gamma-ir-
radiated massive bones renders the percentage of
hydroxyapatite through bone cross-section. The
radical concentration is higher in bone pieces containing more hydroxyapatite.
Fig.1. EPR spectrum of CO2– radical induced in irradiated
bone.
For one-sided irradiation, the distribution of
radicals is similar to dose depth dependence: maximum concentration is at the depth of one centimeter. Concentration difference between the upper
and lower part is about 60% indicating that the applied dose does not guarantee sterility of the bone
(Fig.2A). In case of two-sided irradiation, the distribution of radical concentration is much more flat
and the difference between the highest and lowest
values is about 30% (Fig.2B).
The dose distribution during electron beam irradiation was estimated using a PVC foil dosimeter
(spectrophotometric method) as well as a powder
alanine dosimeter (EPR dosimetry). In both cases
the dosimeters were placed between two bigger
bone parts and then one-sided irradiated. The alanine powder was placed in small flat bags. The alanine from each bag was measured separately. The
results confirmed that the profile of distribution
is rather complex because of the complicated shape
31
Fig.2. Dose distribution in one-sided (A) and two-sided (B) massive bone grafts.
of irradiated object and the presence of bone channels. For both dosimeters, the maximum dose was
equal to about 120% of the initial value, and the
dose distribution was very similar to radical concentration distribution.
It is concluded that for massive bone fragments
one-sided irradiation does not guarantee sterilization of the whole fragments, therefore two-sided
irradiation should be applied as a routine in that
case.
RADIATION CHEMISTS VIEW ON PANSPERMIA HYPOTHESIS
Zbigniew P. Zagórski
The year 2006 was the last full year of my participation as the member of Managing Committee in
the European action in chemistry COST D27 (Prebiotic chemistry and early evolution), as the only
radiation and radiochemist in the Committee. The
field is closely connected to the so-called astrobiology, which deals with life and prebiotic chemical compounds present anywhere in the universe.
Problems involve transportation of that material
in any directions, what can be involved in the origin of life on earth.
The very old [1] concept of panspermia hypothesis may be traced to Greek philosophers. Even now,
the idea that the transportation of spores from the
universe is responsible for the origin of life on
earth, is always widely accepted as long as it is not
confronted with conditions in the universe. These
are characterized mainly by the existence of invisible, but chemically and biologically active ionizing
radiations. Their intensity is sufficient to kill highly
organized life and also primitive life, if the time of
interaction is long enough. We have presented the
quantitative relationships on practically all workshops organized during COST D27 meetings and
other conferences, e.g. on ISSOL 05 [2], stressing
the chemical mechanism of the irreversible radiation damage to dry spores. The best description of
possibilities of spores to survive the transportation
in the universe is the table published by Benton
Clark [3], then slightly modified [4]. Clarks paper
is seldom quoted; it is simply non-existent among
enthusiasts of panspermia.
The doses which decide about very low probability of panspermia are similar to doses applied
in technology of radiation sterilization, widely used
for killing all microorganisms in medical devices and
medicaments [5]. The radiation should not damage
the sterilized material, which survives the irradiation with a minimal loss of active compound or remains with negligible degradation of material, usually a polymer. The same applies to celestial bodies:
if the sojourn in space is comparatively short, the
only change, however important, is the killing of life,
e.g. of spores which otherwise would be the seeds
of life transported to earth. As one can see from
the Clark table, the time of travelling in space with
resulting sterilization only, is astronomically speaking short. However, the real sojourn in radiation
fields lasts very much longer and the absorbed, additive doses grow [6].
Clark’s table (in modified version see [4]) shows
more than when and in what object the spores will
be inactivated. What happens during longer stays,
especially to objects of small size like cosmic dust,
easily penetrated not only by electromagnetic ionizing radiations like gammas, but also by particles
like protons and by heavier ions, present in galactic cosmic rays? These objects are absorbing mammoth doses of radiation energy, which causes many
chemical reactions. The next to sterilization dose
is the dose not very much higher, causing abstraction of parts of biopolymers or parts of organic
compounds. There are many examples of such reactions, the most general is the fact common in
32
radiation chemistry, i.e. the abstraction of a group
which leaves in the molecule a site with unpaired
electron.
Another example is the destruction of chirality.
Abstraction of a group, e.g. of ammonia from the
α-carbon in an amino acid, turns off the asymmetry
of the remaining radical. The free radical can attach
a group, and the new compound will be chiral, if
the group is different from the remaining three.
Therefore, if the original amino acid was a pure
enantiomer, any products of the subsequent reaction will keep chirality, but will be racemic, 1:1 D
to L. Hypothetical homochirality of a compound
achieved (perhaps) far from the Earth will be lost
during the travel.
Moving to higher doses resulting from even
longer stays in the universe, we are turning into
the zone of complete degradation, and sometimes
even to disappearance of an organic compound.
The Scheme shows possible degradation reactions.
Scheme.
The final result can depend on the surrounding,
whether oxidative presence of oxygen, or reducing,
or vacuum. In both two last named cases, the final
product can be nano-sized carbon dust, and such
reaction is called radiation-induced carbonization.
Large objects staying for a long time in space
obtain highest doses of ionizing radiation at the
surface, gradually diminishing towards the inside.
The depth dose can be estimated from the Clark
table. The surface of the object is the most irradiated part and the best known object is the planet of
Mars [7]. Its regolith is not only completely sterilized but also relieved from organics. Perhaps part
of organics has been degraded to elementary carbon, present, if so, as black dust moved with the
Martian thin CO2-wind. Anyway, chances for detection of organics on the surface of Mars are poor.
Similar conclusions have been drawn by photochemists, assuming devastating chemical influence
of deep UV reaching the surface of Mars. Their argument is poor, because supposed the Martian organics show usually no absorption in UV, but even
in the presence of chromophoric groups the effect
is of low importance, because the depth of penetration is shallow. Therefore, the deciding influence of
ionizing radiation is more important.
The low temperature of space on the route of
moving objects is not a protecting factor, because
radiation-induced reactions proceed with low activation energy and presented chemical effects
observed at liquid nitrogen temperatures are not
dramatically lower in comparison to those at ambient temperatures.
The common reaction of abstraction of hydrogen, not limited to spores but of general occurrence
[8], corroborates well with characteristic feature
of organic compounds, identified spectroscopically
in interstellar spaces of the universe. They are as
poor in hydrogen as possible, e.g. methyltriacetylene
(C7H4), methylcyanodiacetylene (C6NH3), cyanoallene (C4NH4), ketenimine (C2NH3), cyclopropenone (C6OH2) and many polyaromatics. The
remaining hydrogen atoms are difficult to detach
during absorption of ionizing radiation, because
they usually belong to structures, mainly polyunsaturated and aromatic which possess the ability
to dissipate the absorbed ionization energy without ionization.
The question remains why the life on earth is
not destroyed after sufficiently long action of ionizing radiation. The ionizing radiation which impregnates the universe is reaching the surface of
earth in much reduced intensity, due to the shield
of the atmosphere, equivalent to 3 meters of concrete. Even the most penetrating galactic cosmic
rays, which reach the earth in cascades of secondary ionizing radiations are responsible for only
small contributions to mutations forming in living
organisms. Other ionizing radiations coming from
outer space, like gamma bursts, proton beams from
events in the Sun and other stars, are almost fully
absorbed. Therefore, the contribution of space
radiation to the radiation background on earth is
only similar to the present level supplied by radioactive material on earth. The deciding fact causing
not the inactivation of life on earth but, vice versa,
even some positive effects, is the interaction of
radiation with living matter. Whereas the DNA in
the living species, i.e. in aqueous suspensions, when
damaged slightly by ionizing radiation can be repaired, the DNA in dry spores is effectively, irreversibly damaged by the very first doses of radiation. The effect is additive, and even low doses are
damaging, after accumulation of elementary acts,
mainly of hydrogen abstraction, over ages. Repaired
damages to living populations do not accumulate.
The by-product of low level radiation damage are
possible mutations, like many other factors in the
environment. They occur only due to the action on
living organisms, they do not occur when spores
are irradiated, when irreversible changes take place.
The soon coming fifth anniversary of the COST
action D27 asks for formulation of conclusions. Intensive, also experimental investigation of the fragment of the action connected with panspermia and
more, i.e. the action of ionizing radiation in the
universe on objects travelling in space, demands
revision of some well established opinions. Theoretical considerations as well as experimental simulations show that these objects are not only sterilized,
what demands comparatively low doses, but also
deprived of its homochirality, if any, and eventually
even freed from organic compounds. Therefore, here
are examples of defined conclusions:
The very thoroughly investigated Murchison
meteorite, supposed to originate ca. 4 Giga years
ago and bringing to the earth samples of organic
compounds, including amino acids from the beginning of the solar system, could not be so old as
claimed. Such a long sojourn in space is connected
with the deamination of amino acids and related
loss of homochirality. The ancient origin of presence of any organic compounds is highly doubtful.
The lifetime of Murchinson meteorite should be estimated in millions and not milliards (US – billions)
of years. The identity of organic matter found in
hundreds of published papers indicates that this
object has been ejected from earth later than 200
million years ago, that means not earlier than
deposites of coal have been formed on earth. Especially polyaromatics and lignine related compounds indicate the origin in large coal deposits,
covering a lot of earth surface. Specialists in considerations of ejection of meteorites from Mars,
which have reached Earth agree that ejections from
Earth to Earth are a little bit less probable, but not
impossible [9]. The matching of location and time
of oblique strike of an asteroid on Earth demands
more analysis and studies.
The second, but not last conclusion refers to
Mars, an object lasting under the ionizing radiation
for Giga years. Assuming that 4 Giga years or so
ago, Mars had oceans of water, the organic soup
was formed, not concluding into creation of life. If
water has evaporated and disappeared, the organic
matter should remain, but in the next millions of
33
years it was radiolysed down to inorganic remains.
Therefore, there should be no hope to find organic
matter whatsoever on Mars. And really, no traces
of organics have been found yet. Actual efforts to
refine methods of investigation for organic matter
look like waste of money.
The work was supported by the Polish Ministry
of Scientific Research and Information Technology and by the European Project COST D27 (Prebiotic chemistry and early evolution).
References
[1]. Luisi P.L.: The emergence of life, from chemical origins to synthetic biology. Cambridge University Press,
Cambridge 2006.
[2]. Zagórski Z.P.: Origins Life Evol. Biosphere, 36, 244-246
(2006).
[3]. Clark B.C.: Origins Life Evol. Biosphere, 31, 185-197
(2001).
[4]. Zagórski Z.P.: Postępy Techniki Jądrowej, 46, 42-52
(2003), in Polish.
[5]. Zagórski Z.P.: Sterylizacja radiacyjna (Radiation sterilization). 2nd ed. Instytut Chemii i Techniki Jądrowej,
Warszawa 2007 (in Polish).
[6]. Zagórski Z.P.: Radiat. Phys. Chem., 66, 329-334 (2003).
[7]. Zagórski Z.P.: Nukleonika, 50, Suppl.2, S59-S63
(2005).
[8]. Zagórski Z.P.: Indian J. Rad. Res., 3, 89-93 (2006).
[9]. Artemieva N. (Institute for Dynamics of Geospheres,
RAS, Moscow, Russia): private communication
(21.11.2006).
MODIFIED BENTONITE FILLERS IN POLYMER COMPOSITES
Zbigniew Zimek, Grażyna Przybytniak, Andrzej Nowicki, Krzysztof Mirkowski
In our previous work, maleic anhydride (MA) was
grafted on the inorganic surface of bentonites containing montmorillonite (MMT) [1]. The main conclusion driven from the studies was that maleic anhydride reacts via the anhydride group with active
ionic sites of bentonite forming a salt-like compound.
Irradiation with electron beam leads to the breakage of double bond in maleic anhydride and to the
production of new organic phases. The range of ionizing radiation doses was found to optimize filler
production [2,3].
In the recent work, we have used the obtained
fillers to prepare composites with polypropylene (PP)
and compare properties of the pure polymer and
polypropylene composites with bentonite modified
ammonium salts.
Isotactic polypropylene (iPP) Malen P J601 was
purchased from Basell Orlen Polyolefines. Unmodified bentonite Tixogel VP (TVP) containing >90%
montmorillonite in the form of sodium salt was
obtained from Riedel-deHaen. Two kinds of unmodified Polish bentonites were received from
Mine “Zebiec”, Starachowice: “Special”, containing
more than 70% of pure montmorillonite and type
“SW”, containing ca. 50% of pure montmorillonite.
Samples of Polish bentonites “Special” modified
with ammonium salts (benzyldodecyldimethyl and
didecyldimethyl bromides) were obtained from
Rzeszów University of Technology and extra pure
samples of montmorillonite were obtained from
Wrocław University of Technology.
Maleic anhydride was absorbed on bentonites
from 10% w/w solution in acetone for half an hour.
The solids were washed with acetone (to remove
excess of anhydride) and dried for 6 h under low
pressure at 30oC. The samples of MMT/MA were
irradiated with 10 MeV electron beam. The overall
doses were 26, 52, 78 or 104 kGy. All the samples,
before testing and mixing with a polymer, were
ground and sieved in order to select fraction of particles below 70 μm, used for further processing.
The composites of polypropylene and modified
bentonites were prepared in a Brabender mixer in
the temperature range of 185-210oC. After mixing,
the samples were pressed in the form of foils of a
thickness of about 0.35 mm.
For scanning electron microscopy (SEM), the
foils were frozen in liquid N2 and broken. SEM
photos at different magnifications were obtained
using a Zeiss SEM microscope after gold deposition.
Structure of modified montmorillonite was
studied by the WAXD (wide-angle X-ray diffraction) method using a URD-6 X-ray diffractometer
with graphite monochromatized Cu-Kα radiation.
SEM photos were obtained with a Jena DSM 942
(Germany) scanning electron microscope with different magnification.
34
The mechanical properties: tensile strength,
yield stress and elongation at break were tested
using a universal testing machine Instron 5565. All
the measurements were performed at ambient temperature according to PN/ISO-527 standard.
Infrared (IR) measurements were conducted on
a Bruker FTIR spectrometer in single reflection
mode (ATR), using a Si prism.
WAXD diffractograms of pristine and modified
with maleic anhydride bentonite “Special” are shown
in Fig.1. The results clearly confirm the presence
of montmorillonite in bentonites which is characterized by specific reflection to the planes (001) and
a periodic distance. Diffractogram (b) of modified
montmorillonite reveals a new peak at the position
2θ=21o what has to be assigned to the changes in
the structure in (002) plane and might suggest that
maleic anhydride is attached to the surface of montmorillonite layers.
IR spectra recorded for montmorillonite, maleic andydride modified montmorillonite before and
after irradiation with a dose of 75 kGy, do not show
details of bond type between montmorillonite and
maleic anhydride forming before and after irradiation with electron beam (Fig.2). This is probably
due to low concentration of organic compounds in
the modified montmorillonite. Only the presence
of maleic anhydride is visible in the spectra of modi-
Fig.1. WAXD diffractograms of: (a) bentonite “Special”,
as purchased, (b) bentonite “Special” after absorption of maleic anhydride and irradiation with a dose
of 26 kGy.
(002). The basal spacing of the montmorillonite is
1.55 nm calculated from the peak on diffractogram
a (position 2θ=5.7o). Upon modification with maleic anhydride, a diffraction peak of bentonite is
almost at the same place (2θ=5.6o, d=1.58 nm)
(Fig.1, diffractogram b) proving that the spacing
between layers is not changed significantly and that
the anhydride is not intercalated between intergallery
layers of montmorillonite. However, intensity of the
lines becomes lower what must result from greater
disorder of the layered silicates, while maintaining
Fig.2. FTIR (Fourier-transform infrared) spectra of: (a) unmodified bentonite “Special”, (b) bentonite “Special”
modified with maleic anhydride, (c) bentonite “Special” modified with maleic anhydride and irradiated
with a dose of 78 kGy.
fied montmorillonite as a band in 1600 cm–1 region
(C=O band of carbonyl compound).
SEM photos at different scale levels of polypropylene foils containing 2.9 wt% of “Special” montmorillonite modified with maleic anhydride and
Fig.3. SEM images of polypropylene filled with bentonite “Special” modified by didecyldimethylammonium bromide
(cross-section of thin foil) at different magnifications.
35
Fig.4. SEM images of polypropylene filled with bentonite “Special” modified by maleic anhydride and irradiated with a
dose of 26 kGy (cross-section of thin foil) at different magnifications.
irradiated with a dose of 50 kGy (Fig.3) were compared with similar photos of foil obtained from
polypropylene containing 2.9 wt% of “Special” montmorillonite modified with didecyldimethylammonium bromide (Fig.4). Photos of the selected composite confirm homogeneity of material obtained
from polypropylene and montmorillonite modified
by maleic anhydride, and subsequently irradiated.
At the micrometer level, images indicate that aggregates of a few micrometers are statistically dispersed in the matrix. On the basis of the consistuents
corresponding to 5 μm one can conclude that there
are particles strongly interacting with the matrix.
Their structure is indistinct, borders between components are blur, it seems that fragments of fillers
are separated by a polymer. Such a picture indicates
on apparent compatibility between fillers and the
matrix. Some tactoids that contain montmorillonite
layers are not parallel thus, disorder of clay significantly increases during mixing of the polymer with
fillers. SEM photos of polypropylene mixed with
ammonium salt modified montmorillonite show
excellent homogeneity of the obtained samples. No
mineral parts of dimensions above 500 nm are visible. Magnification is too low to confirm exfoliation of montmorillonite, but on the basis of visible
structure of the polymeric mixture it is very probable. Presented photos confirm that the laboratory
method used by us for the preparation of composite samples was correct.
Mechanical properties of the original polypropylene and composites of montmorillonite based
on polypropylene are collected in Table. Presented
data are the average values calculated from three
independent measurements. Since the addition to
polymeric matrix more than 5% w/w of the filler
causes a significant growth of viscosity in melted
state, the experiments were performed at a concentration of ca. 2.9% w/w of dispersed phase. Samples
of polypropylene mixed with unmodified bentonite,
except for one composite from a very fine, laboratory purified sample of montmorillonite, showed
insufficient mechanical properties: they were very
fragile and cracked at low elongation. One of the
Table. Mechanical properties of polypropylenes filled with modified bentonites.
36
representative examples of these results is shown
in Table.
In all the composites the yield stress is unaffected
or slightly increased in comparison with the pristine
polymer, while the tensile strength decreases for
all the studied components. The elongation at break
drops for Tixogel VP and “SW” composites from
790 to 686% and 549%, respectively, and increases
to 808% when clay loading is bentonite “Special”.
Generally speaking, the presence of the montmorillonite, even upon modification, does not have a
large effect on the mechanical properties of the
composites, but the role of purity of montmorillonite is visible. Unexpectedly, poor results are obtained for composites of polypropylene and montmorillonite “Special” modified with two types of
ammonium salt, although the samples observed in
SEM have shown excellent dispersion of the fillers
in the polymer matrix.
The best mechanical properties exhibit polypropylene filled with extra fine, laboratory prepared
montmorillonite modified with maleic anhydride
and irradiated; quality of composites containing (in
order) “Special”, Tixogel VP, and “SW” bentonites
are lower. The melt transition of polypropylene is
162oC and increases upon dispersion of montmorillonite in the matrix.
Modification of the different types of bentonite by absorption of maleic anhydride, followed by
irradiation with electron beam shows that particles
obtained in this process are good fillers for the production of composites on the basis of polypropylene. Some properties of final materials are better
than those of initial polypropylene, especially for
composites obtained from modified and irradiated
montmorillonite with low impurity level.
Ionizing radiation facilitates compatibilization
of MMT/MA fillers with the matrix due to introduction of organophilic bridges between dispersed
minerals and polypropylene. However, anhydrides
are not able to intercalate significantly into interlayer galleries increasing d-spacing. The proposed
processing might reduce the contribution of maleic
anhydride and inhibit the degradation associated
with the presence of larger amount of anhydride.
This work was supported by the State Committee for Scientific Research (KBN) – grant
PBZ-KBN-095/T08/2003.
References
[1]. Zimek Z., Przybytniak G., Nowicki A., Mirkowski K.:
Modification of montmorillonite fillers by ionizing
radiation. In: INCT Annual Report 2005. Institute of
Nuclear Chemistry and Technology, Warszawa 2006,
pp. 34-35.
[2]. Polish Patent Application P. 379779 (2006).
[3]. Filho F.G.R., Jeferson T., Melo A., Rabello M.S., Silva
M.L.: Polym. Degrad. Stabil., 89, 383-392 (2005).
POLY(SILOXANEURETHANE) UREAS
BASED ON ALIPHATIC AND AROMATIC DIISOCYANATES
MODIFIED BY IONIZING RADIATION
Ewa M. Kornacka, Grażyna Przybytniak, Janusz Kozakiewicz1/, Jarosław Przybylski1/
1/
Industrial Chemistry Research Institute, Warszawa, Poland
Ionizing radiation is often used to sterilize medical
devices made from polymeric materials. However,
except lowering the level of bioburden, irradiation
affects physicochemical and mechanical properties
of polymers leading usually to degradation or/and
crosslinking. A proportion between both processes
determines final effect. Among products that are
supposed to be sterilized are polyurethanes used as
scaffolds for culturing of biological (e.g. human)
cells for tissue engineering purposes. Recently, segmented polyurethanes have been studied extensively due to their biocompatibility and excellent
mechanical properties [1]. One of the interesting
examples of such a material is polyurethane containing siloxane soft segments that provide hydrolytic stability, elasticity and chemical inertness. It
Scheme.
seems that during irradiation urethane-based products can undergo chain scission at urethane hard
regions as well as at siloxane segments. The character of isocyanates used for polymerization, proportions between NCO and OH groups and the length
of siloxane chains determine resistance of materials
towards ionizing radiation. Data obtained from the
recent investigations show that radical processes in
aliphatic poly(siloxaneurethane) ureas (PSURURs)
proceed predominantly in siloxane segments [2].
Nevertheless participation of urethane domains also
must have an influence on direction and yield of
radiation-induced reactions. Their contribution is
determined by NCO/OH ratio as the excess of NCO
groups is converted to urea bonds in a moisture-curing processes. The length of isocyanate sequences
in hard segments increases with concentration of
free isocyanate units in a prepolymer [3]. Hard and
soft segments create two distinct microphases (or
in some cases even macrophases). On the other
hand, it is generally accepted that urethane or urea
groups form extensive hydrogen bonding systems.
Yilgör et al. found that the strength of hydrogen
bonds between urethanes is much weaker than between urea links due to highly polar character of
the later group [4]. Thus NCO/OH ratio changes
properties of urethane based polymers and is supposed to modify their radiation resistance. On the
other hand, quantum mechanical calculations indicated the absence of interaction between silicones
and urea groups [5].
The polyurethane based materials were prepared from methylene di(p-phenyl isocyanate) or
isophorone diisocyanate, oligosiloxanediol and
water used as a chain-extending agent (Scheme).
The synthesis was performed with the prepolymer
method [1].
Samples of structures shown in Table were investigated by electron paramagnetic resonance
(EPR) after exposure to a dose of 6 kGy in a 60Co
gamma source (Issledovatel) under cryogenic conditions, i.e. at 77 K, since free radicals appeared to
be unstable at ambient temperature.
EPR measurements were performed on an
X-band Bruker ESP 300 spectrometer. Spectra
were recorded directly upon irradiation of the
samples and after their annealing to indicated temperatures.
Samples of PSURURs investigated by gas chromatography were irradiated with a 10 MeV electron beam generated in a linear electron accelerator Elektronika 10/10 to indicated doses. The total
doses were obtained by multipass exposure (30 kGy
per one pass).
The yield of hydrogen in the gas phase volatilize from irradiated at room temperature polymers was determined with a gas chromatograph
Shimadzu-14B. The thermoconductivity method
was used for detection.
Table. Composition of PSURUR.
Fig.1. EPR spectra of listed in Table PSURURs irradiated
to a dose of 6 kGy at 77 K.
associated with the occurrence of methylene radical,
≡SiCH2 that was identified also in oligosiloxanediols
applied as substrates in PSURUR synthesis [2].
One representative EPR spectrum recorded for
oligosiloxanediol of n=10 is shown in Fig.2(a). The
proportion 1:2:1 among lines characteristic of interaction of two equivalent protons is perturbed
due to sharp singlet situated in the middle of the
spectrum that has been attributed to the silicon
radical ≡Si . Thus, the methylene radical is produced by hydrogen abstraction whereas the silicone one by losing the methyl group. An evidence
for Si-C bond scission might be also found in some
spectra detected upon irradiation. Enlargement of
the scale leads to the disclosure of quartet characteristic of the methyl radical, A(3H)=2.3 mT. The
gaseous product decays just at 77 K, therefore only
traces of CH3 were detected in some samples
(Fig.2(c)). The efficiency of methylene radical production in siloxane segments was determined on
the basis of analysis high field peak indicated in
Fig.1 with an arrow in all experimental spectra. This
external line does not represent superposition of
signals but exclusively a side peak of the triplet.
Depending on the structure of PSURURs, either
spectrum shown in Fig.2(a) or a signal of its analogue for n=30 were used for quantitative analysis.
Relative concentration of methylene radicals depends on –[Si(CH3)2O]n– size; for n=30 the contribution is significantly higher than for n=10, both in
aromatic and aliphatic urethanes (Fig.3). Introduction of aromatic rings determines also relative concentration of siloxane radicals. Aliphatic PSURURs
show a smaller relative contribution of paramagnetic
·
·
·
The EPR spectra recorded under cryogenic
conditions for PSURURs of structures presented
in Table are shown in Fig.1.
A triplet of hyperfine splitting near 2.2 mT is
the dominant component of all experimental signals. A centerfield absorption varies and depends
predominantly on the proportions between NCO
and OH groups and a length of –[Si(CH3)2O]n–
units. Previous studies revealed that the triplet is
37
38
·
Fig.3. Relative concentrations of methylene radical ≡SiCH2
determined on the basis of analysis of EPR signals
(see text).
Fig.2. EPR spectrum of (a) oligosiloxanediol, n=10, irradiated at 77 K; (b) signal obtained by subtraction of
spectrum (5) from (3) presented in Fig.1 assigned to
radicals that unpaired spins are localized at heteroatoms; (c) experimental evidence for production of
CH3 .
·
species in siloxane units than aromatic ones since
energy deposited in soft domains and aliphatic regions of hard segments rather induces radicals than
is transformed into heat, as it takes place in aromatic
hard segments. Thus, comparison of the results obtained for samples 1-2 and 5-6 (Fig.3) leads to the
conclusion that the ability to dissipation of ionizing radiation energy by phenyl groups diminishes
the population of radicals.
Distribution of radical centers varies depending
on NCO/OH proportions; the amount of methylene
radicals for n=10 decreases in the following se-
quence 1>3>4, for NCO/OH=2, 2.5, 3, respectively. When the ratio NCO/OH increases, unpaired
spins more frequently are localized at urethane and
urea bonds. Character of the intermediates is unknown as the EPR spectra that could be assigned
to such radicals take the shape of unresolved singlet
(Fig.2(b)). The signal represents radicals of unpaired
spin localized at heteroatoms.
Lost of hydrogen atoms is expected in both segments, hard and soft. Yields of the product measured
by the gas chromatography method are shown in
Fig.4. Emission of H2 in aliphatic PSURURs, 2 and
6, significantly prevails over that found for aromatic
polyurethanes. The results directly indicate that
deposited radiation energy initiates radical processes more effectively if polymeric chains comprise
isophorone ring instead of phenyl groups.
The yield of hydrogen abstraction for aromatic
PSURURs is above three times smaller than for
their aliphatic analogues as can be concluded
from the comparison of G(1) and G(2), as well as
G(5) and G(6) values. Dissipation of radiation energy by aromatic rings involves protection against
radical processes not only in urethane segments but
also in siloxane domains. The G values of aromatic
PSURUR are comprised in the narrow range from
0.20 to 0.36/100 eV. It seems that the influence of
NCO/OH ratio plays an insignificant role in hydrogen release.
Fig.4. Radiation yield of hydrogen determined by gas chromatography (A) and consumption of oxygen resulting from
radical processes (B).
Simultaneously, with radiation yield of H2, the
consumption of oxygen from the space above the
sample inserted in the vial was estimated (Fig.4(b)).
Considerable scattering of results makes detailed
analysis impossible. However, all G(O2) values for
aliphatic PSURURs are in a similar range as G(H2)
data found for aromatic analogues. Thus, unexpectedly, O2 consumption in aliphatic PSURURs
is much lower than the hydrogen yield. Such a disproportion between results might be tentatively
interpreted as a result of very efficient recombination between carbon centered radicals leading
to crosslinking. It seems that in aliphatic PSURURs
the yield of oxidation processes is very limited,
however this suggestion needs further investigations.
In aromatic PSURURs, the concentration of
radicals situated at hard segments is lower than in
aliphatic ones due to efficient dissipation of ionizing radiation energy. Therefore, the relative concentration of methylene radicals is higher and the
yield of dehydrogenation is much smaller than in
39
polyurethanes prepared from isophorene cyanate.
To some extent the protection effect spreads over
the whole polymeric material. Proportion between
urethane and urea groups do not influence hydrogen abstraction processes that proceed only in
hydrocarbon regions or in methyl groups of siloxane
units. It seems that aliphatic PSURURs have a tendency to efficient crosslinking.
References
[1]. Kozakiewicz J.: Advances in moisture-curable siloxane-urethane polymers. In: Advances in urethane science
and technology. Eds. K.C. Frisch, D. Klempner. Lancaster-Basel: Technomic Publ. Co. Inc., 2000, vol. 14,
pp. 97-149.
[2]. Kornacka E.M., Kozakiewicz J., Legocka I., Przybylski
J., Przybytniak G., Sadło J.: Polym. Degrad. Stabil.,
91, 82 (2006).
[3]. Kwiatkowski R., Włochowicz A., Kozakiewicz J., Przybylski J.: Fibres Text. East. Eur., 11, 5, 107 (2003).
[4]. Yilgör E., Yilgör I.: Polymer, 42, 7953 (2001).
[5]. Yilgör E., Burgaz E., Yurtsever E., Yilgör I.: Polymer,
41, 849 (2000).
RADIATION EFFECTS IN POLYPROPYLENE/POLYSTYRENE BLENDS
Wojciech Głuszewski, Zbigniew P. Zagórski
Several applications of polymers demand resistance
towards ionizing radiation, e.g. for disposable
medical devices sterilized by radiation, for applications in nuclear industry and in nuclear reactors,
also for outer space localizations etc. Depending
on the nature and extent of radiation damage, solution of the problem consists in application of additives, produced for general application of polymers. They work often very well also as a protection
from radiation damage, especially when they contain aromatic groups which act as energy sink via
energy transfer mechanism. Some additives are not
acceptable, especially in medical applications and
one of the aims of this investigation was to answer
a question if an aromatic polymer as an additive
can limit the extent of radiation damage. However,
the main topic of the project is basic research on
classic aliphatic/aromatic energy transfer, this time
extended from small molecules to polymers.
Freeman [1] first has found that in irradiated
simple system of cyclohexane/benzene, radiolytic
hydrogen was not formed in proportion to the composition, i.e. benzene was reducing the hydrogen
yield to a higher degree than was expected. The
effect was investigated later in several laboratories
and was called “deviation from the mixture law”.
It was investigated also in frozen systems, gaining
interesting facts connected with the solid crystalline state. Deviation from the mixture law was never
investigated systematically in the field of radiation
chemistry of polymers. Albano et al. investigated
the polypropylene/polystyrene (PP/PS) 20/80%
blends, at low doses [2] and high doses [3] (70-400
kGy) with resulting full protection of polypropylene,
to be expected.
As in the case of cyclohexane/benzene system,
the hydrogen production was used as a basic indi-
cation of radiolysis extent, but in the chosen system of polypropylene/polystyrene, also formations
of methane and carbon monoxide (after oxidative
experiments) in the function of dose and composition were studied, as well as kinetics of oxygen
consumption in the presence of air. Further stages
of oxidative degradation of polypropylene were
studied by diffuse reflection spectrophotometry
(DRS) [4,5].
Introduction of small molecule additives into
polymer composition is simple, but preparation of
aliphatic/aromatic polymer blends is more complicated and demanded new procedures. The case
of polypropylene/polystyrene, i.e. of a semicrystalline, nonpolar thermoplastic polymer with a polar,
amorphous polymer is known to be immiscible.
Mechanical mixing proved formation of unsatisfactory blend from the point of view of energy
transfer, but other approaches resulted in a proper
mixture.
Sample “A” was prepared by mixing commercial
polymers: polypropylene Malen P J-400Z*1632/01
from Basell-Orlen and polystyrene from Owispol-Dwory. The proportions were: 0, 10, 25, 50, 75,
100% of polystyrene. In spite of the most thorough
blending injection and pressing in a mechanical
way, the surface area of contact between both polymers was assumed not to be as most favourable
for energy transfer and, therefore, two other procedures of sample preparation have been developed.
Sample “B” was prepared from virgin polypropylene (F 401) in the shape of powder, collected from
the Orlen-Olefins production line, without additives, next impregnated with polystyrene dissolved
in a styrene monomer (fresh distilled, free from
stabilizers) in proportion of polypropylene/polystyrene as above. Afterward, the styrene was removed
40
by evaporation during gentle heating. Sample “C”
was prepared by soaking polypropylene powder with
stabilizer – free styrene and polymerization/grafting in the gamma field from cobalt-60 at a dose
rate of 1.5 kGy/h. All added styrene has polymerized
totally, but the adjusted percentage was checked
gravimetrically as in sample ”B”. Polymerization
grafting of styrene proceeds in a chain mechanism
in the presence of polypropylene, with high radiation yield (12 000 effects/100 eV), due to the generous supply of free radicals by irradiated polypropylene. Styrene alone (the same batch), gamma- or
electron beam irradiated, polymerizes very slowly
and the progress of reaction can be followed by the
increase of viscosity only. All proportions of both
polymers were checked by weighing the final preparations. All irradiations, except gamma exposure
mentioned above, were done with electron linacs,
“Elektronika” 10/10 (10 MeV, 9 kW) or “LAE 13/9”
(up to 13 MeV, 9 kW straight beam, or 6 kW bent
beam of improved monoenergetic spectrum) [6].
Determination of hydrogen, methane, and secondary product carbon monoxide as well as of oxygen
consumption were done by gas chromatography
using a Shimadzu GC 2040 and GC 2010, molecular sieves 5A, in carrier gas argon.
The applied methods of analysis and investigation, i.e. gas chromatography together with diffuse
reflection spectrophotometry have shown to be
effective in recognition of protection effects in aliphatic/aromatic blends of polymers. Key intermediates and final products of radiolysis have been
determined, i.e. hydrogen, methane and carbon
monoxide.
Fig.1. Radiation yield of hydrogen in the function of
polypropylene/polystyrene composition. A curve
does not start at the same point as curves B and C,
because a commercial polypropylene containing already additives was in this case used. Curves B and
C start from virgin polypropylene. Dose – 25-100
kGy.
For the preparation of blends and mixtures of
aliphatic/aromatic polymers three methods have
been proposed. Conventional blending of polypropylene and polystyrene in Brabender and/or by
injection does not give desired results of protec-
Fig.2. Radiation yield of methane in the function of polypropylene/polystyrene composition. A curve does not
start at the same point as curves B and C, because a
commercial polypropylene containing already additives was in this case used. Curves B and C start from
virgin polypropylene. Dose – 25-100 kGy.
tion against radiolysis of polypropylene by polystyrene (Figs.1 and 2). Mechanical methods cannot secure sufficiently large interphase for energy
transfer. Classical case of previously investigated,
protection phenomena, i.e. benzene/cyclohexane
was effective only in liquid state or frozen from the
gas phase. Application of grafting of styrene on
polypropylene, by two slightly different procedures
resulted in a proper response to expected protection effect. It extended, according to a vague estimate to be a distance of 9-12 mers of polypropylene. Thus, the classical case of radiation protection
effect in the benzene/cyclohexane system has been
extended into the field of polymers. The solid state
system benzene/cyclohexane shows energy transfer
only if it is crystallized from the gas phase to secure
close contact of constituents. In the case of polymeric
system of polypropylene/polystyrene, the mechanical mixing is not sufficient and the effect of energy
transfer occurs only in the case of impregnated and
grafted samples. Chains of both polymers, aliphatic
and aromatic must have sufficient area of contacting, or exhibit low distance sites for energy transfer
to the aromatic structure, which is the sink of energy.
This investigation was supported by a grant No.
0989/T08/2005/28 from the Polish Ministry of Education and Science.
References
[1]. Freeman G.R.: J. Chem. Phys., 33, 71 (1960).
[2]. Albano C., Reyes J., Ichazo M., Gonzáles J., Hernández M., Rodrígues M.: Polym. Degrad. Stabil., 80, 251
(2003).
[3]. Albano C., Reyes J., Ichazo M.N., González J., Rodríguez M.: Nucl. Instrum. Meth. Phys. Res. B, 208, 485
(2003).
[4]. Zagórski Z.P.: Int. J. Polimer. Mater., 52, 323 (2003).
[5]. Zagórski Z.P.: Rafalski A.: Radiat. Phys. Chem., 48,
595 (1996).
[6]. Zagórski Z.P.: Radiat. Phys. Chem., 22, 409 (1983).
41
APPLICATION OF GAS CHROMATOGRAPHY TO STUDY
POSTIRRADIATION PROCESSES OF POLYMER OXIDATION
Wojciech Głuszewski, Zbigniew P. Zagórski
Oxidation of polymers in the atmospheric environment is responsible for the degradation of properties. These processes are initiated by increased
temperature and/or by UV light. Conventional prevention of these undesired phenomena in application of commercial polymers is the addition of
photostabilizers and antioxidants. Radiation processing, e.g. radiation sterilization by electron beam
or gamma radiation causes additional oxidation of
polymers already during irradiation (polyethylene
– PE, polypropylene – PP and many others), as well
as oxidation by oxygen after irradiation, by a chain
mechanism, in particular in the case of polypropylene. The last mentioned reaction prevents the
application of common polypropylene for production of medical objects to be sterilized by ionizing
radiation. Conventional additives mentioned above
do not help in full extent, therefore additional components are looked for, in particular among specific aromatic compounds.
Observation of dynamics of oxidation processes
in polymers is comfortable by the gas chromatographic method [1]. One record secures determination of abstracted hydrogen, carbon monoxide
and methane (Fig.1). The present report shows also
the advantages of oxygen determination, in particular the loss of oxygen, consumed in oxidation of a
inhomogeneity (in comparison to scanned beam)
of the radiation field is neutralized by a special alanine – powder dosimetry, with the diffuse reflection spectrophotometry (DRS) measuring method
[3]. The method is using the fact that the free radical derived from alanine shows an optical absorption spectrum. The use of straight electron beam is
similar to its use in the first versions of our pulse
radiolysis system. Application of higher, kilogray
doses proved to be more convenient by conventional, technological irradiation on a conveyor, by
Fig.2. Radiation yields of H2, O2 and CO in the function of
postirradiation time (polypropylene).
Fig.1. Chromatographic retention (column packed with
molecular sieves 5A): H2, O2, N2, CO and CH4.
polymer. Therefore, the determination of oxidation
rate is easily measured, as well as the formation of
one of the oxidation products (Fig.2).
The integration of irradiation and gas chromatography determination, for the case of solids involved a special approach to the specific technique
of electron beam irradiation of cells closed with
septa, and consideration of different solubility of
hydrogen in a variety of polymers, resulted in new
procedures. Three milliliter glass vials, closed by
septa, are filled only in one third with a sample
and only this part is irradiated with a straight beam
of electrons from the linear electron accelerator
LAE 13/9, leaving the rubber septa intact. This
technique allows the application of small doses of
radiation energy, by triggering single pulses [2].
The use of straight beam of electrons has created some problems with dosimetry. The increased
the bent beam of electrons. The septa are covered
with a thick hood made of lead in this case. Experiment with an empty vial did not show the presence
of hydrogen, what has demonstrated no significant irradiation of septa made from rubber. This
technique was applied for high doses only; application of this mode for low doses of radiation yields
erratic doses, because of the structure of the beam.
That limitation has been recognized already before the construction of the machine and cannot
be avoided due to the pulsing regime of the accelerator action and scanning frequency of 5 Hz. Lower
doses were applied in a 60Co gamma source, with
due analysis of differences of radiation quality in
comparison to the electron beam, if any.
A gas chromatograph Shimadzu GC 2014 has
been installed in an air conditioned and thermostatted (23.5oC) room. The column was 1 m long
packed with molecular sieves 5A, the detector was
thermo-conductivity (TCD-2014) element by Shimadzu. The carrier gas was argon (99.99%). Operations were done with syringes (volume – 10, 25
and 500 μL). The system was working at 220oC, on
the column kept at 40oC and the detector at 120oC.
The rate of flow of carrier gas was 10 mL/min.
Parameters of separations are as follows:
- H2: retention time – tR(H2)=1.48 min, coefficient
of oxygen – R(H2-O2)=2.7, coefficient of peak
symmetry – As(H2)=1.1, number of theoretical
shelves – N(H2)≈86;
42
- O2: retention time – tR(O2)=2.77 min, coefficient
of hydrogen – R(O2-H2)=2.5, coefficient of nitrogen – R(O2-N2)=3.7, coefficient of peak symmetry – As(O2)=1.2, number of theoretical shelves
– N(O2)≈488.
Fig.5. Relation between polystyrene concentration in
polypropylene/polystyrene blends and radiation yield
of postirradiation oxidation processes (postirradiation time: 24-108 h).
Fig.3. Relation between naphtalene concentration in
polypropylene and radiation yield of oxygen.
The described method has proved its efficiency
in the description of protective action of naphthalene towards degradation of polypropylene [4]
(Fig.3). That method helped also to show that the
rate of radiation-induced oxidation of polypropylene at low temperature (under liquid nitrogen) is
higher than at ambient temperature (Fig.4). That
is the first exception of the rule of rather lowered
radiation yields of radiation-induced reactions at
cryogenic temperatures. Further investigations in
The gas chromatographic method has been
applied also in the study of postirradiation oxidation processes of ageing polymers (Fig.5). The loss
of oxygen helped to trace the oxidation process, and
the parallel production of hydrogen has helped to
estimate the participation of aromatic compounds
in the process of blocking peroxide groups and
crosslinking with the polypropylene chain. These
processes interrupt the cycle of polymer degradation and can help in branching of chains, thus improving properties of the material. Analysis of the
influence of polystyrene (PS) content on the oxidation process shows that the protection effect is
higher in the case of samples undergoing a longer
ageing process. One can explain that by the improved
contact of aromatics with the polypropylene matrix.
These few examples have shown that a simple
and sensitive at the same time analytical method
helps to investigate not only radiation oxidation
phenomena but also photo- and thermooxidation.
The investigation was supported by a grant No.
0989/T08/2005/28 from the Polish Ministry of Education and Science.
References
Fig.4. Relation between polystyrene concentration in
polypropylene/polystyrene blends and radiation yield
of oxygen in temperature: -196oC, z +22oC.
this fragment of radiation chemistry will show to
what extent physical conditions in the system are
responsible for that exceptional behaviour.
[1]. Zagórski Z.P., Głuszewski W.: Application of gas chromatography to the investigations on polypropylene
radiolysis. In: INCT Annual Report 2005. Institute of
p. 42
[2]. Głuszewski W, Zagórski Z.P.: Tworzywa Sztuczne i Chemia, 3 (Suppl.), 28 (2006), in Polish.
[3]. Zagórski, Z.P.: Int. J. Polym. Mater., 52, 323 (2003).
[4]. Głuszewski W., Zagórski Z.P.: Radiation effects on
PP/PS blends as model of aromatic protection effects.
Nucl. Instrum. Meth. Phys. Res. B, submitted.
CHEMICAL-RADIATION DEGRADATION
OF NATURAL POLYSACCHARIDES (CHITOSAN)
Andrzej G. Chmielewski, Wojciech Migdał, Urszula Gryczka, Wojciech Starosta
Naturally occurring polysaccharides have a wide
range of applications in agriculture, medicine and
cosmetics, food industry and water waste treatment.
Chitin is second, next to cellulose, most abundant
polysaccharide on the earth. It is present in crustacean shells, insect exoskeletons and fungal cell walls.
Chitosan, (1-4)-2-amino-2-deoxy-β-D-glucan, is
deacetylated derivative of chitin. Commercially
available chitosan possesses high molecular weight
and low solubility in most solvents what limits its
applications. The solubility of chitosan can be improved by decreasing its molecular weight [1].
Water soluble chitosan can be prepared through
oxidative degradation with hydrogen peroxide in
concentration higher than 1 M [2]. Low molecular
weight chitosan can be prepared by chemical, radiation or enzymatic degradation of a high molecular weight polymer. Radiation is one of the most
popular tools for modification of polysaccharides.
For decreasing of the polymerization degree, combined chemical-radiation methods can also be used.
Chitosan oligomers were obtained through irradiation of chitosan dissolved in acetic acid [3]. Another
popular method is also chemical degradation with
hydrogen peroxide which even in small quantity
reduces gradually molecular weight of chitosan [2].
Treating plants with oligochitosan increase their
disease resistance and also plant growth is stimulated. Degraded polysaccharides such as alginate,
chitosan or carrageenan can increase tea, carrot or
cabbage productivity by 15 to 40% [4]. Chitosan irradiated with 70-150 kGy strongly affect the growth
of wheat and rice plant and reduces damages caused
by vanadium. [5]. Alginate degraded with radiation
at concentration 20-50 ppm promotes the growth
of rice seedlings, at a concentration of 100 ppm it
causes an increase of peanut shoots by about 60%
compared to control [6]. Foliar application of
chitosan on pepper plants reduces their transpiration and water use and the biomass-to-water ratio
is significantly better in the treated plants compared
to the control plants [7]. Chitosan can also be used
in plant protection from diseases because it is a
strong antimicrobial agent [8].
The goal of this work was to use radiation for
polysaccharide structure modification. Depolymerization of chitosan can be carried out by radiation
or oxidative degradation with hydrogen peroxide
43
Fig.2. Radiation and chemical-radiation degradation of
chitosan.
[η] = K·Mwa
where: [η] – intrinsic viscosity; M w – average
molecular weight; K and a – constants for chitosan
independent of molecular weights, K=1,81·10–3
cm3/g and a=0.93 determined in 0.1 M acetic acid
and 0.2 M sodium chloride solution at a temperature of 25oC [9]. Results of vicometric measurement of chitosan modified with ionizing radiation
are shown in Fig.1.
Results shown in Fig.2 indicate that irradiation
of a dry powder of chitosan lead to the reduction
of molecular weight. The Mw decreased remarkably with increasing dose up to 200 kGy. For higher
doses, there was no significant change in molecular weight. Hydrogen peroxide caused breaking of
1,4-β-D-glucoside bonds, used at small concentration caused a rapid decrease of molecular weight.
Increasing concentration or reaction time did not
affect the further decrease of polymerization degree. Chitosan degraded with the chemical-radiation method attained 95% mass reduction. Using
hydrogen peroxide at the first stage of degradation
the required doses of radiation can be decreased
what is much more appropriate from the economical point of view.
Figure 3 shows the X-ray diffraction patterns
of initial chitosan and modified chitosan. Initial
chitosan and after radiation exhibited two characteristic peaks at 2θ=8.9o and 2θ=20.2o. There is no
change in intensity of the peaks. Radiation degradation did not destroy crystal structure of chitosan.
Fig.1. Results of vicometric measurement of chitosan modified with ionizing radiation.
combined with irradiation with electron beam.
Efficiency of degradation methods was verified by
viscometric measurements using an Ubbelohde
capillary viscometer k=0.01073. Average molecular weights were calculated from the equation:
Fig.3. X-ray diffraction patterns of (a) initial chitosan, (b)
chitosan after radiation degradation with a dose of
250 kGy and (c) chitosan after chemical-radiation
degradation.
44
For chitosan after chemical-radiation degradation,
the first peak is not observed and the peak at
2θ=20.2o is much less intensive. The results show
that chemical-radiation degradation of chitosan
caused destruction of the crystal structure.
References
[1]. Mao S., Shuai X., Unger F., Simon M., Bi D., Kissel T.:
Int. J. Pharm., 281, 45-54 (2004).
[2]. Tian F., Liu Y., Hu K., Zaho B.: Carbohydr. Polym.,
57, 31-37 (2004).
[3]. Choi W.S., Ahn K.J., Lee D.W., Byun M.W., Park H.J.:
Polym. Degrad. Stabil., 78, 533-538 (2002).
[4]. Kume T., Nagasawa N., Yoshii F.: Radiat. Phys. Chem.,
63, 625-627 (2002).
[5]. Tham L.X., Nagasawa N., Matsuhashi S., Ishioka N.S.,
Ito T., Kume T.: Radiat. Phys. Chem., 61, 171-175
(2001).
[6]. Hien Q.N., Nagasawa N., Tham L.X., Yoshii F., Dang
V.H., Mitomo H., Makuuchi K., Kume T.: Radiat.
Phys. Chem., 59, 97-101 (2000).
[7]. Bittelli M., Flury M., Cambell G.S., Nichols E.J.: Agric.
For. Meteorol., 107, 167-175 (2001).
[8]. Zheng L.Y., Zhu J.F.: Carbohydr. Polym., 54, 527-530
(2003).
[9]. Roberts G.A.F., Domszy J.G.: Int. J. Biol. Macromol.,
4, 374-377 (1982).
DSC STUDIES OF GAMMA IRRADIATION EFFECT ON INTERACTION
OF POTATO STARCH WITH THE SELECTED FATTY ACIDS
AND THEIR SODIUM SALTS
Krystyna Cieśla, Hubert Rahier1/
1/
Department of Physical Chemistry and Polymer Science, Vrije Universiteit Brussel, Belgium
Differential scanning calorimetry (DSC) appeared
to be the appropriate method for detection of
gamma irradiation influence on starch interaction
with lipids [1-3]. Structural modification of macromolecules and possible changes in the lipid surrounding induced by gamma irradiation, as well
as possible modification of the lipid molecules,
were found to affect the properties of the inclusion
amylose-lipid complexes formed with naturally
occurring lipids on heating wheat starch and flour
(A-type) [1,2]. Our preliminary DSC studies have
also shown differences between the complexes
formed by irradiated and the non-irradiated potato
starch (B-type) and admixed 1-mono-lauroyl glycerol [3].
Currently, the effect of potato starch irradiation with 60Co gamma rays using a 30 kGy dose
was studied on its interactions with two fatty acids
(lauric and palmitic) and their sodium salts.
Irradiations with 60Co gamma radiation were
carried out in a gamma cell “Issledovatel” in the
Department of Radiation Chemistry and Technology, Institute of Nuclear Chemistry and Technology.
DSC studies were carried out using a DSC calorimeter of TA Instruments instaled in Vrije Universiteit Brussel (Belgium). DSC studies were carried
out during several heating-cooling-heating cycles
with a heating and cooling rate of 10oCmin–1. The
Universal Thermal Analysis Package was applied
for data analysis. The suspensions placed in hermetically closed pans were characterized by the surfactant : polysaccharide : water ratio of 1:10:10.
This corresponds to 0.498 mmol of lauric acid,
0.390 mmol of palmitic acid, 0.458 mmol of sodium
laurate and 0.359 mmol of sodium palmitate per
1 g of starch. DSC studies were carried out during
several heating-cooling-heating cycles with a heating and cooling rate of 10oCmin–1. Additionally,
some complementary studies were continued with
a heating and cooling rate of 5oCmin–1 applying
the smaller lipid to starch ratios. These values correspond to 0.274 and 0.137 mmol of sodium laurate
or sodium palmitate per 1 g of starch and 0.274
and 0.68 mmol of palmitic acid per 1 g of starch.
Melting of dry solid lauric and palmitic acids
are accompanied by endothermal effects with
peaks at 45.2 and 65.5oC. Melting of both sodium
salts occurs at a considerably higher temperature
and is accompanied by double thermal effects with
peaks at ca. 122 and 135oC. No influence of water
presence was noticed on the temperature range of
melting of both fatty acids, while melting of both
sodium salts occur under such conditions at a considerably lower temperature. During the first heating, melting of lauric acid and sodium laurate in
water takes place in a temperature range lower
Fig.1. Thermal effects attributted to the melting of amylose-lipid complexes recorded during the first and
third heating of the system containing lauric acid
admixed to the non-irradiated and irradiated starch
(at weight ratio equal to 1:10).
than gelatinization (the example in Fig.1; thermal
effect recorded at a temperature below 60oC).
Melting of sodium palmitate starts also at a lower
temperature but continues during gelatinization
while sodium palmitate melts in the same tempera-
Fig.2. Thermal effects attributted to the crystallization
amylose-lipid complex recorded during the first and
third cooling of the system containing lauric acid
(at weight ratio equal to 1:10).
45
separate enthalpies of both processes was, however, less evident.
During the subsequent cooling and heating
cycles, the processes of crystallization and melting
of the amylose-lipid complexes and of free lipid,
present in excess in the system, took place.
The differences were noticed between thermal
effects recorded for the non-irradiated and irradiated starch during the first cooling and during the
subsequent heating and cooling routes. However,
only on addition of lauric acid the results correspond
well to those obtained previously for the complexes
formed in wheat starch with naturally occurred
lipids, or in the complexes formed by potato starch
with mono-lauroyl-glycerol [1-3]. Transformations
of starch lipid complexes occur then at lower temperature in the irradiated than in non-irradiated
samples containing lauric acid as well on heating
and on cooling (Figs.1 and 2) and are accompanied
by a smaller enthalpy. Melting and crystallization
processes taking place during the course of thermal analysis induces in both cases ordering in the
complex structure (proved by an increase in the
enthalpy and temperature of the complex transitions). However, that effect is considerably larger
in the case of non-irradiated starch than in the case
of irradiated starch.
ture range as starch gelatinizes. Formation of the
inclusion complex (exothermal) occcurs during
gelatinization of starch (endothermal). Accordingly, the lower total enthalpy was determined on
the basis of the second thermal effect than that
expected for gelatinization of pure starch present
in the system containing simultaneously lauric acid,
sodium laurate or sodium palmitate. Transition of
the resulting amylose-lipid complex occurs in the
range of higher temperatures. In the case of palmitic
acid addition, decrease of joint enthalpy of gelatinization and melting of lipid, in relation to the
Fig.3, Thermal effects recorded during the third heating and
the third cooling of the system containing sodium
palmitate admixed to the non-irradiated and irradiated starch (at weight ratio equal to 1:10).
Fig.4. Thermal effects recorded during the first, second and
third cooling of the system containing sodium palmitate admixed to the non-irradiated and irradiated
starch (at weight ratio equal to 1:10). The enthalpies
determined for the first, second and third crystallization of the free-lipid phase in the non-irradiated system are equal to -6.0, -4, 8, -3,7 and the irradiated
system -3.8, -7.0, -8.6. The enthalpy determined for
melting of this phase during heating was equal to 9.4
and 9.2 both on the third and second heating of these
systems.
46
Fig.5. Thermal effects attributed to the melting of amylose-lipid inclusion complexes recorded during the
second and third heating of the system containing
sodium laurate admixed to the non-irradiated and
irradiated starch (at weight ratio equal to 1:10).
uted to the differences in the structure of the intermediate phase containing lipid and the non-irradiated and those containing lipid and the irradiated
starch. Furthermore, after thermal treatment an
increase in the enthalpy of crystallization is observed
in the system containing the irradiated starch, while
a decrease in enthalpy of crystallization occurs in
that containing the non-irradiated starch (Fig.4).
This points out the weaker interaction between free
lipids and non-irradiated starch as compared to the
irradiated starch with additional weakening caused
by thermal treatment of the irradiated system, in
contrary to the strengthening induced in the non-irradiated starch. Simultaneously, no differences
were noticed between enthalpies determined for
the second and the third melting of this phase in
both systems (Fig.4, the caption).
Similar results as in the system containing sodium
palmitate were obtained in heating the system containing sodium laurate with that difference that
exothermal process accompanies melting of the
complex formed in the mixtures containing the irradiated starch (Fig.5). This process probably con-
In contrary to the previously examined systems,
thermal effect that can be attributed to melting of
the amylose-lipid complex occurs at higher temperature during heating of the system containing
sodium palmitate and the irradiated starch as compared to that containing the non-irradiated one
(Fig.3). However, similarly as in the previous cases,
crystallization of the complex was observed at considerably lower temperature in the case of irradiated starch as compared to the non-irradiated one
and was accompanied additionally by the endothermal process occurring in a low temperature range
(Fig.3). Moreover, the differences were noticed between the route of melting and crystallization of free
lipid phase (examples in Fig.4). Therefore, melting
occurs at lower temperature in the case of non-irradiated than irradiated starch. This can be attrib-
Fig.6. Thermal effects attributed to the melting of amylose-lipid inclusion complexes recorded during the
second and third heating of the system containing
palmitic acid admixed to the non-irradiated and irradiated starch (at weight ratio equal to 1:10).
Fig.7. Thermal effects recorded during the first, second and
third cooling of the system containing palmitic acid
(at weight ratio equal to 1:10). The enthalpies determined for the first, second and third crystallization
of the free-lipid phase in the non-irradiated system
are equal to -6.0, -4, 8, -3,7 and in the irradiated system -3.8, -7.0, -8.6. The enthalpy determined for melting of this phase during heating was equal to 9.4 and
9.2 both on the third and second heating of these
systems.
sist in crystallization of the complex phase during
melting (resulting probably in the increased peak
temperature) and was not detected in non-irradiated starch. The other difference is that crystallization taking place at the first, second and third cooling of the complexes formed in both irradiated and
non-irradiated starch was always accompanied by
single exothermal effects with a peak at 89-90oC.
A similar conclusion concerning the irradiation
effect on weakening the starch interaction with the
free lipid phase can be, however, derived as in the
system containing sodium palmitate.
Formation of the inclusion complex occurs with
low efficiency in palmitic acid addition and during
the third heating small effects of the complex melting were detected only in the non-irradiated starch
(Fig.6). However, a strong interaction were noticed
between the starch and free-lipid phase (Fig.7). This
concerns probably formation of the so-called surface complex. In fact, the homogeneous residues
were obtained after thermal analyses performed
with a small palmitic acid content. These interac-
47
tions were considerably smaller in the irradiated
starch as compared to the non-irradiated starch.
Although the differences were noticed between
structural properties of the connections formed
between the irradiated and non-irradiated starch
with all the examined ligands, the effect of irradiation differs depending on the ligand. Moreover, the
differences were detected between the influence of
thermal treatment on these properties.
The work was sponsored in the frame of Ministry
of Scientific Research and Information Technology
research grant No. 2P06T 026 27.
References
[1]. Cieśla K., Eliasson A.-C.: Radiat. Phys. Chem., 68,
933-940 (2003).
[2]. Cieśla K., Eliasson A.-C.: J. Therm. Anal. Calorim.,
79, 19-27 (2005).
[3]. Cieśla K., Eliasson A.-C.: DSC studies of gamma
radiation effect on the amylose-lipid complex formed
in wheat and potato starches. Acta Aliment., in press.
SURFACE TENSION STUDIES
OF BINDING CETYLTRIMETHYLAMMONIUM BROMIDE
TO GAMMA IRRADIATED AND NON-IRRADIATED
POTATO AMYLOPECTIN
Krystyna Cieśla, Henrik Lundqvist1/, Ann-Charlotte Eliasson1/
1/
Department of Food Technology Engineering and Nutrition, University of Lund, Sweden
Decrease in molecular weight and the order in
starch granules affects gelatinization processes in
both A and B types of starch [1-4]. Accordingly,
the influence of gamma irradiation was discovered
on the interaction of A-type starches with naturally
occurring lipids [2,3]. In regard to the structural
modification of macromolecules and the formation
of short molecular products, differences were also
found between the possibilities for binding at ambient temperature of iodine by the irradiated and
non-irradiated starch and the structure of the resulting products [4]. Accordingly, gamma radiation is
also expected to modify interaction of B-type starches
with admixed surfactants: binding of the ligands and
the product properties.
Surface tension measurements have appeared
useful in studying the interaction of iodine and surfactants with starch polysaccharides [5,6]. This is
because that surface tension can be considered as
a measure of the monomer surfactant in solution.
Therefore, the more the monomer of surfactant in
solution, the more the surface tension will decrease
before micelles of surfactant start to form. At present, our preliminary results are shown dealing with
the effect of irradiation on binding of cetyltrimethylammonium bromide (CTAB) on starch polysaccharides. The method was applied for examination of
the process taking place at only slightly elevated temperature enabling to obtain homogeneous CTAB
solution.
Waxy potato starch (a pure potato amylopectin)
was obtained due to genetic engineering methods
and was kindly supplied by Lyckeby Stärkelsen
(Sweden). The native dry amylopectin was irradiated with 60Co gamma rays with a 30 kGy dose in a
gamma cell “Issledovatel” installed in the Department of Radiation Chemistry and Technology,
Institute of Nuclear Chemistry and Technology.
Moreover, commercial potato starch was used for
the complementary experiments using a Brookfield
voscometer. Native dry potato starch or 1% starch
gels were irradiated with doses of 10, 20 and 30 kGy.
Axisymmetric drop shape analysis (ADSA) with
a Tracker instrument (IT Concept, Longessan,
France) installed at the University of Lund (Sweden)
was applied for surface tension studies. A syringe
with a u-shaped needle was lowered into the sample
cell and an air bubble was produced from the syringe.
The dynamic surface tension was measured by filming the rinsing buble and analysing the contour of
the bubble. The experiments were performed at
27oC (above the Kraft temperature of CTAB). CTAB
was gradually introduced to 0.25% polysaccharide
gel solutions and the effect of addition each portion of surfactant was studied on their surface tension. The dynamic surface tension was monitored
for one hour in each measurement and the equilibrium surface tension was determined as the
value when a stable level was reached. The curves
representing dependence of equilibrium surface
tension on CTAB concentration were then constructed accordingly to the method described by
Lundquist et al. [6]. Appearance of the free CTAB
induces a decrease in surface tension, while stabi-
48
lization of surface tension indicates the formation
of micelles. The amount of CTAB bound to the
solution is thus shown by the difference between
the total amount of CTAB added and the amount
of free CTAB. Micelles start to form at such CTAB
concentration when the free energy of the surfactant in the micelles is less than in the surfactant –
polysaccharide aggregates or as free monomer in
solution. The critical association concentration of
CTAB is very low and in the present experiment
binding of CTAB to polysaccharides starts at the
moment when the first portion of CTAB is added
[6]. It was also discovered [6] that the same amount
of CTAB can be bound to starch polysaccharides,
independently on its structure (34 mmol CTAB per
mol glucose units). Four sets of experiments were
performed for each irradiated and non-irradiated
starch.
Differences were observed between the route of
surface tension changes taking place due to CTAB
addition to the non-irradiated and irradiated amylopectin solutions (Fig.). Binding of CTAB to the
irradiated starch appeared more “co-operative” than
binding of CTAB to the reference non-irradiated
starch. The “more co-operative type of binding is
shown by the more sigmoidal shape of the curve
Fig. Equilibrium surface tension of CTAB – 0.25% potato
amylopectin solution non-irradiated and irradiated
using a 30 kGy dose.
representing the dependence of surface tension on
CTAB concentration (Fig.). This occurs despite
the fact that binding of CTAB to potato amylopectin was proved to be, in general, of Langmuir type
(apart from the first stage of process when electrostatic interaction of CTAB with starch phosphate groups takes place) [6]. This means that
binding occurs to a number of the equivalent sites
on polysaccharides and the process is not influenced by the fraction of bound ligands. In opposite, binding of CTAB to amylose was found to be
a cooperative process. This means that the formation of the individual complexes is coupled to each
other. The increase in co-operative type of binding
after irradiation might be thus explained in terms
of appearance of the polysaccharide fraction con-
taining less branched molecules or even straight
amylose chains as a result of radiation-induced
scission of the strongly branched polysaccharide
chains.
Complementary studies were conducted using
a Brookfield viscometer for the gels prepared on
the way of prolonged heating at 90oC of commercial potato starch (non-irradiated and irradiated
using various doses) with CTAB (at starch : CTAB
mass ratio equal to 1:0.08). Irradiation with a dose
of 30 kGy of dry native starch induces ca. a 45-fold
decrease in viscosity of its gel formed with CTAB
addition (from 47.5 to 1.1 cP determined in the
case of 1.2% solutions) and ca. an 11-fold decrease
after irradiation with a dose of 10 kGy (to 4.27 cP).
This correspond to 12-fold decrease discovered
after irradiation with the same dose of 10 kGy in
gels formed using starch alone (from 105 to 8.8 cP
determined for 2% solutions). The differences
between viscosities of both types of gels prepared
using the irradiated and control starch result due
to decrease in swelling power (by 2.5 times) and
the essential increase in the amount of the soluble
polysaccharide (at least 4 times) induced by irradiation [4]. Therefore, no particular conclusion
concerning the irradiation effect on capability of
starch for CTAB binding can be drawn on the basis
of the experiment performed for potato starch at
high temperature, similarly as on the basis of the
surface tension studies carried out at low temperature for potato amylopectin. However, the capability for further binding of CTAB was significantly
reduced when gel solution was submitted to irradiation before addition of CTAB. This was shown
by the presence of the crystallites of CTAB in the
products obtained after addition of CTAB to the
irradiated gels, while no free CTAB can be detected
in the case of those obtained under the same conditions but using the non-irradiated gels. Irradiation
of the gels result in the more evident decrease in
the viscosity of the starch-CTAB system. A 50-fold
decrease in the viscosity was found already after
irradiation with a 10 kGy dose (to 1.1 cP), with no
particular influence on further dose increase to 20
and 30 kGy.
The work was done in the frame of the Polish
Ministry of Scientific Research and Information
Technology research grant No. 2P06T 026 27.
References
137-148 (2002).
933-940 (2003).
[3]. Cieśla K., Eliasson A.-C.: J. Therm. Anal. Calorim.,
79, 19-27 (2005).
[4]. Cieśla K., Eliasson A.-C.: DSC studies of gamma radiation effect on the amylose-lipid complex formed in wheat
and potato starches. Acta Aliment., in press.
[5]. Svensson E., Gudmundson M., Eliasson A.-C.: Colloid.
Surfaces B: Biointerfaces, 6, 227-233 (1996).
[6]. Lundqvist H., Eliasson A.-C., Olofsson G.: Carbohydr.
Polym., 49, 43-55 (2002).
49
GAMMA IRRADIATION INFLUENCE
ON STRUCTURE OF POTATO STARCH GELS STUDIED BY SEM
Krystyna Cieśla, Bożena Sartowska, Edward Królak1/, Wojciech Głuszewski
1/
Analytical Centre, Warsaw Agricultural University, Poland
Decrease in molecular weight and ordering in
starch granules induced by gamma irradiation influences its gelling properties. An essential decrease
in swelling power occurs after irradiation of starch
and flour [1,2] and the resulting gels reveal significantly decreased viscosities as compared to those
of the reference non-irradiated gels. This suggests
that irradiation modifies structural properties of the
gels. Accordingly, at present the studies dealing with
the influence of gamma irradiation on the structure
of starch gels were initiated applying scanning electron microscopy (SEM). Several procedures of gels
preparation were tested in purpose to select proper
conditions that could enable to observe differences
between the SEM images obtained for the non-irradiated gels and those irradiated applying various
doses. The influence of each procedure on the resulting images was analysed. The differences between the photos taken for the particular gels were
related to the differences between their physical
properties.
Solid potato starch (laboratory extracted) was
irradiated with 60Co gamma rays in a gamma cell
“Issledovatel” installed in the Department of Ra-
diation Chemistry and Technology, Institute of
Nuclear Chemistry and Technology (INCT). The
doses of 5, 10, 20 and 30 kGy were used. Swelling
power of these samples were examined using the
modified procedure of Eliasson et al. described in
details in [3]. Moreover, viscosity of the gels (2 wt%)
were determined using a Brookfield viscometer.
Gels containing 10 wt% dry matter were prepared on the way of heating starch suspensions for
45 min in glass tubes placed in a heating chamber
stabilized at 100oC. These gels were submitted to
four experimental procedures. The first series of gels
was rapidly frozen in liquid nitrogen and examined
directly at depressed temperature. The second series was also rapidly frozen in liquid nitrogen but
afterwards lyophilized. The third series was obtained
on the way of rapid freezing, further storage at -18oC
for two weeks followed by chemical staining and
critical point drying. The fourth series was prepared
on the way of chemical staining and critical point
drying of the gels obtained after slow cooling and
storage at 4oC for 2 days. Chemical staining was
performed accordingly to the modified procedure
of Kaczyńska et al. [4].
0 kGy
20 kGy
0 kGy
30 kGy
Fig.1. Images recorded (at magnification x600) at depressed temperature for the gels frozen in liquid nitrogen: upper
row – fractures, non-irradiated and irradiated; lower row – surfaces, non-irradiated and irradiated.
50
0 kGy
0 kGy
5 kGy
5 kGy
10 kGy
10 kGy
20 kGy
20 kGy
30 kGy
30 kGy
Fig.2. Typical areas of the gels recorded after rapid cooling at liquid nitrogen and further lyophilization: upper row –
fractures, lower row – surfaces. Magnification of all images is x1000.
51
0 kGy
0 kGy
5 kGy
5 kGy
10 kGy
10 kGy
20 kGy
20 kGy
30 kGy
30 kGy
Fig.3. Typical images obtained for the gels recorded after chemical staining followed by the critical point drying: upper
row – fractures of the gels obtained on the way of rapid freezing (all at magnification x1000), lower row – gels
slowly cooled and stored at 4oC (at magnification x500).
52
SEM studies were conducted using a DSM 942
Scanning Electron Microscope (Zeiss-Leo production) for measurements carried out at ambient
temperature of dried samples covered with a thin
gold layer. The instrument is installed in the INCT.
The rapidly frozen gels were examined at depressed
temperature (-15oC) at low vacuum using a Quanta
200 Microscope (FEI) installed at the Analytical
Centre, Warsaw Agricultural University. The fractures and surfaces of gels were examined.
Images of all the non-irradiated gels indicate a
honey-comb structure, independently of the way of
further treatment, with that difference that lyophilization induces thinning of the comb walls, as compared to the samples examined directly after freezing or those submitted to the chemical staining.
Smooth areas, but with oriented fractures, have
appeared after irradiation of the rapidly frozen gels
examined at depressed temperature both at the
fractures and at the surfaces (Fig.1). Smoothing
shows a higher homogeneity of the irradiated gels.
Orientation results probably due to the preparation
procedure and is caused by the weak internal forces
of the soft irradiated gels as compared to the gravitation force or to the applied mechanical stress.
Both homogeneity of the gels and the weakening
of their internal forces was proved by a decrease in
viscosity. Therefore, a 12-fold decrease in viscosity
was found already after irradiation with a dose of
10 kGy (from 105 cP determined for the non-irradiated 2% gel to 8.8 cP). Swelling power decreases
linearly with irradiation dose applied. The amount
of gel formed after irradiation with a 30 kGy dose
is equal to ca. 0.35% of that formed before irradiation [1].
Similarly, irradiation induces the appearance
of flat and smooth structural elements in the case
of rapidly frozen but lyophilized gels (Fig.2). This
was observed already after irradiation performed
using a dose of 5 kGy. Moreover, further cracking
of these smooth surfaces led to the appearance of
lamellar structure. Further increase in the size of
lamellas, and, consequently, the formation of large
blocks (observed in the gels fractures) as well as
the secondary porosity detected on their surfaces
result with increasing irradiation dose.
Similar observation concerning orientation and
the lamellar structure formation can be done for
the fractures of the rapidly frozen and chemically
stained gels (with orientation starting from a 10
kGy dose radiation) (Fig.3) as in the case of these
lyophilized after freezing. Smoothness of the surfaces and a lamella size increased with irradiation
dose alike in the case of lyophilized gels, while surface porosity of secondary type was avoided in contrary to these gels owing to the chemical staining.
Fragile, brittle gels were obtained after storage
at 4 o C followed by chemical staining (Fig.2).
Smoothing of the gels can be stated after irradiation with 5 kGy, while the lamellar structure results
at higher doses (10 kGy) with further rupture of
the lamellas (20 and 30 kGy). The radiation effect
was, however, less evident than in the other cases.
This occurs probably because of the influence of
staining procedure on the final structure of these
soft gels.
Our results show that SEM enable to observe the
differences between the structure of the non-irradiated potato starch gels and those irradiated applying various doses. The appropriate preparation procedures were selected enabling to detect structural
modification of gels. Moreover, the relationship
was found between modification of gel structure
and the applied dose. Similar irradiation influence
on gel surfaces and fractures can be stated on the
basis of SEM images obtained after rapid freezing
of gels independently of their further treatment.
The radiation effect on the images of the gels slowly
cooled and stored at 4oC was, however, less evident.
The differences in structural properties of gels
shown by SEM result due to the radiation-induced
weakening of the internal forces in gels and increase in their homogeneity.
The work was sponsored in the frame of the
Polish Ministry of Scientific Research and Information Technology research grant No. 2P06T 026 27.
References
[1]. Cieśla K., Eliasson A.-C.: DSC studies of gamma radiation effect on the amylose-lipid complex formed in
wheat and potato starches. Acta Aliment., in press.
[2]. Cieśla K.: J. Therm. Anal. Calorim., 74, 1271-1286
(2003).
[3]. Eliasson A.-C.: Starch/Stärke, 37, 411-415 (1985).
[4]. Kaczyńska B., Autio K., Fornal J.: Food Struct., 12,
217-224 (1993).
RADIOLYTIC DEGRADATION OF FUNGICIDE CARBENDAZIM
BY GAMMA RADIATION FOR ENVIRONMENTAL PROTECTION
Anna Bojanowska-Czajka, Przemysław Drzewicz, Zbigniew Zimek, Bogdan Szostek1/,
Henrietta Nichipor2/, Marek Trojanowicz
1/
2/
DuPont Haskell Laboratory for Health and Environmental Sciences, Newark, USA
Institute of Radiation Physical-Chemical Problems, National Academy of Sciences of Belarus,
Minsk, Belarus
Intensive growth of various industrial branches and
the use of chemicals in agriculture results in increasing flux of anthropogenic toxic pollutants to natural environment. A significant group of these pollutants are pesticides, because of the wide use in
contemporary agriculture, their toxicity and in many
cases slow degradation in natural environment.
Pesticide residues are detected both in the environment (waters, soil), and also in vegetables and fruits,
as well as in processed food. Hence, constant need
Fig.1. Structure of carbendazim.
for improvement and simplification of analytical
methods for the determination of pesticides in various samples is obvious, as well as development of
technologies for their effective removal from industrial wastes and environmental media.
53
The aim of this study was to develop a high
pressure liquid chromatography (HPLC) method
for simultaneous determination of carbendazim
and its decomposition products, identification of
products of gamma radiolysis of carbendazim and
examination of different factors affecting the efficiency of radiolytic degradation of carbendazim,
including dose rate, initial concentration and pH
of irradiated solutions.
For monitoring the effectiveness of radiolytic decomposition of carbendazim and studies of mechanism of this process, investigation on the development of HPLC method enabling simultaneous
determination of carbendazim and products of its
Fig.2. The effect of initial concentration of carbendazim in gamma-irradiated aqueous solutions on (A) yield of decomposition at different irradiation doses and (B) the magnitude of the dose required for 90% decomposition of
pesticide.
Fungicides and chemicals used for the destruction of unwanted fungi in various applications, are
employed on a large scale since the 1960s, and since
then their use constantly increases. Species of most
common use for this purpose are thiabendazole,
fuberidazole, benomyl, methyl thiophanate and
carbendazim (MBC – methyl-2-benzimidazole carbamate) [1]. Carbendazim is also a product of hydrolysis of benomyl and methyl thiophanate. The
structure of carbendazim is shown in Fig.1. It is used
for protection of crops, fruits and vegetables
against fungal diseases, and also for protection of
harvested products during their storage and transportation. Its toxicity is well documented [2], hence
its residues are considered as environmental pollutants.
Methods of decomposition of carbendazim, described so far in the literature are based on photolysis by UV irradiation in various chemical conditions [3-7]. The main subject of those works was
the determination of yield of carbendazim photolysis at different pH of irradiated solutions and
various concentrations of dissolved oxygen. The
efficiency of carbendazim decomposition is facilitated by alkaline pH, where the non-dissociated
form of the substrate is present (protonation constant for carbendazim pKa=4.2), and in the presence of oxygen in irradiated solution [6].
degradation observed in similar processes has been
carried out. These products include benzimidazole,
2-aminobenzimidazole, aniline, o-phenylenediamine and 2-hydroksybenzimidazole. It was found
that pH of the eluent affects significantly retention time of the determined compounds and shape
of chromatograms. The pH 8.0 and wavelength 277
nm were selected as optimum for separation in further measurements.
Effect of the initial concentration and pH
It was found that the radiation dose needed for
90% degradation of carbendazim increases almost
linearly with the value of initial concentration of
fungicide in the examined concentration range
20-100 μmol L–1 (Fig.2). The reported measurements have been carried out in aqueous solution at
pH 7.
In preliminary experiments with carbendazim
the effect of pH on the yield of decomposition of
carbendazim was examined in solutions non-irradiated and gamma-irradiated. It is reported in
the literature and confirmed experimentally in
this work that aqueous solutions of carbendazim
in acidic and neutral media are stable for at least
3-4 months, while slow hydrolytic decomposition
occurs at highly alkaline solutions (Fig.3), where
2-aminobenzimidazole has been detected by
HPLC.
54
Fig.3. Protonation equlibrium and hydrolysis of carbendazim [6].
In gamma-irradiated aerated solutions of carbendazim 100 μmol L–1 in the pH range from 3 to
10 practically complete decomposition has been observed at small doses up to 0.6 kGy (Fig.4). In alka-
Radiolytic decomposition in oxidating
and reducing conditions
Irradiation of aqueous solutions of carbendazim
has been carried out in different conditions, where
solutions were saturated with air, argon or nitrogen
monoxide, and without or with added tert-butanol,
hence the different products of water radiolysis predominate in further reactions with the target compound (see Table in Fig.5). In solutions saturated
with nitrogen monoxide, efficient scavenging of solvated electrons and hydrogen radicals takes place [8]:
H + N2O → N2 + OH k = 2.1 x 106 mol–1 L s–1
eaq + N2O → N2 +OH – k = 9.1 x 109 mol–1L s–1
and as result of that, the largest yield of hydroxyl
radicals is obtained. The addition of tert-butanol
to irradiated solutions is used to scavenge hydroxyl
radicals according to the reaction [9]:
OH + (CH3)3COH → H2O + CH2C(CH3)2OH
k = 6 x 108 mol–1L s–1
So, in such case reducing conditions exist and radical reactions with solvated electron or hydrogen radicals predominate. In solution containing tert-butanol
in acidic media additionally solvated electron is
scavenged, hence the reaction with hydrogen radicals predominates. In solutions saturated with argon
in neutral media all three main oxygen containing
radicals can react with the target pesticide.
In experiments carried out at different irradiation doses it was found that in conditions where
hydroxyl radical predominates the yield of carbendazim decomposition is the largest, that means the
irradiation does need for more complete decom-
·
·
·
Fig.4. The effect of pH of irradiated solutions of carbendazim on yield of decomposition at initial concentration 100 μM.
line solutions it occurs slightly faster and this can be
attributed to simultaneous hydrolysis. It is opposite to observations reported for photochemical decomposition, which was strongly affected by pH of
the initial solution of carbendazim [6].
·
·
Fig.5. Radiolytic decomposition of aqueous 100 μM solutions of carbendazim in different conditions: N2O-saturated solution
at pH 7.0 (z), saturated solution at pH 7 (), argon-saturated solution at pH 1.5 with added 106 μM tert-butanol
(c) and argon-saturated solution at pH 7.0 with added 106 μM tert-butanol (T).
55
Fig.6. Chromatograms obtained for 100 μM aqueous solutions of carbendazim at pH 7.0 gamma-irradiated with 0.2 kGy
dose: (A) before irradiation, (B) irradiated in the presence of 106 μM tert-butanol saturated with argon, and (C)
saturated with nitrogen monoxide. Eluent – 10 mM amonium acetate pH 8.0 with acetonitrile-gradient program.
Column – Phenomenex C18(2) Luna 5 μM (250×4.6 mm). Flow rate – 1 mL/min. Detection at 277 nm. Peak
assignment: (1) benzimidazole, (2) product of reaction with tert-butanol, (3) carbendazim, (4) product of reaction
with tert-butanol, (5) 5-hydroxycarbendazim, (6) hydroxybenzimidazole, (7) 6-hydroxycarbendazim.
position of fungicide is the smallest (Fig.5). Much
less efficient is the decomposition in reducing conditions, where both reactions with solvated electron or hydrogen radical predominate. At a 0.6 kGy
dose, only 50% yield of carbendazim decomposition is observed, while in oxidizing conditions decomposition occurs with 100% yield. In aerated
solutions at a dose of 0.6 kGy also satisfactory 90%
yield of decomposition is observed, which is important from eventual practical applications, where
saturation with nitrogen monoxide would be too
difficult and expensive.
The identification of products formed in radiolytic
decomposition of carbendazim, in various conditions is important for the determination of mech-
anism of occurring processes. In photochemical
processes as the main product of decomposition of
carbendazim, 2-aminobenzimidazol has been identified [7], while when the process was carried out in
the presence of hydrogen peroxide hydroxy derivatives of carbendazim were postulated [3]. In our experiments carried out in different conditions, with
HPLC measurements using mass spectrometry detection different products of decomposition were
found in different conditions (Fig.6). When oxidation with hydroxyl radicals predominate as the products of radiolysis hydroxybenzimidazol and two isomers of hydroxycarbendazim were identified, while
in reducing conditions the main product in the applied conditions benzimidazole was found.
Fig.7. Comparison of experimental results with kinetic modelling for radiolytic decomposition in different conditions: (A)
effect of initial concentration, (B) irradiation of aqueous 100 μM solutions of carbendazim: N2O-saturated solution
at pH 7.0 (z), saturated solution at pH 7 (), argon-saturated solution at pH 1.5 with added 106 μM tert-butanol
(c) and argon-saturated solution at pH 7.0 with added 106 μM tert-butanol (T). Full points – experimental results,
open points – calculated data.
56
Further research will be focused on comparison of experimental data for irradiation in different conditions with modelling based on available
reaction rate constants for radical reactions, and also
a study of similar processes in natural matrices of
industrial wastes. Some preliminary results on comparison of kinetic modelling with experimental
data for the effect of initial concentration and irradiation of carbendazim solutions in different conditions are shown in Fig.7. The observed correlation is especially satisfactory for irradiation in different conditions with different doses.
References
[1]. Modern selective fungicides. Ed. C.J. Delp. Wiley,
London 1987, pp. 233-244.
[2]. Tomlin C.: The pesticide manual. 10th ed. British Crop
Protection Council, Bracknell, London 1994.
[3]. Mazellier P., Leroy E., De Laat J., Legube B.: Environ.
Chem. Lett., 1, 68-72 (2003).
[4]. Mazellier P., Leroy E., De Laat J., Legube B.: New J.
Chem., 26, 1784-1790 (2002).
[5]. Fleeker J.R., Lacy H.M.: J. Agric. Food Chem., 25,
51-55 (1977).
[6]. Pandés R., Ibarz A., Esplugas S.: Water Res., 34,
2951-2954 (2000).
[7]. Boudina A. Emonelin C., Baaliouamer A., Grenier-Loustalat M.F., Chovelon J.M.: Chemosphere, 50, 649-655
(2003).
[8]. Buxton G.V., Greenstock C.L., Helman W.P., Ross A.B.:
J. Phys. Chem. Ref. Data, 17, 513-531 (1988).
[9]. Wojnárovits L., Takács E., Dajka K., Emmi S.S., Russo
M., D’Angelantoniano M.: Radiat. Phys. Chem., 69,
217-219 (2004).
COMPARISON OF PPSL AND TL METHODS FOR THE DETECTION
OF IRRADIATED FOOD AND FOOD COMPONENTS
Grzegorz P. Guzik, Wacław Stachowicz
At present, the main food products being suspected
as treated with the use of ionizing radiation are
spices. Thermoluminescence (TL) examination of
minerals isolated from spices is the best, most sensitive method for the detection of irradiation in
these substances. However, mineral separation is
time-consuming and needs special care. Therefore,
the accomplishment of one TL analysis lasts usually
a few days. The second analytical method adapted
for the detection of radiation treatment in spices is
pulsed photostimulated luminescence (PPSL). In
contrast to the latter, the method is simple and fast
but has some limitations. In general, it is less sensitive than the TL method and is not capable of
measuring the luminescence in all kinds of spices.
Having both methods in the Laboratory of
Detection of Irradiated Food, Institute of Nuclear
Chemistry and Technology (INCT), we performed
a series of parallel experiments to prove the applicability of the PPSL method to detect irradiation
in the variety of spices, herbs, composites with spices
and herbs admixed, and some other food products.
Current research programme covers the PPSL
analysis of archival samples examined earlier by the
TL method followed by the evaluation and comparison of the results obtained with both methods.
Mineral debris of silicates and bioinorganic
composites (calcite and hydroxyapatite) are the
natural contaminants of spices, herbs and seasonings. Mineral in food is composed mainly of quartz
and feldspar, as proved earlier [1]. These debris are
capable of storing steadily the energy of ionizing
radiation in charge carriers trapped at structural,
interstitial or impurity sites. Charge carriers stable
at ambient temperatures, are freed from mineral
debris by increasing the temperature (TL method)
and/or under IR (infrared) illumination (PPSL
method) [2]. Both methods enable to record the
released energy, but methodological difference
between them lies in the state of samples examined:
TL measures isolated mineral fraction, i.e. silicate
minerals only, while PPSL IR stimulated luminescence the light released from all mineral and/or
crystalline components of the sample [3].
The detailed analytical procedure of sample
preparation for TL measurements are based on
PN-EN 1788:2001 [4]; the sample treatment to proceed PPSL measurements, in turn, are described in
PN-EN 13751:2003 (U) [5].
TL examination is achieved with the use of PC
operated TL reader, type TL/OSL, model TL-DA-15
(Risø National Laboratory, Denmark) under the
following measuring conditions: initial temperature – 50oC, final temperature – 500oC, heating rate
– 6oC/s.
Routinely, the normalizing irradiation with 1 kGy
of gamma rays from a 60Co gamma source is described in [4].
The routine preparation of samples [6] compiles
grinding, washing, density separation of a debris of
minerals contained in investigated products. This
procedures is time-consuming and takes normally
a full workday.
In TL, two criteria for the confirmation of radiation treatment are in force: glow ratio (glow 1/glow
2) and the shape and maximum of radiation inducing TL within the temperature range 150-250oC.
The details can been found elsewhere [4,5].
In contrast to TL, the preparation method of
samples for PPSL examination is simple: the product is dispersed in Petri dishes used for the PPSL
measurement. Some samples require earlier treatments like cutting or grating.
PPSL measurement for customers is being done
by the calibrated measurement, equivalent to the
TL normalizing procedure (re-irradiation with
gamma rays). Such treatment delivers more adequate results, while luminescence measurements
are accomplished before and after exposing the
sample to a defined dose of ionizing radiation. The
recommended calibrating dose as adapted in the
Laboratory is from 1 to 4 kGy [5,7].
Fig. Comparison of the results obtained by means of the
PPSL and TL methods.
Typically, irradiated samples indicate only a small
increase of the PPSL signal, whereas in the non-irradiated ones the increase is markedly higher.
A lower threshold (T1=700 counts/60 s) and an
upper threshold (T2=5000 counts/60 s) are used
to classify the sample as non-irradiated (below 700
counts/60 s) or irradiated (above 5000 counts/60
s) [7-9].
57
There are three types of divergences of the PPSL
method with TL results (Table 1). Nineteen samples
(52.7% of the total number, i.e. above 1/2) could
not be classified by means of PPSL. Three samples
(8.3% of 36 samples in question) were qualified as
non-irradiated (resultant screening measurement
is intermediate, while calibration measurement is
positive) or should not be investigated by means
of the PPSL method. For 14 samples (38.8% of 36
samples in question i.e. above 1/3), the divergences
were caused by too low sensitivity of the PPSL
method. However, for a vast majority of the samples
(almost 2/3), the results obtained by both PPSL
and TL methods were found consistent.
Each type of the three divergences discussed
above compiles the variety of products that are classified in Table 2.
For example, the type “samples nonmeasurable by
means of PPSL; TL only” is represented by several
products classified as: seasonings and spices, plant
extracts, pharmaceuticals, processed food products
and food colouring dyes, respectively.
Table 1. Qualification of samples as measured by the PPSL method.
Signal levels between the two thresholds are classified as intermediate, and, if appear, the sample
needs further investigations by means of the TL
method [5,10].
The total number of samples examined was 100.
Consistent results were obtained with 64 samples
(about 2/3), while non-consistent with 36 samples
(about 1/3) of the total number of samples (Fig.).
Table 2. The products investigated in the Laboratory.
The type ”samples non-irradiated and/or needing
to be approved by TL” gathers the products classified as pharmaceuticals and processed food products only.
And finally, the type ”too low sensitivity of PPSL
method; TL approval recommended” is represented
by the products classified as: seasonings and spices,
row seasoning herbs, plant extracts, pharmaceuti-
58
cals, fresh fruits and vegetables, dried vegetables
and mushrooms, respectively.
As seen, despite the fact that some differences
between the types do appear, it is not possible to
say in advances that a given product will delivered
a given response in PPSL. In other words, each products needs individual treatment.
In conclusion it can be said that PPSL is a very
useful method for the qualification of food samples
suspected to be irradiated, but from the practical
point of view it seems reasonable to construct the
list of food products which can be easily examined
by PPSL and those which should be rather subjected
in advance to TL examination.
The results of TL examination of investigated
samples, as used for present comparison, were delivered by M. Laubsztejn, M.Sc. and Mrs G. Liśkiewicz.
References
[1].
Sanderson D.C.W., Slater C., Cairns K.J.: Radiat.
Phys. Chem., 34, 915-924 (1989).
[2]. The SURRC Pulsed Photostimulated Luminescence
(PPSL) Irradiated Food Screening System. Users
manual. Royal Society of Chemistry, Cambridge 2004,
17 p.
[3]. Soika Ch., Delincée H.: Lebensm.-Wiss. Technol., 33,
440-443 (2000), in German.
[4].
PN-EN 1788:2001: Foodstuffs – Thermoluminescence
detection of irradiated food from which silicate minerals can be isolated.
[5]. PN-EN 13751:2003 (U): Artykuły żywnościowe – Wykrywanie napromieniowania żywności za pomocą
fotoluminescencji.
[6]. Research procedures PB-SLINŻ 03: Research procedures and analysis of the results of the examination
of irradiated food by TL method (Wykonanie badań
i analiza wyników badania napromieniowania żywności metodą termoluminescencji). No. 3/2006 (in
Polish).
[7]. Research procedures PB-SLINŻ 04: Research procedures and analysis of the results of the examination
of irradiated food by PPSL method (Wykonanie
badań i analiza wyników badania napromieniowania
żywności metodą luminescencji stymulowanej światłem). No. 2/2006 (in Polish).
[8]. Guzik G.P., Stachowicz W.: Pomiar luminescencji stymulowanej światłem, szybka metoda identyfikacji
napromieniowania żywności. Instytut Chemii i Techniki Jądrowej, Warszawa 2005. Raporty IChTJ. Seria
B nr 3/2005 (in Polish).
[9]. Sanderson D.C.W, Carmichael L., Fisk S.: Food Sci.
Technol. Today, 12(2), 97-102 (1998).
[10]. Sanderson D.C.W., Carmichael L.A., Naylor J.D.:
Food Sci. Technol. Today, 9(3), 150-154 (1995).
DEVELOPMENT AND ACCREDITATION OF EPR METHOD
FOR DETECTION OF IRRADIATED FOOD CONTAINING SUGAR
Katarzyna Lehner, Wacław Stachowicz
The method for the detection of irradiated foodstuffs containing crystalline sugar by the electron
paramagnetic resonance spectrometry (EPR) is
based on the detection in the investigated product
of stable free radicals evoked by radiation treatment.
The majority of radicals produced by radiation in
food is short lining and decays within a few seconds
or minutes. However, if irradiated product contains
crystalline sugar as one of the composites, the presence of relatively stable radicals in the product is
quite probable. The same concerns other food products containing cellulose or bone, both characterized by the presence of micro-crystalline structure.
The crystalline domains in food, as proved in numerous experiments, are very effective in stabilization of radiation induced radicals that can survive
for months or years.
Due to the fact that in sugar-containing foods,
the variety of mono- and disaccharides appear and
that in various products different proportion between them occur, the EPR spectra recorded may
differ, too. On the other hand, they differ from the
EPR signals of single mono- and/or disaccharides.
The intensity of signals, in turn, depends on the
content of crystalline sugar in the product. So, the
EPR detection of irradiation in sweet foods depends
on the sufficient content of sugar crystals in the food
[1-4].
The method of the detection of irradiation in food
containing crystalline sugar has been validated and
subsequently normalized having actually the status
of European standard PN-EN 13708 [5]. In the
validation procedure the Laboratory for Detection
of Irradiated Food, Institute of Nuclear Chemistry
and Technology (INCT), participated, too [6].
The aim of the present study was to prove the
effectiveness of the detection of irradiation in the
variety of sugar-containing food by the procedure
given in PN-EN 13708 with the use of an EPR spectrometer – EPR-10 MINI installed in the Laboratory. This is the only acceptable way to adapt the
method for routine control of food in the INCT.
The investigated products were dried pineapple,
banana, date, fig, papaya, and raisin. Each product
was divided into four samples irradiated with 0.5,
1 and 3 kGy with 60Co gamma rays from an “Issledovatel” irradiator. The fourth sample was a control.
The EPR measurements have been done in
X-band with the use of the EPR-10 MINI mentioned
above and were conducted during 12 months.
The measuring conditions were as recommended
in PN-EN 13708.
Both the irradiated and non-irradiated samples
were measured together with Mn2+ and DPPH standards to evaluated the g factor in the centre of spectra and spectral width.
The selection of the resultant spectra recorded
through the study is given in enclosed Figs.1-3.
Figure 1 presents the spectra of dehydrated pine-
59
Fig.2. EPR spectra non-irradiated fruits: a) pineapple, b)
fig, c) banana.
change, while its intensity decreased by about 35%
(different attenuation of both spectra). Nevertheless, the identification of irradiation is still simple
after 1 year of storage, too.
The detection level of irradiation in dehydrated
foodstuffs was as follows: after exposure of samples
to 0.5 kGy of gamma rays, the radiation treatment
was reliably detected with pineapple, fig, papaya
and raisin. In banana and date the dose of 0.5 kGy
is not detectable within experimental error. The
exposure to 1 kGy is detectable satisfactory. The
stability of the EPR signals after 12 months of storage was, in general, satisfactory, too. In addition
to banana and date (see above), the dose of 0.5
kGy could be detected at the lowest level of detection with raisin only.
A reasonable reproducibility of the spectra was
achieved with the incidentally selected samples of
fig, papaya and raisin. No influence of the orientation of samples inside the resonant cavity was observed.
Fig.1. EPR spectra irradiated 3 kGy of dehydrated fruits:
a) pineapple, b) banana, c) date, d) fig, e) papaya, f)
raisin.
apple, banana, date, papaya and raisin. The difference in the shape of the spectra reflects the various
proportion and composition of sugars in the products. However, gc factor is in all spectra similar,
about 2.0035, while the spectral width varied from
7.4 to 9.2 mT. Figure 2 shows the EPR spectra of
non-irradiated pineapple, fig and banana. The
spectra are recorded at a high gain (see high noise
level) and differ entirely from those of irradiated
stuffs. The signal, if present, is a narrow singlet
with g about 2.0040. Distinction between irradiated and non-irradiated samples is very simple.
Figure 3 shows the EPR spectra of the same sample
of papaya recorded 1 month and 1 year after radiation treatment. The shape of the signal did not
Fig.3. EPR spectra of papaya 1 month (a) and 1 year (b)
after radiation treatment. Dose – 0.5 kGy.
60
The study was a basis for further validation of
the method followed by its accreditation by the
Polish Centre of Accreditation.
References
[1]. Raffi J., Angel J.-P.: Radiat. Phys. Chem., 34, 6, 891-894
(1989).
[2]. Raffi J., Angel J.-P., Ahmend S.H.: Food Technol.,
3/4, 26-30 (1991).
[3]. Stachowicz W., Burlińska G., Michalik J., Dziedzic-Gocławska A., Ostrowski K.: Radiat. Phys. Chem., 46, 4-6,
771-777 (1995).
[4]. Stachowicz W., Burlińska G., Michalik J., Dziedzic-Gocławska A., Ostrowski K.: EPR spectroscopy for the de-
tection of foods treated with ionising radiation. In: Detection methods for irradiated foods, current status. Eds.
C.H. McMurray et al. The Royal Society of Chemistry,
Information Service, 1996. Special Publication No. 171,
pp. 23-32.
[5]. PN-EN 13708: Artykuły żywnościowe – Wykrywanie napromieniowania żywności zawierającej cukry krystaliczne metodą spektroskopii ESR. Polski Komitet Normalizacyjny, Warszawa 2003 (in Polish).
[6]. Raffi J., Stachowicz W., Migdał W., Barabassy S., Kalman B., Yordanov N., Andrade E., Prost M., Callens
F.: Establishment of an eastern network of laboratories
for identification of irradiated foodstuffs. Final report
of Copernicus Concerted Action CIPA-CT94-0134.
CCE, 1998.
DETECTION OF IRRADIATION IN HERBAL PHARMACEUTICALS
WITH THE USE OF THERMOLUMINESCENCE
AND ELECTRON PARAMAGNETIC RESONANCE SPECTROMETRY
Magdalena Laubsztejn, Kazimiera Malec-Czechowska, Grażyna Strzelczak,
Wacław Stachowicz
In view of the two European Union (EU) directives
on food irradiation (1999/2/EC [1] and 1999/3/EC
[2]) the labelling of radiation treated food is obligatory. This regulation concerns food ingredients too,
independently of their content in the product. For
that reason, more and more frequently such products as dried vegetal extracts and pharmaceuticals
containing vegetal ingredients are delivered to the
Laboratory for Detection of Irradiated Food, Institute of Nuclear Chemistry and Technology (INCT),
for examination. The standardized methods for the
detection of irradiation of foods were typically validated with the use of selected products or groups
of products as spices, herbs, crystalline cellulose and
sugars contained in food, etc.
So, the reliability of these methods is related to these
selected products only.
The aim of research activity of the Laboratory during the year 2006 was to prove the ability of the use
of both thermoluminescence – TL (PN-EN 1788:2002)
[3] and electron paramagnetic resonance spectroscopy – EPR (PN-EN 13708:2003) [4] methods for
the detection of irradiation in pharmaceuticals which
contain vegetal components and typically monoand polysaccharides as cohering agent.
The experiments have been done with the samples
of 5 pharmaceuticals containing all these ingredients. They are available in drugstores and resemble
the samples delivered for examination to the Laboratory. The product appears in the form of coated
pills (4 samples) and capsules (one sample). A part
of the samples was irradiated with a dose of 5 kGy
of gamma rays in November 2003, while the other
remained non-irradiated. It is supposed that the
investigated samples contained garlic powder and
vegetal dry extracts, talc, magnesium stearate, monoand polysaccharides, colloidal silica and dyes like
titanium dioxide.
Irradiated and non-irradiated samples were registered as model samples and labelled in a way adapted
in the Laboratory (Table 1).
Samples for thermoluminescence (TL) examination were subjected to analytical procedure according to PN-EN 1788:2002 in order to attain effective isolation of mineral fraction from the remaining vegetal slurry. Subsequently, the mineral fraction was submitted to TL measurements with the
use of a computer operated TL reader under the
following conditions: initial temperature – 50oC,
final temperature – 500oC, heating rate – 6oC/s. Temperature dependent glow curves were doubly measured: once at the beginning and the second time
after normalized irradiation with a dose of 1 kGy
with gamma rays. The intensity of TL integrated
over the temperature range 150-250oC and the TL
glow ratio for irradiated and non-irradiated samples
are shown in Table 2.
The criterion of the classification of irradiated
foodstuff is based, according to PN-EN 1788:2002,
on the evaluation of the TL glow ratio (glow 1/glow
Table 1. Composition of investigated samples – main constituents.
* Sample irradiated with a dose of 5 kGy of gamma rays.
61
Table 2. Thermoluminescence intensity of mineral fraction isolated from irradiated and non-irradiated pharmaceuticals
integrated over the temperature range 150-250oC with the corresponding TL glow ratios.
2) and on the analysis of the shape of the glow curve
recorded within the temperature range 150-250oC
from the mineral fraction isolated from food. TL
glow ratio of irradiated food sample are typically
greater than 0.1. However, in addition to the determination of glow ratio it is advised – in the Laboratory obligatory – to analyse the shape of the glow
curves (TL vs. temperature relationship) recorded
for both preliminarily isolated mineral fractions,
and the same mineral fraction exposed to normal-
Fig.1. Comparison of glow 1 thermoluminescence curves of
mineral fraction isolated from irradiated (SL/T3/A/06)
and non-irradiated (SL/T4/A/06) pharmaceutical.
ized irradiation. Generally, the glow 1 curve for
irradiated foodstuff has its maximum near to 200oC
(±50oC). The mineral fraction isolated from foods
shows quite often a relatively strong TL at higher
temperature with a maximum or maxima above
300oC. This luminescence is presumably released
from deep structural traps in a mineral and originates from natural radionuclides (i.e. potassium,
thorium, actinium) which appear in rocks and soil.
For example, the glow 1 curves recorded for
samples: SL/T3/A/06 (irradiated) and SL/T4/A/06
(non-irradiated) are shown in Fig.1. The shape and
the temperature of the maxima (about 240oC), as
presented for selected sample, is typical of irradiated products. In comparison, the presented curve
with a low intensity and maximum defined near to
350oC is typical of non-irradiated samples [3,5].
The glow ratios calculated for all, irradiated and
non-irradiated samples are compared in the graph
(Fig.2). The TL glow ratios for irradiated samples
are higher than 0.1, whereas the ratios for non-irradiated samples are in all cases lower than 0.1.
The results obtained in the above described test
examination of pharmaceuticals with TL method
indicate conclusively that it is possible to proceed
the classification of this products whether irradiated or non-irradiated with the use of the criteria
applicable to other food products, i.e. consistent
with PN-EN 1788:2002.
Samples for electron paramagnetic resonance
(EPR) examination were prepared as follows: pills
and a capsule were mechanically crushed and then
the samples weighing about 200 mg each were poured
into thin wall sample tubes for EPR measurement,
4 mm in diameter. For each sample three parallel
aliquots were prepared.
62
Fig.2. Thermoluminescence glow ratios of investigated
pharmaceuticals calculated within the temperature
range 150-250oC.
The samples were measured in the EPR spectrometer Bruker ESP 300 under measuring conditions
recommended in PN-EN 13708:2003 for examination of foodstuffs containing crystalline sugar.
The EPR spectra of the investigated samples are
shown in Fig.3.
The recorded spectra of irradiated pharmaceuticals superpose on several complex spectra that,
ago and then every month during half a year. No
evident decrease of intensity and/or change of shape
of the signals were observed.
The EPR examination of non-irradiated pharmaceuticals results in the recording of a weak single,
symmetric line with g=2.0035 ±0.0035. Similar
single lines are observed in non-irradiated foodstuffs
containing crystalline sugars.
The results of the presented experiments are a
goal recommendation for the application of the relatively simple and fast EPR method for preliminary
examination of pharmaceuticals to prove their irradiation prior to the obligatory TL examination.
Thermoluminescence examination of mineral
fraction isolated from various pills and capsules
of herbal pharmaceuticals can be useful for the
evaluation whether these products were irradiated
or not. The essential condition to proceed correctly
the TL examination of herbal pharmaceuticals in
the form of pills and capsules is a very careful analysis of results and looking deeper in the shape of the
resultant glow curves than in the case of typical foodstuffs.
The EPR examination, in turn, enables the detection of radiation treatment of pharmaceuticals
in pills, if they contain as a binding-flavouring agent
crystalline mono- and/or poly-sugars.
The experiments show conclusively that the next
to TL method used for the evaluation of radiation
treatment of this product, if contains sugars, is the
EPR method.
Present results prove the reliability of both
methods for the detection of irradiation in herbal
pharmaceuticals and are an important step of their
validation, opening perspective of their future application in practice. The examination of other products of this type, containing vegetal components and
sugars, is worthwhile of future including this combined detection method as one of those accredited
in the Laboratory today.
References
Fig.3. EPR spectra (first derivative) of non-irradiated and
irradiated pharmaceuticals.
in the majority, can be assigned to sugar born radicals. The width of the spectra was 7.2-7.6 ±0.2 mT,
while the g factor in the centre of the spectra was
2.0028 ±0.0002. The shape of the spectra is similar, although a slight difference appears in the resolution and intensities of some spectra components.
The signals resemble that of pure crystalline sugar.
The observed EPR signals are stable. This was proved
by the examination of all five samples two years
[1]. Directive 1999/2/EC of the European Parliament and of
the Council of 22 February 1999 on the approximation
of the Member States concerning foods and food
ingredients treated with ionising radiation. Off. J.
European Communities L 66/16-23 (1999).
[2]. Directive 1999/3/EC of the European Parliament and of
the Council of 22 February 1999 on the establishment
of a Community list of food and food ingredients
treated with ionising radiation. Off. J. European
Communities L 66/24-25 (1999).
[3]. Standard PN-EN 1788:2002: Foodstuffs – Thermoluminescence detection of irradiated food from which
silicate minerals can be isolated.
[4]. Standard PN-EN 13708:2003: Foodstuffs – Detection
of irradiated food containing crystalline sugar by ESR
spectroscopy.
[5]. Malec-Czechowska K., Stachowicz W.: Nukleonika,
48, 3, 127-132 (2003).
63
ACTIVITY OF THE LABORATORY FOR DETECTION
OF IRRADIATED FOOD IN 2006
Wacław Stachowicz, Kazimiera Malec-Czechowska, Katarzyna Lehner, Grzegorz P. Guzik,
Magdalena Laubsztejn
In 2006, the activity of the Laboratory for Detection of Irradiated Food, Institute of Nuclear Chemistry and Technology (INCT) was focused on the
following topics:
- development of the methods for detection of
irradiated food implemented and accredited
earlier in the Laboratory;
- implementation and accreditation of two standardized detection methods to be included to
the group of methods adapted for routine analytical service for customers;
- analytical service to fulfil the growing requirements of the customers representing firms and
organizations in the country and from abroad.
The task is to classify the variety of more or less
complex food products delivered for examination whether treated with ionizing radiation or
not.
The development of detection methods accredited in the Laboratory considers, generally speaking, the enlargement of the ability of the methods
to identify radiation treatment in food products of
a more and more complex composition as delivered
very often by the customers for examination. The
of Accreditation Nr AB 262 and concerns the detection of radiation treatment in:
- food containing bone, e.g. meat, poultry, fish and
egg shell (PN-EN 1786:2000) [5];
- food containing crystalline cellulose, e.g. shelled
nuts, selected spices and some fresh fruits, as
strawberries (PN-EN 1787:2001) [6];
- food from which silicate minerals can be isolated, i.e. in the variety of spices, herbs, heir
blends, dried and fresh vegetables, fresh shrimps
(PN-EN 1788:2002) [7];
- food containing crystalline sugar, e.g. dried fruits
like dates, figs, raisins etc. (PN-EN 13708:2003)
[8];
- food giving rise to photostimulated luminescence
(PPSL), e.g. herbs, spices and their composities
(PN-EN 13751:2003) [9].
Article 7 (3) of the Directive 1999/2/EC says: “the
EU Member States shell forward to the Commission every year the results of checks carried out at
the product marketing stage and the methods used
to detect irradiated foods”.
Poland, the EU Member State, is obliged to follow the above regulation since 2004. Thus, the
Table. The total number of samples in the Laboratory for Detection of Irradiated Food from 2004 to 2006 under Chief
Sanitary Inspector of Poland programme.
reason of the growing interest of food trade in the
examination of complex products containing typically only a small admixture of irradiated ingredient (e.g. spices) has its source in the regulation that
are in force in all EU Member Countries now.
These are stated in the Directive 1999/2/EC of the
European Parliament and of the Council [1]. The
document says that if a foodstuff contains irradiated ingredient constituting even less than 2.5%
of the product, it is treated in the same way as a
foodstuff that was irradiated in whole, in 100%.
Taking into consideration the requirements of the
Laboratory customers, we proceed research works
leading to the extension of the applicability of our
detection methods to more complex foodstuffs, too.
The survey of this works can be found in [2-4].
Now-a-day five detection methods implanted
earlier in the Laboratory received PCA (Polish
Centre for Accreditation) Accreditation Certificate of Testing Laboratory Nr AB 262 issued on
25.10.2006 and valid until 24.10.2010.
The list of detection methods, all addressed to
specific groups of foodstuffs is included in the Scope
country wide control and monitoring system of
food to prevent illegal trade of irradiated products has been established by the Chief Sanitary
Inspector of Poland. The samples of food products available in the market are delivered to the
Laboratory from the 16 provincial (voivodeship)
sanitary-epidemiological inspections every year.
In Table, the number of both thermoluminescence (TL) and electron paramagnetic resonance
(EPR) examinations accomplished in the Laboratory within this programme from 2004 to 2006 including foodstuff examined and classification of
samples whether irradiated or not are compiled.
The results of 2004 monitoring is included in
the Report from the Commission on food irradiation for the year 2004 (3.20. Poland) [10].
In 2006, except for the above 39 samples, 339
examinations of foodstuffs delivered by the Laboratory customers from abroad (Germany, Italy,
United Kingdom, Denmark, Switzerland, France,
Thailand – 315 samples) and from domestic firms
(24 samples) have been done. The total number of
samples examined for the customers in 2006 was
64
-
shrimps (18.6%);
herbal pharmaceuticals, herbal extracts (21.7%);
poultry and fish (3.6%);
nuts in shell (7.3%);
fresh fruits – strawberries (1.5%);
others, i.e. instant soups, red fermented rice, all
purpose savoury seasoning (1.7%).
References
[1].
Fig.1. Classification of food samples taken for examination in 2006.
478. 87.9% of the total number of samples were
examined by the TL method (PN-EN 1788:2002)
while 12.1% by the EPR methods (PN-EN 1786:2000
and PN-EN 1787:2001).
Among all food samples examined in 2006,
93.7% were found not to be irradiated, while 6.3%
samples were irradiated (Fig.1).
[2].
[3].
[4].
[5].
[6].
[7].
Fig.2. Assortment of foodstuffs examined in 2006.
The assortment of foodstuffs that were examined
in 2006 (Fig.2) compiles:
- spices, herbs and their blends that may contain
small admixture of irradiated spices as a flavour
ingredient (40.2%);
- seasonings, fresh and dried vegetables (5.4%);
[8].
[9].
[10].
Directive 1999/2/EC of the European Parliament and
of the Council of 22 February 1999 on the approximation of the Member States concerning foods and
food ingredients treated with ionising radiation. Off.
J. European Communities L 66/16-23 (13.3.1999).
Guzik G.P., Stachowicz W.: Comparison of PPSL and
TL methods for the detection of irradiated food and
food components. In: INCT Annual Report 2006. Institute of Nuclear Chemistry and Technology, Warszawa 2007, pp. 56-58.
Laubsztejn M., Malec-Czechowska K., Strzelczak G.,
Stachowicz W.: Detection of irradiation in herbal
pharmaceuticals with the use of thermoluminescence
and electron paramagnetic resonance spectrometry.
In: INCT Annual Report 2006. Institute of Nuclear
Chemistry and Technology, Warszawa 2007, pp. 60-62.
Lehner K., Stachowicz W.: Development and accreditation of EPR method for detection of irradiated
food containing sugar. In: INCT Annual Report 2006.
Institute of Nuclear Chemistry and Technology, Warszawa 2007, pp. 58-60.
PN-EN 1786:2000: Foodstuffs – Detection of irradiated food containing bone. Method by ESR spectroscopy.
PN-EN 1787:2001: Foodstuffs – Detection of irradiated foods containing cellulose Method by ESR spectroscopy
PN-EN 1788:2002: Foodstuffs – Thermoluminescence
detection of irradiated food from which silicate minerals can be isolated.
PN-EN 13708:2003: Foodstuffs – Detection of irradiated food containing crystalline sugar by ESR spectroscopy.
PN-EN 13751:2003: Foodstuffs – Detection of irradiated food using photostimulated luminescence.
Report from the Commission on food irradiation for
the year 2004. Off. J. European Communities EN C
230/28 (23.09.2006), 3.20. Poland.
RADIOCHEMISTRY
STABLE ISOTOPES
NUCLEAR ANALYTICAL METHODS
GENERAL CHEMISTRY
67
103
Ru/103mRh GENERATOR
Barbara Bartoś, Ewa Kowalska, Aleksander Bilewicz, Gunnar Skarnemark1/
1/
Department of Chemical and Biological Engineering, Chalmers University of Technology,
Göteborg, Sweden
The possibility of using electron emitters to cure
cancer metastasis depends on the energy of the
emitted electrons. Electrons with high energy give
a high absorbed dose to large tumors, but the dose
absorbed by small tumors or single tumor cells is
low, because the range of the electrons is too long.
The fraction of energy absorbed within the tumor
decreases with increasing electron energy and decreasing tumor size. For tumors smaller than 1 g,
the tumor-to-normal-tissue mean absorbed dose-rate
ratio (TND) will be low, e.g. for 131I and 90Y, because
of the high energy of the emitted electrons. For
radiotherapy of small tumors, radionuclides emitting charged particles with short ranges (a few
micrometers) are required. The short path length
of particles also may limit toxicity to neighboring
normal tissue.
Using various selection criteria like electron
energy, suitable half-life, low photon/electron ratio
and availability, Bernhardt and co-workers found
that the Auger emitter 103mRh meets these criteria
[1]. 103mRh has a short half-life (56 min) and is produced via β– decay of 103Ru or EC decay of 103Pd.
These mother nuclides have half-lives of 39 and 17
days, respectively, and can be used as generators for
103m
Rh. So far, however, only 103Ru has been tested
as the generator, mainly because it is easy to produce in large amounts, either by fission of uranium
or by neutron activation of ruthenium. For therapeutic applications, the 103mRh would be attached
to, e.g. a peptides or monoclonal antibodies to find
the cancer cells.
The goal of the present work is the elaboration
of a 103Ru/103mRh generator for milking therapeutic
quantities of 103mRh. 103Ru. The mother nuclide of
103m
Rh, was obtained by neutron irradiation of a
natural ruthenium target at a neutron of flux 3x1014
n cm–2 s–1 in the nuclear reactor MARIA at Świerk.
After 36 h irradiation of a 9.6 mg target, 130 MBq
of 103Ru was obtained. The target was then dissolved
in a mixture of NaOH and KIO4. After complete
dissolution of the target, the solution was acidified,
and RuO4 formed was extracted to an organic
(CCl4) phase. To avoid reduction of RuO4 to RuO2,
the organic phase was contacted with a solution
generating Cl2 molecules: 1 M HCl+KIO4. The Cl2
molecules, formed in this solution are distributed
among the two liquid phases keeping RuO4 in the
organic phase. Milking of 103Rh was performed by
shaking the organic phase with 0.01 M solution of
H2SO4 containing 0.2 mg ml–1 of KIO4. In this process 103mRh is totally transferred to the aqueous
phase together with small amounts of 103Ru. The
Table. Distribution coefficient for extractions of 103Ru and
103m
Rh.
aqueous phase was purified from tracers of 103Ru
by three times extraction with CCl4, and finally by
passing through an anion exchange resin. The results of stepwise extractions are presented in Table.
If the ruthenium remained as RuO4 there would
be no problem; it would be easy to wash the rhodium
fraction a few times with a pure organic solvent to
remove the contamination. Unfortunately, a small
fraction of the ruthenium in the aqueous phase is
reduced to RuO4– or RuO2, which are difficult to
remove. The RuO4 was removed by few washings
with CCl4. The residue of 103Ru in the aqueous phase
was absorbed as RuO4– on the anion exchange resin.
The separation process involving three solvent
extractions with CCl4 and adsorption on an anion
exchange resin gave separation factors between
103m
Rh and 103Ru of more than 5x103.
The work was carried out in the frame of Marie
Curie Action for the Transfer of Knowledge – contract No. MTKD-CT-2004-509224 with the European Commission.
References
[1]. Bernhardt P., Forssell-Aronsson E., Jacobson L.,
Skarnemark G.: Acta Oncol., 40, 602-608 (2001).
ZOLEDRONIC ACID LABELED WITH 47Sc AND 177Lu
FOR BONE PAIN THERAPY
Maria Neves1/, Ines Antunes1/, Agnieszka Majkowska, Aleksander Bilewicz
1/
Nuclear and Technological Institute, Sacavém, Portugal
Bisphosphonates (BPs) have a strong affinity for
calcium phosphates and for hydroxyapatite. Because of their chemical structure and the characteristic P-C-P- bond, which is non-biodegradable
and non-hydrolysed in vivo, bisphosphonates have
been the chosen molecules for bone scanning imaging. Some bisphosphonate compounds exhibit
short side chains, such as clodronate andetidronate;
others have aliphatic chains of different lengths bearing terminal amino groups (pamidronate, alendro-
68
nate, and neridronate) or substituted amino groups
(olpadronate and ibandronate). Among the last
generation of bisphosphonates with cyclic side
chains, zoledronate with a nitrogen atom in the
imidazole ring, is the most potent bisphosphonate
described so far to inhibit bone resorption. Bisphosphonates labeled with technetium-99mTc are
main radiopharmaceuticals used for bone scanning
imaging. Bisphosphonates are also able to coordinate β-emitter as 153Sm and 186Re, and found application in clinical nuclear medicine for bone metastasis therapy (Re-186-HEDP-Metastron and
Sm-153-EDTMP-Quadramet). Until now, bisphosphonates were labeled with β-emitters of relatively high energy like 153Sm, 188Re and 166Ho. Due
to a long distance interaction of hard β-particles,
the degradation of bone marrow is observed. To
avoid this harmful effect we plan to apply bisphosphonates labeled with soft β-emitters, e.g. 47Sc and
177
Lu instead of hard β-emitters. The distance of
particles emitted by soft β-emitters in bone is much
shorter, less than 1 mm, therefore bone marrow
would not be affected.
The sample of sodium salt of zoledronic acid
(1-hydroxy-2-imidazol-1-yl-phosphonoethyl) was a
gift from Novartis Pharma AG. Due to the short
half-life of 47Sc, the labeling of bisphosphonates
was studied using the γ-emitting 46Sc (t1/2=83.8 d)
radiotracer.
46
Sc and 177Lu radiotracers were obtained by neutron irradiation of Sc2O3 and Lu2O3 targets at a neutron flux of 3x1014 n cm–2s–1 for 6 h. The specific
activities of the radionuclides obtained were 100
MBq/mg for 46Sc and 700 MBq/mg for 177Lu. The
targets were dissolved in 0.1 M HCl solution. The
radiolabeling efficiency and stability evaluation of
the radiocomplexes were accomplished by ascending instant thin layer chromatography (ITLC) using ITLC-SG (Polygram, Macherey-Nagel) strips
developed with the mobile phase: H2O/NH3 (25:1).
The hydroxyapatite-binding assay was performed according to the procedure described previously
after a slight modification [1]. In brief, to vials containing 1.0, 2.0, 5.0, 10.0 and 20.0 mg of hydroxyapatite, were added 2 ml of saline solution at pH
7.4 and the mixtures were shaken for 1 h. Then, 50
μl of each radioactive preparation was added and
the mixtures was shaken for 24 h at room temperature. All suspensions were centrifuged and the
radioactivity of the supernatant was measured with
well γ-scintillation counter. Control experiments
were performed using a similar procedure in the
absence of hydroxyapatite beads. The percentage
binding of 46Sc and 177Lu to hydroxyapatite (HAP)
was calculated according to HA=(1 – A/B)*100,
where A is the final and B – the initial activity of
solution.
In ITLC studies, 46Sc and 177Lu zoledronate complexes migrate (Rf 0.8-1.0), while the ionic and colloidal radioactive forms of 46Sc and 177Lu remain at
the origin. The labeling efficiency of zoledronate with
177
Lu and 46Sc, obtained from the ITLC studies, is
presented in Fig.1. As shown in Fig.1, 46Sc forms
Fig.1. Dependence of labeling efficiency of zoledronate on
the ligand-to-metal mole ratio.
stronger complexes with zoledronate than 177Lu
does. This results from much smaller ionic radius
of Sc3+ than Lu3+.
The zoleodronates labeled with 46Sc and 177Lu in
molar ratio 100:1 was used for studies of adsorption of labeled bisphosphonates on hydroxyapatite. Adsorption of bisphosphonates on hydroxyapatite is commonly used as model for adsorption
of bisphosphonate radiopharmaceuticals on mineral components of the bones. The dependence of
adsorption percent on the mass of hydroxyapatite
samples are shown in Fig.2.
Fig.2. Percent of 46Sc and 177Lu adsorption on hydroxyapatite as a function of hydroxyapatite mass sample.
The maximum adsorption, higher than 98%,
was achieved by 177Lu-zoledronate using more than
5 mg of hydroxyapatite, and by 46Sc-zoledronate
for more than 20 mg of hydroxyapatite.
The obtained results showed that 46Sc forms
more stable complexes than 177Lu zoledronate complexes, while the adsorption of 177Lu complexes on
hydroxyapatite is higher than that of 46Sc-zoleodronate.
The work was carried out in the frame of Marie
Curie Action for the Transfer of Knowledge – contract No. MTKD-CT-2004-509224 with the European Commission.
References
[1]. Neves M., Gano L., Pereira N., Costa M.C., Costa M.R.,
Chandia M., Rosado M., Fausto R.: Nucl. Med. Biol.,
29, 329 (2002).
69
Rh[16aneS4]211At AND Ir[16aneS4]211At COMPLEXES
AS PRECURSORS FOR ASTATINE RADIOPHARMACEUTICALS
Marek Pruszyński, Aleksander Bilewicz, Michael R. Zalutsky1/
1/
Department of Radiology, Duke University Medical Center, Durham, USA
Alpha-targeted therapy is a significant method for
treatment of small solid tumors and hematologic
malignancies (e.g. leukemias and lymphomas). Recently, these diseases are treated with conventionally 131I or 90Y radiolabelled immunoconjugates, but
without great success. These radionuclides emit beta-particles with ranges much larger than the diameter
of a cancer cell. The maximum beta-energies vary
from 0.5 to 2 MeV and the corresponding ranges
are from 1-10 mm. This results in undesirable irradiation of normal cells such as stem cells in the
marrow, even if the cancer cell is successfully targeted.
The alpha-particles are more suited for tiny clusters of cancer cells and micrometastases, because
of their high energy (enable to make double strand
breaks in DNA) and short range, contributing to
their high linear energy transfer (LET) and radiobiologic effectiveness (RBE).
211
At is one of the most promising alpha-emitters
that has, so far, been studied for cancer therapy.
This isotope is artificially produced in a cyclotron
via the 209Bi(α,2n)211At reaction and has a 7.2 h
half-life that allows sufficient time for its production, synthetic chemistry, quality control, transportation and medical application. It decays by double
branch pathway with a mean alpha-energy of 6.7
MeV. As a consequence of its electron capture
branching to its daughter 211Po, X-rays of 71 to 92
keV are emitted, enabling external imaging (including SPECT) and gamma counting of blood samples
as an additional advantage.
The current study was focused on finding a stable
labelled prosthetic group for the use in labelling
of biomolecules with 211At. Our idea was to attach
the astatide anion using its halogen properties to
soft metal cations, which are complexed by a bifunctional ligand. We decided to use rhodium and
iridium, because they are moderately soft metal
cations, which should form very strong bond with
the soft astatide. The high kinetic inertness of the
low-spin d6 Rh(III) and Ir(III) complexes is also a
very important advantage for the formation of
stable conjugate.
Macrocyclic sulphur ligand 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (16aneS4) was chosen
for model studies because it forms stable complex
with Rh(III) and can be modified to a bifunctional
chelate ligand [1]. Complexes between 211At, Rh(III)
or Ir(III) and thioether ligand were synthesized in
an aqueous ethanolic solution. The formation of
complexes was studied by heating the solution at
different time periods (15-120 min) and over a wide
range of temperature (30-90oC). The pH was varied
from 2 to 7.5 by addition of HNO3 or NaOH. The
quantity of Rh(III)/Ir(III) and 16aneS4 was changed
in the range of 0.125-125 nmol and 2.5-250 nmol,
respectively. All control experiments were carried
out under identical conditions with the exception
that thioether ligand was absent. First optimization of reaction conditions was performed with
125 131
I/ I isotopes and later repeated for 211At. Formation and the radiochemical yield of the complexes were estimated by paper electrophoresis, ion
exchange and high performance liquid chromatography (HPLC) methods. Electrophoresis was performed using Whatman #1 paper strips. Reversed
phase HPLC was carried out using a Beckman
Fig.1. HPLC chromatogram of Rh[16aneS4]211At complex
recorded directly after formation: 1 – free unbounded
astatide, 2 – peak of Rh[16aneS4]211At complex.
Coulter device and a Waters Xterra RP18 column
coupled to a beta-detector for radiometric analysis. The gradient elution system utilized mobile
phase A (deionized H2O) and mobile phase B
(100% acetonitrile) and flow rate of 1 ml/min,
started with 95%A/5%B for 5 min at which time
the linear gradient was initiated over 30 min interval to 100%B. Both mobile phases contained 0.1%
trifluoroacetic acid (TFA). An example of HPLC
radiochromatogram is shown in Fig.1. RP HPLC
and the Waters Sep-Pak (C18) columns were also
used to isolate the complexes from synthesis solution for further stability studies. The in vitro stability of complexes was determined in phosphate-buffered saline (PBS) at 37oC with the 131I isotope
as an analogue of astatine.
Fig.2. Dependence of the complex formation on the Rh(III)
and Ir(III) concentration.
70
Dependence of the Rh3+ and Ir3+ mixed ligand
complex formation on the metal cations and sulphur
ligand concentration are shown in Figs.2 and 3. In
Fig.4. Yield of the complexes vs. pH of reaction.
Fig.3. Dependence of the complex formation on the
16aneS4 concentration.
Figure 4, the influence of pH of the solution on
the reaction yield is presented. Maximum complex
formation yields 75 and 80% for Rh[16aneS4]211At
and Ir[16aneS4]211At, respectively, were obtained
at pH 3-5 after heating for 1-1.5 h at 75-80oC. The
optimal concentration of Rh(III)/Ir(III) was 62.5
and 250 nmol for sulphur ligand. The yield of the
reaction with 211At was high, but less than with its
analogue 131I. Paper electrophoresis analysis indi-
cated the expected cationic character of the complexes. Both Rh(III) and Ir(III) complexes with 131I
showed a good stability at pH 7.4 PBS after 51 h
of incubation. The stability studies in human serum
and biodistribution of complexes in normal mice
are in progress.
Part of the work was carried out in the frame of
Marie Curie Action for the Transfer of Knowledge
– contract No. MTKD-CT-2004-509224 with the
European Commission.
References
[1]. Venkatesh M. et al.: Nucl. Med. Biol., 23, 33 (1996).
FORMATION KINETICS AND STABILITY OF SOME
TRI- AND TETRAAZA DERIVATIVE COMPLEXES OF SCANDIUM
Agnieszka Majkowska, Aleksander Bilewicz
Radionuclides with medium energy beta-emission
and a several day half-life are attractive candidates
for radioimmunotherapy. Among the most promising in this category is 47Sc [1]. It has desirable nuclear
properties since it is a beta-emitter (Eβ1=600 keV,
Eβ2(max)=439 keV) with a 3.35 d half-life. In addition, 47Sc has a primary gamma ray at 159 keV
that is suitable for imaging. The methods for production high activities of 47Sc was described by
Kolsky et al. [2]. Enriched 47TiO2 target was irradiated with high energy neutrons (En>1 MeV) to
produce 47Sc via the 47Ti(n,p)47Sc reaction. These
authors also developed a new separation scheme
based on cation exchange on a Dowex AG 50W
resin with elution of 47Sc using HCl/HF solution.
Sc3+ of ionic radius 74.5 pm (CN=6) is chemically similar to Ga3+, In3+, Y3+ and to the heaviest
Fig.1. Ligands selected for complexation of Sc3+ cations.
lanthanides, therefore ligands developed for these
cations should be suitable for chelating 47Sc. In
order to find the best chelators for attaching 47Sc to
biomolecules the formation of Sc3+ complexes with
1,4,7,10-tetraazacyclododecane-1,7-bis acetic acid
(DO2A), 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) and 1,4,7-triazacyclononane-1,4,7 triaacetic acid (NOTA), were studied
by capillary and paper electrophoresis and thin
layer chromatography (TLC). The formulae of the
ligands are presented in Fig.1.
The DOTA and DO2A ligands were purchased
from Macrocyclics. The NOTA ligand was synthesized by reaction of 1,4,7-triazacyclononane with
bromoacetic acid. Chemical purity of the product
was checked by mass spectrometry (MS) and nuclear magnetic resonance (NMR) methods. Stabil-
ity constants of scandium macrocyclic complexes
were determined using capillary electrophoresis.
The Sc3+ complexes were synthesized by mixing of
1.5 mM aqueous solution of a given ligand with
1.5 mM aqueous solution of Sc3+, at pH=3 for
DOTA and NOTA, and at pH=5 for DO2A. When
the complexation process reached equilibrium (8
days), small aliquots of the solution were injected
into the capillary to determine the concentrations
of the complex, free Sc3+ and ligand, respectively.
A typical electrophorogram is presented in Fig.2.
Fig.2. Electrophorogram of ScCl2 and DOTA mixture at
buffer pH 3, applied voltage – 10 kV, capillary – 50
μm, length – 25 cm, detection wave length – 222 nm.
Initial concentration ScCl2 and DOTA – 1.5 mM.
The conditional stability constants were calculated based on the determined equilibrium concentration of the free ligand using the procedure
described by Zhu and Lever [3]. Taking into account the stepwise k1, k2, k3 and k4 protonation
constants of DOTA, the stability constants were
calculated. The results are presented in Table. As
shown in Table, Sc3+ forms most stable complexes
with the DOTA ligand similarly to the lanthanides
and Y3+.
71
Table. Stability constansts of Sc3+ and Lu3+ complexes with
DOTA, DO2A and NOTA ligands.
The electrophoresis and ion exchange studies
indicate that Sc3+ forms complexes with different
charge: anionic with DOTA, neutral with NOTA
and cationic with DO2A. Therefore, we can conclude that in DOTA complexes, Sc3+ has a coordination number of 8, while in NOTA and DO2A
exhibit a coordination number of 6.
The kinetics of Sc3+ DOTA complex formation
was measured at pH=2, 3 and 4. The formation of
the complex under this condition is quite rapid.
The half-time of the equilibrium was reached in
300 s at pH=2.04, in 236 s at pH=3 and in 106 s at
pH=4.
The high thermodynamic stability and inertness
of the studied scandium chelates indicate that 47Sc
labeled biomolecules could be an alternative to 90Y
and 177Lu radiopharmaceuticals.
Part of the work was carried out in the frame of
References
[1]. Mausner L.F., Kolsky K.L., Joshi V., Srivastava S.C.:
Appl. Radiat. Isot., 49, 285-294 (1998).
[2]. Kolsky K.L., Joshi V, Mausner L.F., Srivastava S.C.:
Appl. Radiat. Isot., 49, 1541-1549 (1998).
[3]. Zhu X, Lever S.Z.: Electrophoresis, 23, 1348-1356
(2002).
IN VITRO STABILITY OF TRICARBONYLTECHNETIUM(I) COMPLEXES
WITH N-METHYL-2-PYRIDINECARBOAMIDE
AND N-METHYL-2-PYRIDINECARBOTHIOAMIDE – HISTIDINE
CHALLENGE
Monika Łyczko, Jerzy Narbutt
The strategy to design new 99mTc radiopharmaceuticals involves incorporation of the radionuclide
into biologically active molecules, which requires
chelating 99mTc at an appropriate oxidation state
and linking the obtained chelate to the biomolecule.
The chelates should be stable, kinetically inert,
small in size and moderately lipophilic. As a part of
our systematic studies [1-3] on tricarbonyltechnetium(I) chelates with the derivatives of picolinic and
thiopicolinic acids: N-methyl-2-pyridinecarboamide (LNO) and N-methyl-2-pyridinecarbothioamide (LNS); we studied the stability of these complexes using histidine challenge method. Histidine
and cysteine challenge tests are often used to determine in vitro stability of technetium complexes [4,5].
The 99mTc-LNO and 99mTc-LNS complexes were
obtained from their tricarbonyl precursor, fac-[99mTc(CO)3(H2O)3]+, as described elsewhere [1].
Under conditions of the challenge experiments
(0.07 M Cl–), two forms of the complexes were distinguished, [ 99m Tc(CO) 3 L NX (H 2 O)] + and/or
[99mTc(CO)3LNXCl] (X=O or S), the equilibrium
between these two forms being dependent on the
ligand, LNX. The formation of each complex was
confirmed by high performance liquid chromatography (HPLC) analysis. Molecular structure of the
complexes was confirmed by infrared (IR) studies
on the analogous 99Tc and rhenium complexes followed by X-ray diffraction studies on the latter
[1,6,7], and also by advanced quantum chemistry
calculations [2].
Histidine challenge experiments were performed
by adding 0.5 mL of aqueous phosphate buffer
solution (pH 7.4) containing 2·10–3 M histidine, to
0.5 mL of the 99mTc complex solution containing
excess (2·10–3 M) of LNO or LNS. The samples were
72
Fig.1. HPLC chromatogram of the [99mTc(CO)3LNO] complex after incubating (0.5 h, 37oC) with histidine solution (the concentrations of histidine and LNO are
equal to 1·10–3 M). Peaks: 1 – [99mTc(CO)3(H2O)3]+
(at 4.5 min) practically absent, 2 – TcO 4– , 3a –
[99mTc(CO)3LNO(H2O)]+, 3b – [99mTc(CO)3LNOCl], 4
– [99mTc(CO)3histidine].
incubated at 37oC and analyzed by means of HPLC
after 0.5, 2 and 24 h. After incubating the 99mTc-LNO
complex for 0.5 h, a new peak of a moderate height
appeared in the chromatogram at 12.4 min (Fig.1),
which corresponds well to the position of the
[99mTc(CO)3histidine] complex. This means that
histidine partly replaces the LNO ligand in the complex. The relative magnitude of this 12.4 min peak
after incubating the 99mTc-LNO complex for 2 h is
only slightly greater than that after 0.5 h. On the
other hand, in the chromatogram of the 99mTc-LNS
complex practically no peak of the histidine complex was observed even after incubation as long as
24 h (Fig.2). Generally, tricarbonyltechnetium(I)
Fig.2. HPLC chromatogram of the [99mTc(CO)3LNS] complex
after incubating (24 h, 37oC) with histidine solution
(the concentrations of histidine and LNO are equal
to 1·10–3 M). Peaks: 3a – [99mTc(CO)3L NS(H2O)]+
practically absent, 3b – [99mTc(CO)3LNSCl].
complexes with bidentate ligands undergo significant substitution by tridentate histidine [8,9]. In
view of the above information, the 99mTc-LNO complex studied may be considered fairly stable, while
the 99mTc-LNS complex is extremely stable. This difference in the stability of both tricarbonyltechnetium(I) complexes well corresponds to that in their
yields [1]. On the other hand, the more negative
formation energy of the 99mTc-LNO complex calculated for the gas state [2] can result from the different configurations of the substrates and products in the gas state and the aqueous solution, as
well as from different hydration energies of the LNO
and LNS ligands in the solution [2].
Part of the work was carried out in frame of
References
[1]. Łyczko M., Narbutt J.: Tricarbonyltechnetium(I) complexes with neutral bidentate ligands: N-methyl-2-pyridinecarboamide and N-methyl-2-pyridinecarbothioamide. In: INCT Annual Report 2005. Institute of
pp. 71-74.
[2]. Narbutt J., Czerwiński M., Zasępa M.: Tricarbonyltechnetium(I) complexes with N,O- and N,S-donating
ligands – theoretical and radiochemical studies. In:
Proceedings of the DAE-BRNS Symposium on Nuclear
and Radiochemistry NUCAR 2005, Amritsar, India,
15-18.03.2005. Eds. K. Chander, R. Acharya, B.S. Tomar
and V. Venugopal. BARC, Trombay, Mumbai 2005,
pp. 64-67.
[3]. Narbutt J., Zasępa-Łyczko M., Czerwiński M., Schibli
R.: Tricarbonyltechnetium(I) complexes with neutral
bidentate ligands: N-methyl-2-pyridinecarboamide
and N-methyl-2-pyridinecarbothio-amide. Experimental and theoretical studies. In: International
Symposium on Trends in Radiopharmaceuticals
(ISTR-2005), Vienna, Austria, 14-18.11.2005. Book of
extended synopses. IAEA, Vienna 2005, pp. 61-62.
[4]. La Bella R., Garcia-Garayoa E., Bahler M., Blauenstein P., Schibli R., Conrath P., Tourwe D., Schubiger
P.A.: Bioconjugate Chem., 13, 599-604 (2002).
[5]. Alves S., Paulo A., Correia J.D.G., Gano L., Smith
C.J., Hoffman T.J., Santos I.: Bioconjugate Chem., 16,
438-449 (2005).
[6]. Fuks L., Gniazdowska E., Mieczkowski J., Narbutt J.,
Starosta W., Zasępa M.: J. Organomet. Chem., 89,
4751-4756 (2004).
[7]. Gniazdowska E., Fuks L., Mieczkowski J., Narbutt J.:
Tricarbonylrhenium(I) complex with a neutral bidentate
N-methyl-2-pyridinecarboamide ligand, as a precursor
of therapeutic radiopharmaceuticals. In: International
Symposium on Trends in Radiopharmaceuticals
(ISTR-2005), Vienna, Austria, 14-18.11.2005. Book of
extended synopses. IAEA, Vienna 2005, pp. 190-191.
[8]. Schibli R., La Bella R., Alberto R., Garcia-Garayoa
E., Ortner K., Abram U., Schubiger P.A.: Bioconjugate
Chem., 11, 345-351 (2000).
[9]. Bayly S.R., Fisher C.L., Storr T., Adam M.J., Orvig
C.: Bioconjugate Chem., 15, 923-926 (2004).
73
ION EXCHANGE STUDIES
ON THE ORGANOMETALLIC AQUA-ION fac-[99mTc(CO)3(H2O)3]+
IN ACIDIC AQUEOUS SOLUTIONS
Zbigniew Samczyński, Monika Łyczko, Rajmund Dybczyński, Jerzy Narbutt
The “semi aqua-ion” fac-triaquatricarbonyltechnetium(I) (fac-[99mTc(CO3)(H2O)3]+), 1, is a well
known precursor of potential diagnostic radiopharmaceuticals labelled with 99mTc [1,2]. The carbonyl
ligands are very strongly attached to the central
metal ion due to dπ→pπ back-bonding. Substitution of bi- or tridentate chelating ligands for the
labile water molecules leads to the formation of
numerous complexes, both thermodynamically
stable and moderately kinetically inert. This inertness can be explained by the d6 electron configuration of the central metal ion in the octahedral
environment [1]. Both 1 and its Re(I) analog (1a)
are much more acidic than the aqua-ions of other
monovalent metals. Titration experiments with
macroamounts (10–3 M solutions of Re or 99Tc) resulted in: for 1a pKa≈7.5 [3], and for 1 pKa>8 [1]
or pKa≈8.7 [4]. Oligomerization of the hydrolyzed
species in macroamounts was also observed [1-4].
In aqueous halide solutions the water molecules in
1 are partly substituted by halide ions with the formation of rather weak neutral and anionic halide
complexes [4,5]. The aim of the present work was
to study speciation of 1 at n.c.a. level in acidic aqueous solutions, and in particular the ion exchange
behaviour of the various Tc(I) species.
The complex 1 was obtained following Alberto’s
method [1]. The yield exceeded 95%, the main impurity being the non-reacted 99mTcO4– anion (2) as
detected by high performance liquid chromato-
Fig.1. Electrophorograms of slightly alkaline aqueous solutions of 1: (A) pH 8.65 – the peak moved to the
cathode – [99mTc(CO)3(H2O)3]+ (1); (B) pH 9.20 –
the peak remained at the origin (75 mm from the
cathode) – the neutral [99mTc(CO)3(H2O)2OH] complex (4).
graphy (HPLC). Another impurity, 99mTcO2 (3) removed on a guard C-18 HPLC column, could not
be detected this way. To study the hydrolysis of 1 in
water at higher pH and to confirm the sign of the
electric charge on 1 we used paper electrophoresis
with radiometric detection of 99mTc. The pH of the
initial alkaline solution of 1 (soon after synthesis)
was adjusted to a required value in the range of
1.0÷10.7, by adding some HClO4 or NaOH, and
then 10 μL of the solution was brought on the centre
of a paper stripe (1×15 cm) soaked with an electrolyte of the same pH. The electrophoresis was carried
out at 100 V out for 20 min. A large broad peak
was observed on the electrophorograms, either migrating to the cathode in the pH range of 1.0÷8.65,
or remaining in the origin at pH≥9.2 (Fig.1). The
positively charged species was undoubtedly 1, while
that remaining in the origin would be the neutral
[99mTc(CO)3(H2O)2OH] complex (4) – the product of deprotonation of 1 at higher pH. Basing on
this, we estimate the pKa of 1 to be in the range of
8.8÷9.0, which is consistent with the data for the
macroamounts [1,4]. In the acidic and neutral solutions small amounts of impurities, probably 2 and
3, were also detected, either remaining in the origin
or slowly migrating to the anode. At pH>9 these
small peaks were overlapped by the large, broad peak
of 4.
The ion exchange studies were carried out with
acidic (HNO3 and HCl) solutions, pH<2, at room
temperature. Two different ion exchange resins were
used:
- an amphoteric resin with aminophosphonic
groups, Purolite S-950, 35-65 μm;
- a strongly basic anion exchanger, Dowex 1X4,
200-400 mesh.
Strongly acidic cation exchanger of the gel type,
Dowex 50WX4, appeared inconvenient for this
study because of rather low affinity for 1 and significant peak tailing.
In order to separate 99mTc(I) species from the
impurities 2 and 3, the amount of which increased
with ageing the solution, the dynamic (chromatographic) method of study was applied. Glass columns (0.071 cm2 × 8 cm) were filled with the given
resin, and then washed with either 0.05÷2 M HNO3
(Purolite S-950), or 0.1÷12 M HCl (Dowex 1X4).
99m
Tc samples (50 μL each) in HNO3 or HCl solutions of the same concentration were introduced
on the top of the resin bed, and then the 99mTc
species were eluted from the column at the average
flow rate of 0.64 mL/min. Three 99mTc species were
found in the HNO3 effluent from the column filled
with the amphoteric resin: a small peak of 3 in the
free volume, the main peak of 1, and a peak of 2
of varying magnitude (Fig.2).
The distribution ratio, Di, of the given species i
was determined from the position of its peak on
the chromatogram:
74
Fig.2.
99m
Tc species eluted with 0.3 M HNO3 from amphoteric ion exchange resin, Purolite S-950, loaded with
aged solution of [99mTc(CO)3(H2O)3]+. The numbers
denote the Tc(I) species defined in the text.
(1)
Di = (Vmax,i – V0)·m–1
r
where Vmax,i – effluent volume at the peak maximum
of the species i [mL]; V0 – sum of the dead volume
of the column and the free volume of the resin bed
[mL]; mr – mass of the dry resin [g].
The use of the dynamic method at the slow kinetics of redox reactions of 99mTc (see above) allowed
us to determine the distribution ratios, Dm, of the
99m
Tc compounds at each valence state of technetium,
Tc(m). In the experiments with the HNO3 solutions
we dealt with only one chemical form of 99mTc(I),
1. The slope of linear function logDI vs. log[HNO3],
equal to -0.96 ±0.04 (Fig.3), combined with the
results of the electrophoretic studies, confirms the
+1 charge of 1. The cation 1 is not very hydrophilic: in 1 M HNO3 we have DI=12 mL g–1. The
slope of linear function logDVII vs. log[HNO3],
whole range of HNO3 concentrations studied, so
DIV=0.
On the contrary to the HNO3 systems, only one
large peak was observed in the HCl effluents from
the anion exchanger columns. In this peak various
chemical forms of Tc(I) were eluted altogether:
the precursor 1 and three chloride complexes –
[Tc(CO)3(H2O)2Cl] (5), [Tc(CO)3(H2O)Cl2]– (6)
and [Tc(CO)3Cl3]2– (7), in dynamic equilibrium
[4,5]. Although the equilibrium between 1, 5, 6 and
7 establishes slowly in the NMR time-scale [5], it
is very fast in the time-scale of the ion exchange
experiment (minutes). The latter results in the elution of all these Tc(I) species in the common single
broad peak. In some experiments at DI>10, a small
peak of 3 could be distinguished in the HCl effluent, at the free volume (DIV=0). On the contrary
to the Purolite S-950/HNO3 system, the peak of 2
was never observed in the HCl effluent. That was
due to a very high affinity of the pertechnetate ion,
2, to the Dowex 1X4 resin in the chloride form.
The expected DVII values for the Dowex 1X4/HCl
systems were too large to be experimentally determined.
Fig.4. Distribution ratio of the [99mTc(CO)3]+ species, DI,
in the system anion exchange resin Dowex 1X4/HCl,
as a function of HCl concentration.
Figure 4 shows the dependence of DI (determined from equation 1) on the molar concentration of HCl in the Dowex 1X4/HCl system. Let
us denote the [Tc(CO)3(H2O)3–iCli]1–i formula as
MCl1–i
and assume that the two anionic species
i
formed, 6 and 7 adsorb on the Dowex 1X4 resin
(R-Cl) according to the anion exchange equation:
i
⎯⎯
→ Ri–1MCli + (i – 1)Cl– (2)
(i – 1)RCl + MCl1–i
i
←⎯
⎯
K
Fig.3. The dependence of the distributions ratios, DI and
DVII, of two ionic 99mTc species on the HNO3 concentration in the system Purolite S-950/HNO3 solutions.
equal to -1.00 ±0.05 (Fig.3), corresponds to the –1
charge of 2. The anion 2 is rather strongly adsorbed
on the amphoteric resin studied. On the other hand,
99m
TcO2 is not adsorbed on the resin within the
where Ki denotes the equilibrium constant of the
anion exchange reactions. Ki may be expressed by
the mass action law using thermodynamic activities
of the participating species, provided the activity
of water (solvant) does not change within the whole
range of concentrations studied (constant ionic
strength). This asumption, however, can hardly be
satisfied in ion exchange experiments at a broad
range of the electrolyte (HCl) concentrations. Assuming that also the neutral form, 5, is adsorbed on
the Dowex-1 resin according to (2), we may express
the distribution ratio of Tc(I) as follows:
⎧ 3
⎫ ⎧ 3
⎫
D I = ⎨∑ [R i −1MCli ]⎬ × ⎨∑ [MCl1i −i ]aq ⎬
⎩ i =1
⎭ ⎩ i =0
⎭
−1
(3)
where square brackets denote the molar concentrations of the given species in the aqueous phase
(index aq) and those in the resin phase (no index).
Assuming Ki to be constant values, and including
the constant value [RCl]i-1 into the Ki, we arrive at:
DI =
A[Cl− ]aq
2
+ β3 [Cl− ]3aq
1 + β1[Cl− ]aq + β2 [Cl− ]aq
(4)
where β1, β2 and β3 are the concentrational stability constants of the chloride complexes 5, 6 and 7
in aqueous solution:
−1
−i
βi = [MCl1i −i ]aq × [M + ]aq
× [Cl − ]aq
(5)
and A=K1β1+K2β2+K3β3. Considering A to be a
constant (which is a very rough assumption), and
basing on the experimental dependence of logDI
(determined from equation 1) on log[HCl] in the
Dowex 1x4/HCl system (Fig.4; the solid line is the
75
best-fit polynomial (4)) we evaluated for the three
chloride complexes fac-[99mTc(CO)3(H2O)3–nCln]1–n
the values: β1=0.45, β2=0.085, β3=0.0046 (dm3 mol–1
units). The values obtained are less (by the factor
of 2.4÷3) than the literature values of the respective concentrational stability constants, determined
by 99Tc-NMR for the macroamounts of Tc at a constant ionic strength (I=4) at 22oC [5]. Taking into
account that the ion exchange experiments were
carried out at varying ionic strength of the HCl
solutions (I=0.1÷12) we consider our values for
n.c.a. amounts of Tc at 25oC to be unexpectedly
good approximations for the literature stability
constants.
References
[1]. Alberto R., Schibli R. , Waibel R., Abram U., Schubiger
A.P.: Coord. Chem. Rev., 190-192, 901-919 (1999).
[2]. Alberto R.: Top. Curr. Chem., 252, 1-44 (2005).
[3]. Egli A. et al.: Organometallics, 16, 1833-1840 (1997).
[4]. Suglobov D.N. et al.: In: Technetium, rhenium and other
metals in chemistry and nuclear medicine. 6. Eds. M.
Nicolini, U. Mazzi. SGEditoriali, Padova 2002, pp.
123-126.
[5]. Gorshkov N.I., Lumpov A.A., Miroslavov A.E.,
Mikhalev V.A., Suglobov D.N.: Czech. J. Phys., 53,
A745-A749 (2003).
SYNERGISTIC EFFECT
OF NEUTRAL BIDENTATE N-HETEROCYCLIC LIGANDS
ON THE SEPARATION OF Am(III) FROM Eu(III)
BY SOLVENT EXTRACTION WITH
TETRADENTATE 6,6’-BIS-(DIETHYL-1,2,4-TRIAZIN-3-YL)-2,2’-BIPYRIDINE
Jerzy Narbutt, Jadwiga Krejzler
The research in the partitioning of long-lived radionuclides of minor actinides (An) from nuclear wastes,
directed on their further transmutation, is an important programme in Europe and in several nuclear countries in the world. In particular, it is the
subject of an integrated project EUROPART realized in the 6th Framework Programme of EU within
EURATOM [1]. One of the numerous extraction
systems proposed for the selective separation of
minor actinides from lanthanide (Ln) fission products (the SANEX process) was the subject of our
recent studies [2,3].
N-tetradentate heterocyclic ligands, the derivatives of 6,6’-bis-(1,2,4-triazin-3-yl)-2,2’-bipyridine
(BTBP), have been selected as most promising ex-
tractants for the SANEX process, very selectively
extracting actinides(III) over lanthanides from HNO3
solutions [4,5]. Solvent extraction of Am(III) and
Eu from 1 M HNO3 by 6,6’-bis-(diethyl-1,2,4-triazin-3-yl)-2,2’-bipyridine (C2-BTBP, scheme 1),
with high SFAm/Eu, has been reported [5].Very slow
kinetics of extraction with these lipophilic N-tetradentate ligands, not acceptable in technology, can
be improved by the use of “phase transfer reagents”,
but at the cost of somewhat lowered the An/Ln separation factor, SFAn/Ln [4].
Scheme 2. 5,6-dimethyl-3-pyridin-2-yl-1,2,4-triazine (PT).
Scheme 1. 6,6’-bis-(5,6-diethyl-1,2,4-triazin-3-yl)-2,2’-bipyridine (C2-BTBP).
In the present work, we investigated the effect
of bidentate N-heterocyclic ligands, 5,6-dimethyl-3-pyridin-2-yl-1,2,4-triazine (PT, scheme 2) [6], and
5,5',6,6'-tetraethyl-3,3'-bi-1,2,4-triazine (TT, scheme
3) [6], on the efficiency of the Am(III)/Eu(III) separation by solvent extraction with C2-BTBP. Preliminary liquid-liquid distribution studies have shown
that both C2-BTBP and TT are very lipophilic and
exhibit very low basicity (pKa<<1), while PT is
76
moderately lipophilic and moderate weakly basic
(pKa≈2.7). Dilute 1,1,2,2-tetrachloroethane solutions of C2-BTBP (and its mixtures with PT or TT)
were used to extract carrier-free 152Eu and 241Am
from 1 M HNO3. The test tubes with the two liquid
phases were mildly (60 times per min) mechanically
Scheme 3. 5,5',6,6'-tetraethyl-3,3'-bi-1,2,4-triazine (TT).
shaken at a temperature of 25oC for various time
intervals (from 10 to 180 min). Other experimental
details are described elsewhere [3].
Figure 1 presents the dependence of the distribution ratios of the metal ions, DAm and DEu, on
the extraction time in all the systems studied. In
no system studied the extraction equilibrium was
attained even after 180 min of the slow shaking. In
the system with 0.05 M C2-BTBP alone all the extraction parameters: DAm, DEu and SFAm/Eu are much
Fig.1. Kinetics of solvent extraction of Am(III) (full symbols)
and Eu(III) (open symbols) in the systems: 0.05 M
C2-BTBP (squares), 0.05 M C2-BTBP+0.5 M PT
(circles) and 0.05 M C2-BTBP+0.5 M TT (triangles)
in 1,1,2,2-tetrachloroethane/1 M HNO3 at 25oC.
lower than the respective values reported for the
same system, but under vigorous 60 min shaking,
e.g. SFAm/Eu=160 [5]. Moreover, the rate of Am extraction appears somewhat less than that of Eu.
Therefore, the SFAm/Eu value also increases with the
time of extraction (Fig.2).
The 1,1,2,2-tetrachloroethane solutions of PT
and TT alone, 0.2÷1.5 M, do not noticeably extract
Am(III) ions from 1 M HNO3 (DAm<10–4), which is
consistent with the data by Hudson et al. [6]. Figure
1 shows that the bidentate ligands, PT and TT,
either improve the kinetics of solvent extraction of
Am(III) and Eu(III) ions with C2-BTBP or cause
a thermodynamic synergistic effect in extraction of
both metal ions, much stronger for Am than for Eu.
A great increase in the DAm values is observed when
comparing to the system with C2-BTBP alone, while
the respective increase in the DEu values is relatively
less. This difference leads to a sygnificant increase
also in the SFAm/Eu values which grow with the time
of extraction more and faster than that in the system with C2-BTBP alone (Fig.2).
Fig.2. The increase in the Am(III)/Eu(III) separation factor
with the time of solvent extraction of Am(III) and
Eu(III) in the systems: 0.05 M C2-BTBP (squares),
0.05 M C2-BTBP+0.5 M PT (circles) and 0.05 M
C2-BTBP+0.5 M TT (triangles) in 1,1,2,2-tetrachloroethane/1 M HNO3 at 25oC.
The enhancement of the extraction exerted by
the TT ligand is somewhat greater than that from
PT. All the experimental quantities, DAm, DEu and
SFAm/Eu, observed after 180 min mild shaking in the
mixed-ligand systems seem to approach the equilibrium values. The fact that the DAm and DEu values
are by 2÷4 times lower than the respective equilibrium values reported for the system with C2-BTBP
alone [5] may be interpreted as due to the higher
C2-BTBP concentration in that reference system
(0.068 M). Surprisingly, however, the highest separation factors, SFAm/Eu, in the C2-BTBP+PT and
C2-BTBP+TT systems, 230 and 340, respectively,
are significantly greater than the reported reference
value, 160 ±16 [5]. On the other hand, all the DAm,
DEu and SFAm/Eu values observed in our system with
C2-BTBP alone are clearly non-equilibrium quantities, even after 180 min mild shaking.
If further studies confirm this preliminary observation that 180 min mild shaking makes it possible to reach equilibrium in the mixed-ligand extraction systems studied, while not in the system
with C2-BTBP alone, we will be able to conclude
that the synergism observed is of kinetic origin. In
that case the bidentate ligands studied will be considered the phase transfer regents which do not
decrease the SFAm/Eu value observed in the system
with C2-BTBP alone, surely because of the selectivity of the ligands for Am(III) over Eu(III) ions.
The other option, i.e. the thermodynamic synergism due to preferential formation of mixed-ligand
Am(III) complexes, is less probable because both
tetradentate and bidentate ligands studied are neutral molecules of the same chemical character, which
can hardly exert synergistic effects in solvent extraction of metal ions.
The work was carried out within the European
Commission project EUROPART (contract No.
FI6W-CT-2003-508854) and was co-financed by the
Polish Ministry of Education and Science (decision
No. 619/E-76/SPB/6). We thank our EUROPART
partner, Dr. M.R.St.J. Foreman, for supplying us
with the extractants studied. We also thank Prof.
S. Siekierski for discussion and Mrs. W. Dalecka
for technical assistance.
References
[1]. Madic C., Lecomte M., Dozol J.-F., Boussier H.: Advanced chemical separation of minor actinides from high
level nuclear wastes. In: Proceedings of the Conference
EURADWASTE’04, Luxembourg, 29.03.-01.04.2004.
EUR 21027.
[2]. Narbutt J., Krejzler J.: Separation of Am(III) from
Eu(III) by mixtures of triazynylbipyridine and bis(dicarbollide) extractants. The composition of the metal complexes extracted. In: INCT Annual Report 2005. Institute of Nuclear Chemistry and Technology, Warszawa
2006, pp. 74-76.
77
[3]. Krejzler J., Narbutt J., Foreman M.R.St.J., Hudson M.J.,
Casensky B., Madic C.: Czech. J. Phys., 56, D459-D467
(2006).
[4]. Geist A., Hill C., Modolo G., Foreman M.R.St.J.,
Weigl M., Gompper K., Hudson M.J.: Solvent Extr. Ion
Exch., 24, 463-483 (2006).
[5]. Drew M.G.B., Foreman M.R.St.J., Hill C., Hudson M.J.,
Madic C.: Inorg. Chem. Commun., 8, 239-241 (2005).
[6]. Hudson M.J., Foreman M.R.St.J., Hill C., Huet N.,
Madic C.: Solvent Extr. Ion Exch., 21, 637-652 (2003).
ESTIMATION OF CYTOSTATIC AND ANTIMICROBIAL ACTIVITY
OF PLATINUM(II) COMPLEXES WITH THIOUREA DERIVATIVES
Elżbieta Anuszewska1/, Bożena Gruber1/, Hanna Kruszewska1/, Leon Fuks,
Nina Sadlej-Sosnowska1/
1/
National Medicines Institute, Warszawa, Poland
cis-Platin (cis-diamminedichloroplatinum(II),
CDDP) is used in clinical practice as one of the most
effective anticancer drugs. Unfortunately, its usefulness is limited due to the growing resistance of
tumor cells, and significant side effects of the drug.
It has been found that direct structural analogues
of cis-platin, e.g. diaminocyclohexane (DACH)
platinum(II) complexes, do not show the expected
improvement of the clinical efficacy in comparison with the parent drug. Thus, since a few years
after the discovery of CDDP a continuing effort is
being made to develop other platinum complexes in
order to overcome the above shortcomings [1,2].
In the last two decades, the interest in platinum(II) complexes with chelating ligands containing both nitrogen and sulfur donor atoms has increased, because these complexes seem to exhibit
either higher anticancer activity or reduced toxicity
in relation to known metal containing drugs [3].
As a result of these studies, a number of novel platinum(II) complexes sufficiently interesting for clinical trials have been synthesized. However, only a
few of them have overcome the parent drug in their
efficacy [4]. On the other hand, several combined
chemotherapeutic procedures consisting in the
application of various platinum(II) complexes together with compounds containing S-donor groups
(in this case called chemoprotectants) have been
tested with the aim of reducing the platinum-based
side effects.
As a result of our previous studies [5,6], a question arises whether complexes containing the
PtII(R1R2tu) fragment, where (R1R2tu) denotes a
differently substituted thiourea (tu) molecule,
might exhibit the desired biological activity. Literature data suggest, that platinum(II) complexes
with certain thiourea derivatives (in particular containing the acridine fragment, called ACRAMTUs
[7,8]) can really be potential pharmaceuticals. The
mode of their therapeutic action differs, however,
from that established for the cis-platin. Our searching for the platinum(II) complexes with ligands
containing the thiourea derivatives focused on the
Scheme. N-tetrahydrofurfurylthiourea (1) and N-2-methyltetrahydrothiophenethiourea (2).
synthesis as well as the physicochemical and cytotoxic characterization of the compounds with the
non-acridine thiourea derivatives. The main objective of the presented study was to determine biological, i.e. cytotoxic and antimicrobial activity of
platinum(II) complexes with N-2-tetrahydrofurfurylthiourea (1) and N-2-methyltetrahydrothiophenethiourea (2), see Scheme. MTT assay (test for measuring cell growth with colorimetric assay using
yellow colorimetric indicator: MTT – 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide)
was performed as described by Gruber and Anuszewska [9].
In addition to the cytotoxic properties, biological activity of the platinum complexes against different microorganisms was tested. The antimicrobial activity was expressed by minimal inhibitory
concentration (MIC). Results of the MIC measurements are presented in Table 1.
The results are displayed on the bar char, where
L(O) and L(S) stand for the platinum(II) complex
with 1 and 2, respectively (Fig.1).
It can be seen that both complexes are especially
efficient against Staphylococcus epiderminis: platinum(II)-1 complex inhibited growth of the strain
at a concentration of 5 mM, whereas platinum(II)-2
was active against Staphylococcs epidermidis at 2.5
mM. The latter was also active against Bacillus
pumilus at a concentration of 5 mM. All other
bacterial strains were inhibited by platinum(II)-1
complex at a concentration of 10 mM, and by
platinum(II)-2 at a concentration of 20 mM. On
the other hand, the fungal strains were resistant
to both compounds even at the highest concentration, i.e. of 20 mM.
78
Table 1. MIC values of the investigated platinum(II) complexes.
Table 2. The IC50 values of the investigated platinum(II)
complexes.
Cytotoxic activity of the complexes was determined with the use of MTT test. As shown in Table
2 and Fig.2, all kinds of cells examined exhibit comparable sensitivity to both platinum(II)-1 and platinum(II)-2 complexes. The less sensitive to the
platinum(II) complexes appeared HeLa cells (an
The obtained data indicate that mammalian
cells are about 10 times more sensitive than bacterial cells with reference to the platinum complexes
studied.
Stability of both complexes, with 1 and 2, in the
standard aqueous physiological solution was checked
by recording their UV-Vis spectra (200-800 nm,
nmax=235 nm) vs. time. No changes in the spectra
have been detected within one week. The HPLC
chromatograms of samples withdrawn occasionally
from the saline solutions of the complexes during
one week (isocratic elution using a CH3CN-H2O
mixture, vol:vol=20:80; 230 nm) did not exhibit
noticeable changes either.
As a result of the presented work, we can conclude that the biological activity of both platinum(II)-1 and platinum(II)-2 complexes, determined as their cytostatic IC50 and antimicrobial
MIC values, is not very high. The same concerns
the results obtained already for the standard L1210
murine leukemia cell line [10]. However, the found
cytotoxicity is significantly improved as compared
to that of platinum(II) complexes with the unsubstituted thiourea molecules [5]. These results moti-
Fig.1. Activity of the investigated platinum(II) complexes
against the bacterial strains.
immortal cell line derived from cervical cancer cells
taken from Henrietta Lacks, who died from her
cancer in 1951), while the most sensitive were WS1
cells – normal human fibroblasts.
Fig.2. Activity of the investigated platinum(II) complexes
against the tumor cells.
vate us to continue the investigations, in particular
on platinum(II) complexes with other thiourea derivatives, possibly useful in the chemotherapy.
References
[1].
Cvitkovic E., Spaulding J., Bethune V., Martin J.,
Whitmore W.F.: Cancer, 39, 1357 (1977).
[2]. Burchenal J.H., Kalaher K., Dew K., Lokys L.: Cancer
Treat. Rep., 63, 1493 (1979).
[3]. Faraglia G., Fregona D., Sitran S., Giovagnini L.,
Marzano C., Baccichetti F., Cesellato U., Graziani R.:
J. Inorg. Biochem., 83, 31 (2001).
[4]. Canetta R., Rozencweig M., Wittes R.E., Shacter L.P.:
In: Proceedings of the Fifth Nagaya International
Symposium on Cancer Treatment. Excerpta Medica,
Tokyo 1990, pp. 318-323.
[5]. Fuks L., Sadlej-Sosnowska N., Samochocka K., Starosta W.: J. Mol. Struct., 740, 229 (2005).
79
[6].
Fuks L.: Pt(II) chloride complexed by tetrahydrofurfuryl- or tetrahydrotiophenylthiourea: structural and
biological features. 3rd Cental European Conference
Chemistry towards Biology, Kraków-Przegorzały,
Poland, 08-12.09.2006.
[7]. Hess S.M., Anderson J.G., Bierbach U.: Bioorg. Med.
Chem. Lett., 15, 443 (2005).
[8]. Choudhury J.R., Bierbach U.: Nucleic Acids Res.,
33, 5626 (2005).
[9]. Gruber B.M., Anuszewska E.L.: Toxicol. In Vitro,
16, 663 (2002).
[10]. Fuks L., Kruszewski M., Sadlej-Sosnowska N.: Structural studies and cytotoxicity assays of platinum(II)
chloride complexed by (tetrahydrothiophene)thiourea. In: INCT Annual Report 2005. Institute of Nuclear Chemistry and Technology, Warszawa 2006, pp.
68-70.
TRANSITION METAL SORPTION BY ALGINATE BIOSORBENT
Dorota Filipiuk1/, Leon Fuks, Marek Majdan2/
1/
2/
Białystok Technical University, Poland
Maria Curie-Skłodowska University, Lublin, Poland
Contamination of aquatic environment by various
pollutants (synthetics, organic, heavy metals, etc.)
causes imbalance in natural functioning of the ecosystem. Heavy metals cause particularly severe
damage to the living systems at various levels. Main
sources of heavy metal contamination are: (i) urban
industrial aerosols created by combustion of fuels,
metal ore refining and other industrial process; (ii)
liquid and solid wastes generated from animals and
humans; (iii) mining activities; and (iv) industrial
and agricultural chemicals. The most important
feature that distinguishes heavy metal ions from
other toxic pollutants is their non-biodegradability.
The toxicity due to metal ion is owing to their ability
to bind with protein molecules and prevent replication of DNA and subsequent cell division [1].
To avoid health hazard, it is essential to remove
these toxic heavy metals from water before their
intake by living organisms.
Search for new technologies involving the removal of toxic metals from wastewaters has directed
attention towards biosorption, i.e. metal binding
by various biological materials. Biosorption can be
defined as the ability of biological materials to accumulate heavy metals from aqueous solutions
through metabolically mediated or physicochemical pathways of uptake [2]. Algae, bacteria and fungi
and yeasts have proved to be potential biosorbents
of metal ions [3]. The major advantages of biosorption over conventional treatment methods include:
(i) low cost, (ii) high efficiency, (iii) minimization
of chemical and/or biological sludge, (iv) no additional nutrient requirement; (v) easy regeneration of
biosorbent, and (vi) possibility of metal recovery [4].
Biosorption process involves a solid phase
(sorbent or biosorbent; biological material) and a
liquid phase (solvent, normally water) containing
a dissolved species to be sorbed (sorbate, metal
ions). Due to higher affinity of the sorbent for the
sorbate species, the latter is bound by different
mechanisms.
The biosorption equilibrium of heavy metals was
modelled using adsorption-type isotherms. The
Langmuir [5] and Freundlich [6] models are used
as the most popular ones. The form of the Langmuir
model is
qe =
(b)(q m )(Ce )
1 + (b)(Ce )
(1)
where: qe – the sorption capacity at equilibrium
[mol g–1], qm – maximum sorption capacity [mol g–1],
Ce – equilibrium concentration of metal ion [mol L–1],
b – the Langmuir model constant [L/mol].
The form of the Freundlich model is
qe = K(Ce)1/n
(2)
where K and n – the Freundlich model constants
(dimensionless).
Seaweeds are accounted among the most popular biosorbents because their macroscopic structures
offer a convenient basis for production of sorbent
particles suitable for sorption process. Brown marine algae tend particularly to sequester heavy metals
[7,8], in particular cell wall material obtained from
Sargassum biomass [9]. As a result, ion exchange
properties of certain natural polysaccharides have
been studied in detail, and it was found that bivalent
metal cations exchange with counter ions coming
from the polysaccharides, e.g. alginic acid (Scheme)
according to the following reaction [3]:
Scheme. Alginic acid carbohydrate chain.
80
Table. Isotherm model constants and correlation coefficients for biosorption of the selected divalent transition metal
cations (concentrations expressed in mol L–1).
*) Co=0.0005 mol/L.
2NaAlg + Me2+ ↔ Me(Alg)2 + 2Na+ (3)
In the presented paper, sorption data for the
selected divalent transition metal cations are reported, obtained from a batch equilibrium sorption
procedure using calcium alginate pellets. The sor-
thetic aqueous solutions containing a given metal
ion of known concentration. Then, the equilibrium
metal content was determined spectrophotometrically using 4-(2-pyridylazo)resorcinol (PAR) as an
indicator. The amounts of metal sorbed by the algi-
Fig.1. Langmuir adsorption isotherms for Mn(II) and Ni(II) ions.
bent studied is comparable at low price to the original alginic acid, however its mechanical, chemical and thermal resistance significantly exceeds
those of the acid.
Experiments were performed by shaking (6 h)
the weighed amount of calcium alginate with syn-
nate were calculated as the difference between the
initial and equilibrium concentrations in the aqueous phase. The best fit parameters of equations (1)
and (2) were obtained by regression analysis using
the software package Microcal Origin for Windows
(release 6.0). Table shows the model constants and
Fig.2. Freundlich adsorption isotherms for Cu(II) and Cd(II) ions.
correlation coefficients for the isotherms, determined
for the divalent transition metal cations studied.
Figures 1 and 2 present the Langmuir and Freundlich
isotherms determined for some of the metal ions
studied.
The essential characteristics of the Langmuir
isotherms can be expressed in terms of a dimensionless constant, called the separation factor or equilibrium parameter (RL) defined as:
RL = 1/(1+bCo)
(4)
where: b – the Langmuir constant mentioned above,
Co – initial concentration of the metal cation. According to McKay [10] the RL value indicates the
type of isotherm as follows: RL>1 – unfavourable,
RL=1 – linear, 0<RL<1 – favourable and RL=0 –
irreversible. The RL values found for the initial
metal concentration of 0.5 mmol L–1 are slightly
smaller than unity. The K and n parameters calculated from the slopes of the Freundlich plots vary
within the ranges 0.0279÷1.6943 and 0.7107÷1.0266,
respectively. The obtained RL values, being between 0 and 1, indicate for the favourable description of the process by the Langmuir model. The
experimental values of n close to unity for all the
investigated cations indicate for poor fitting of the
process by the Freundlich theory, as discussed elsewhere [11].
The R2 values for the Langmuir isotherm higher
than respective values for Freundlich equation ob-
81
served for the majority of the metal ions, indicate
that a monolayer coverage on the surface of the
calcium alginate is formed in the process. This
means that the sorption proceeds on the functional
groups/binding sites of the sorbent. The process
should be regarded as monolayer adsorption.
References
[1].
[2].
[3].
[4].
[5].
[6].
[7].
[8].
[9].
[10].
[11].
Kar R.N., Sahoo B.N., Sukla L.B.: Pollut. Res., 11,
1-13 (1992).
Fourest E., Roux J.-C.: Appl. Microbiol. Biotechnol.,
37, 399-403 (1992).
Volesky B.: Biosorption of heavy metals. CRC Press,
Boca Raton, Florida 1990, 396 p.
Kratochvil D., Volesky B.: Water Res., 32, 2760-2768
(1998).
Langmuir I.: J. Am. Chem. Soc., 40, 1361-1403 (1918).
Freundlich H.: Z. Phys. Chem., 57 A, 385-470 (1907),
in German.
Volesky B., Holan Z.R.: Biotechnol. Progr., 11,
235-250 (1995).
Volesky B.: Hydromeallurgy, 71, 179-90 (2003).
Fourest E., Volesky B.: Appl. Biochem. Biotechnol.,
67, 33-44 (1997).
Mckay G., Blair H.S., Gardener J.R.: J. Appl. Polym.
Sci., 27, 3043-3057 (1982).
Kadirvelu K., Namasivayam C.: Environ. Technol.,
21, 1091-1097 (2000).
GALLIUM AND INDIUM ISOTOPE EFFECTS
IN THE DOWEX 1-X8/HCl SYSTEM
Irena Herdzik, Wojciech Dembiński , Witold Skwara, Ewa Bulska1/, Agnieszka Wysocka1/
1/
Faculty of Chemistry, Warsaw University, Poland
In recent studies on the fractionation of gallium
and indium by chemical methods we have discovered the gallium and indium isotope effects in the
system: strongly acidic cation exchanger (Dowex
50W-X8)/HCl [1,2].
The aim of the present work was to seek similar
chemical isotope effects of the same elements in the
analogous system: strongly basic anion exchanger
Dowex 1-X8/HCl solution. The experimental
method was the same as that used in the earlier
studies. A long glass chromatographic column, 0.5
cm in inner diameter, was filled with the Dowex
1-X8 resin, 200-400 mesh up to the bed height of
95 cm. The “merry-go-round” elution method was
used with the flow rate of the effluent (HCl at a
given concentration) of 0.11 ml/min. The concentrations of the HCl were selected in such a way as
to obtain moderate values of the distribution coefficient of the metal ions, required for chromatographic experiment. At the HCl concentration
equal to 2.5 M for Ga3+ and 1.0 M for In3+, the Kd
values were close to 4 (Fig.1). Two cycles of the elution were done for gallium and 5 cycles for indium.
During the last cycle the 1 ml fractions of the effluent were collected. The contents of indium and gallium in the consecutive fractions were evaluated
by spot tests with alcoholic solution of alizarin and
with aqueous Rhodamine B, respectively [3], and
then quantitatively determined in selected samples
by atomic absorption analysis with flame atomization.
The ratio (R) of the isotope concentrations,
[113In]/[ 115In] and [ 69Ga]/[ 71Ga], in the selected
fractions of the effluent was determined using an
inductively coupled plasma mass spectrometer
(ICP-MS) Perkin Elmer Elan 6100. The relative
Fig.1. Kd of indium and gallium vs. HCl concentration in
the Dowex 1-X8/HCl system.
82
standard deviation of these measurements was
usually 0.05÷0.07%. Prior to the analysis, chlorides
were removed from the samples by evaporating
with 4 M HNO3 to dryness and dissolving the residue in 0.1 M HNO3. The local separation factors,
defined as qi =Ri/Rfeed, or the local separation gains,
defined as εi=ln(qi), were calculated from these
data.
Fig.3. Isotope separation gain of indium and gallium vs.
eluted fraction. X-asis in Z units.
Fig.2. Isotope separation gain of indium (in 1.0 M HCl)
and gallium (in 2.5 M HCl) vs. eluted fraction of the
metal.
Figure 2 shows the results of the separation
experiments, performed with 1.0 M HCl for indium,
and in 2.5 M HCl for gallium. The opposite slopes
of the S-shape curves demonstrate opposite sign
of the indium and gallium isotope effects. The resin
phase was enriched with the light isotope of gallium and the solution with the heavy isotope. The
light isotope of indium was accumulated in the solution whereas the heavy isotope – in the resin
phase. The value of the unit separation factor for
gallium was found to be ε=+5.9x10–4, and for indium ε=-1.5x10–4. The opposite signs (using the
same convention) of the isotope effects in the systems with the cation and anion exchanger reflect
the difference in the stability constants of the chloride complexes of the metals, for Ga 3+ – log
β1=0.01; while for In3+ – log β1=2.32, log β2=3.62
and log β3=4.0 [4]. The unit separation factor was
calculated on the basis of the Glueckauf approxi-
mation, under the assumption that the shape of
the eluted band resembles the normal distribution
[5,6]. According to this theory, ε is equal to S/N0.5,
where S is the slope of linear function of εi vs. the
eluted fraction (Δn/n) at the X-axis scaled in standardized differences (Z) of normal distribution
(Fig.3), and N is the number of theoretical plates
passed by the band.
This work was supported by the State Committee for Scientific Research (KBN), under grant No.
4 T09A 057 25.
References
[1]. Dembiński W., Herdzik I., Skwara W., Bulska E., Wysocka A.: Indium isotope effect in the Dowex 50-X8/HCl
system – comparison with the isotope effect of gallium.
In: INCT Annual Report 2005. Institute of Nuclear
Chemistry and Technology, Warszawa 2006, pp. 77-78.
[2]. Dembiński W., Herdzik I., Skwara W., Bulska E., Wysocka A.: Nukleonika, 51, 217-220 (2006).
[3]. Feigl F., Anger V.: Spot tests in inorganic analysis. 6th
ed. Elsevier, Amsterdam-London-New York 1972, pp.
233-247.
[4]. Smith M.R., Martell A.E.: Critical stability constants.
Vol. 4. Inorganic complexes. Plenum Press, New York
and London 1976, pp. 109-110.
[5]. Glueckauf E.: Trans. Faraday Soc., 51, 34-44 (1955).
[6]. Glueckauf E.: Trans. Faraday Soc., 54, 1203-1208
(1958).
PROFICIENCY TESTING SCHEME PLANTS 6 – DETERMINATION
OF As, Cd, Cu, Hg, Pb, Se AND Zn
IN DRY MUSHROOM POWDER (Suillus bovinus)
Halina Polkowska-Motrenko, Ewelina Chajduk, Jakub Dudek, Monika Sadowska-Bratek,
Michał Sypuła
Proficiency testing (PT) schemes are one of the
elements of quality assurance and quality control
system in chemical measurements. PTs are one of
the instruments of independent assessing the quality of routine measurements. Participation in PT
enables laboratories to demonstrate the reliability
of the data they are producing. It is also one of
the requirements of the international standard
ISO/IEC 17025:2005 [1] and can be used by accreditation bodies in accreditation decisions. The
(INCT) has been involved in providing PT since
2003. PT scheme PLANTS has been designed for
the purposes of laboratories from Poland and
Central and Eastern Europe determining trace elements in food of plant origin. PT PLANTS 6 –
Determination of As, Cd, Cu, Hg, Pb, Se and Zn
in dry mushroom powder (Suillus bovinus) has
been conducted in 2006. The adopted strategy of
the PT scheme complies with the ISO/IEC Guide
43-1:1997 [2], ISO 13528:2005 [3] and IUPAC harmonized protocol [4].
Test material
Preparation of test material
Wild mushrooms (ca. 60 kg) were collected in
the forest in north-west Poland, cleaned from dust,
soil and attached mosses. The end part of stalks were
removed. Mushrooms (caps and stalks) were then
cut into small pieces and air dried in a dryer accord-
83
ing to a procedure commonly used by food concentrate producers (mainly 25oC, from time to time
60oC). Dried mushrooms were milled in a centrifugal mill made of stainless steel and sieved by stainless steel sieves. The fraction of particles with diameter ≤1 mm was collected. This fraction (ca. 5
kg) was then homogenized by mixing and bottling
of 20 g test samples. Care was taken to avoid contamination. In order to ensure the long-term stability of the test samples radiation sterilization was
carried out. All bottles with the test material were
irradiated with electron beam (energy 10 MeV, 9
kW) from a linear accelerator LAE-13/9 (Depart-
Table 1. Results of As, Cd, Cu, Hg, Pb, Se and Zn determination provided by the reference laboratories.
84
ment of Radiation Chemistry and Technology,
INCT). The sterilization dose was 30 kGy.
Moisture determination
The procedure of moisture determination was
established on the basis of water desorption curves
determined at different temperatures. The reference point has been chosen on a plateau that ensures satisfactory reproducibility of the results. It
has been recommended to dry subsamples of the
material for 24 h at 50oC. In this case, the uncertainty associated with moisture content determination was evaluated to be ≤1%.
Homogeneity testing
Homogeneity testing was carried out according to the ISO 13528:2005 standard [3]. Contents
of the elements in question in 10 randomly selected
bottles were determined by the atomic absorption
spectrometry (AAS) method. Two samples of 250
mg were taken from each bottle and analyzed. Mean
value (Xmean), standard deviation of mean value
(Sx), repeatability standard deviation (Sr) and between samples standard deviation (Ss) were calculated using the following equations:
Xmean = ΣXaverage/g
Xaverage = (xt,1 + xt,2)/2
Sx = (Xmean − Xaverage )2 /(g −1)
Sr = (x t ,1 − x t ,2 ) 2 /(2g)
Ss = Sx 2 − (Sr 2 / 2)
where: Xaverage – average result for t bottle, t – bottle
number (t=1, 2, 3,…, g).
The material is considered to be homogeneous
if:
^
Ss < 0.3σ
^
where σ is standard deviation for proficiency assessment.
On the basis of obtained results, it has been
found that the material could be considered as homogenous for the sample masses ≥250 mg for all
the determined elements.
Assigning property values
Some of the test samples were selected randomly and analyzed by a group of reference labo-
ratories. The obtained results are summarized in
Table 1. The assigned values and their uncertainties (Table 2) were calculated as the robust averTable 2. Assigned values and their uncertainties.
* Expanded standard uncertainty (k=2).
age of the results reported according to the procedure recommended by the ISO 13528:2005 standard [3].
Calculation of performance statistics
For the purpose of performance evaluation,
the z-score and En-test score have been employed.
En-test was used only when a participating laboratory reported its own estimation of uncertainty.
The value of the z-score was calculated using the
equation:
x –x
z = lab ^ ref
σ
where: xlab – result reported by participating laboratory, xref – assigned value, ^
σ – standard deviation
for proficiency assessment calculated from Horwitz’s
formula [5]:
^
σ = 0.02 c0.8495
where c is concentration of the element in g g–1.
The ^
σ values are equal to 0.065 mg kg–1 for As,
0.053 mg kg–1 for Cd, 1.05 mg kg–1 for Cu, 0.036
mg kg–1 for Hg, 0.085 mg kg–1 for Pb, 0.209 mg kg–1
for Se and 5.25 mg kg–1 for Zn.
The value |z|<3 has been set as an acceptance
level for this PT.
Table 3. Number of PT participating laboratories determining individual elements, number of applied methods and
number of accepted results.
85
Fig.1. Results of laboratories participating in PT (z-score)
for As determination.
for Hg determination.
for Cd determination.
for Zn determination.
The value of the En-test score are calculated from
the following equation [11]:
cepted on the basis of z-score value. Some examples
of summary results are shown in Figs.1-4.
En =
x lab − x ref
2
U 2ref + U lab
where U is expanded standard uncertainty (k=2).
The value |En|≤1 has been set as an acceptance
level for this PT.
Eighteen Polish laboratories participated in the
PT. Seventeen laboratories provided the results.
Number of PT participating laboratories determining individual elements, number of applied methods
and number of accepted results are summarized
in Table 3.
As can be seen, the performance of the participating laboratories can be recognized as satisfactory. Only 5 from 89 provided results are not ac-
References
[1]. ISO/IEC 17025:2005 – General requirements for the
competence of testing and calibration laboratories.
ISO, Geneva 2005.
[2]. ISO/IEC Guide 43-1:1997 – Proficiency testing by interlaboratory comparisons. Part 1: Development and
operation of proficiency testing schemes. ISO, Geneva
1997.
[3]. ISO 13528:2005 – Statistical methods for use in proficiency testing by interlaboratory comparisons. ISO,
Geneva 2005.
[4]. Thompson M., Ellison S.L.R., Wood R.: Pure Appl.
Chem., 78, 1, 145-196 (2006).
[5]. Thompson M.: Analyst, 125, 385-386 (2000).
NEW POLISH CERTIFIED REFERENCE MATERIALS
FOR INORGANIC TRACE ANALYSIS:
CORN FLOUR (INCT-CF-3) AND SOYA BEAN FLOUR (INCT-SBF-4)
Halina Polkowska-Motrenko, Rajmund Dybczyński, Ewelina Chajduk, Bożena Danko,
Krzysztof Kulisa, Zbigniew Samczyński, Michał Sypuła, Zygmunt Szopa
Certified reference materials (CRMs) are an important element of the metrological system. In
chemical measurements, CRMs are used as an internal tool of quality assurance for checking accuracy of results and for validation of measurement
methods [1-3]. As CRMs should be as similar to
the analyzed material as possible, the potential de-
mand for suitable CRMs in very big. The production and use of CRMs should meet requirements
of international guidelines [4-8]. The Institute of
Nuclear Chemistry and Technology (INCT) has
issued two new materials of biological origin lately,
namely: Corn Flour (INCT-CF-3) and Soya Bean
Flour (INCT-SBF-4). The general strategy of prepa-
86
ration and certification of CRMs developed in the
INCT [3] has been employed. The concentration
level of trace elements in these matrices are much
lower than in the biological type CRMs issued previously by the INCT and differ strongly in fat content what is important for the way of decomposition
of the sample. So, INCT-CF-3 and INCT-SBF-4
supplement the issued CRMs and should fulfill specific laboratory needs.
Origin, preparation and testing
of the materials
Collection, grinding and sieving
Both raw materials were chosen from among
the materials present on the Polish market. Corn
flour was prepared from corn grown in Poland and
soya bean flour from soya grown in India. Corn flour
was produced by ViVi-Tak s.c. (Poland) according to Polish standard PN-A-74205:1997, then
sieved through the 250 μm nylon sieves and stored
in a polyethylene (PE) bag. Soya bean was milled,
sieved through the 150 μm nylon sieves and stored
in a PE bag. Approximately 50 kg of sieved corn
flour and soya bean flour were collected.
Homogenization and preliminary homogeneity
testing
In order to homogenize, the whole lot of each of
flours (ca. 50 kg) was transferred to a 110 dm3 PE
drum, placed in a homogenizer and the material
was mixed by the rotation for 20 hours. After this
time, a preliminary homogeneity testing was performed determining selected elements in the samples
randomly selected from the drum by the X-ray fluorescence (XRF) method. It was found that the
materials did not show any significant inhomogeneity. The materials were then distributed in 50 g
portions (future CRM) into 150 cm3 polypropylene
(PP) bottles with a screw-on cap and 10 g portions
(intercomparison sample) into 60 cm3 poly(ethylene
tetraphtalate) (PET) bottles, respectively.
Determination of particle size
Examination by optical microscopy revealed that
Martin’s diameter (arithmetic mean of the maximum
distance between opposite sides of a particle and
a distance in perpendicular direction) of over 98%
of particles of INCT-CF-3 was below 25 μm and
over 90% of particles of INCT-SBF-4 was below
50 μm.
Final homogeneity testing
Homogeneity have been studied by the determination of selected element contents in 100 mg
samples using instrumental neutron activation
analysis (INAA). For INCT-CF-3, these were Br,
Co, Fe, K, Mn, Na, Rb and Sc and Co, Fe, K, Sc
and Zn for INCT-SBF-4. The results (variances and
means) for six samples randomly taken from different containers and for six samples from a single
container (also randomly chosen) were compared
by means of Fisher’s test (F-test) and t-Student’s
test (t-test). No significant differences in variances
and means were found. Hence, the materials can be
considered as homogeneous for the sample masses
≥100 mg.
Determination of total water content
Total water content in the candidate reference
materials was determined in the Institute for Ref-
erence Materials and Measurements – IRMM (Gell,
Belgium) laboratory using the Karl-Fischer titration
method. It amounted to 11.09 g/100 g with relative
expanded uncertainty of 11.3% in INCT-CF-3 and
7.33 g/100 g with relative expanded uncertainty of
10.9% in INCT-SBF-4.
Radiation sterilization
All containers with the candidate CRMs were
sterilized by irradiation with electron beam (energy 10 MeV, 9 kW) from a linear accelerator
LAE-13/9 (Department of Radiation Chemistry
and Technology, INCT). The sterilization dose was
28 kGy.
Stability testing
Long-term stability was checked by comparing
the results obtained for one bottle (randomly
chosen) stored under controlled conditions: in an
air-conditioned room at 20oC (normal storage).
Samples of the CRM (ca. 100 mg) were taken from
the bottle after 0, 20 and 32 months of storage and
concentration of six selected elements (Co, Fe, K,
Rb, Sc and Zn) was determined by the INAA
method. Short-term stability was examined by the
determination of concentrations of the above mentioned elements in the bottle stored in the CO2
incubator (ASAB) at 37oC, 100% humidity and 5%
CO2. Statistical evaluation of the obtained results
using t-Student’s test [9] indicates that there are
no significant differences between the results obtained in both experimental conditions examined
and that no significant trends can be observed. Consequently, it can be stated that the material is stable
in time. The test is being continued and stability
of INCT-CF-3 and INCT-SBF-4 will be monitored
during all storage.
Determination of dry mass
In order to refer the results of analysis to the
same dry state of the material, a methods of water
determination on the basis of water desorption
curves determined at few temperatures were established. The reference points have been chosen on
a plateau that ensures satisfactory reproducibility
of the results. It has been recommended to dry
the subsample of the materials for 24 h at 80oC.
The standard uncertainty due to moisture content
determination was established on the basis of replicate measurement to be 0.51 and 0.45% for
INCT-CF-3 and INCT-SBF-4, respectively.
Characterization of the materials
The assignment of the certified values for element concentrations has been based on the results
of the interlaboratory comparison organized in the
years 2004-2005. Ninety two laboratories from 19
countries participated in the intercomparison. The
laboratories were asked to analyze two candidate
CRMs and a CRM of their own choice for a quality assurance (QA) reason. Moreover, the participating laboratories were asked to analyze the CRM
sent together with the intercomparison samples,
the identity of which was known only to the organizer. The results of the analysis of that CRM were
then applied in the process of the certification. Two
data sets were created and evaluated: the first –
“original” – consisted of all results reported by the
laboratories and the second – “alternative” – con-
Fig.1. Comparison of central values and their confidence
limits for Co in INCT-SBF-4 obtained by various
approaches to the background of original range of
results submitted by participants.
sisted of the results provided by the laboratories
for elements certified in the CRMs when the confidence limits of the laboratory results overlapped
with the confidence limits of the CRM, i.e. when
there is fulfilled the condition:
x CRM − x lab ≤ k CRM ⋅ u CRM + k lab ⋅ u lab
(1)
–
where: xCRM – certified value, xlab – laboratory mean,
u – combined standard uncertainties, k – coverage
factors at a level of confidence of 95%.
A method of data evaluation leading to assignment
of certified values was the same as that used previously in our Laboratory [10]. This approach is being based on outlier’s rejection procedure which
uses concurrently four statistical tests (Dixon,
Grubbs, skewness and kurtosis) at the significance
Table 1. Certified values for Corn Flour (INCT-CF-3).
87
Fig.2. Comparison of the certified values and their confidence limits and the result obtained by the definitive
method for Mo in INCT-CF-3 on the background of
original range of results submitted by the participants.
level of 0.05, followed by calculation of the overall
means of results remaining after outlier rejection,
standard deviations, standard errors, confidence
intervals. The results of the evaluation of both data
sets, i.e. original and alternative one were very similar in the most cases.
For some elements, the results obtained by the
radiochemical neutron activation analysis (RNAA)
definitive method [11-18] were also employed in
the process of certification, as it is illustrated in
Figs.1 and 2 and as it was done previously with the
respect to the former CRMs issued by the INCT.
The certified values for Al, Ba, Br, Ca, Co, Cs, Cu,
K, La, Mg, Mn, Ni, P, Rb, S, Sr, Th and Zn were
88
Table 2. Certified values for Soya Bean Flour (INCT-SBF-4).
determined using the alternative database. In such
a way, these data are traceable to the existing CRM.
On the other hand, the use of the CRM confirms
the validity of the applied method of data evaluation
[17]. The values for other elements were derived from
the original database. The combined standard uncertainty of certified values uc consists of four uncertainty contributions, which are associated with
Fig.3. Frequency of the use of analytical technique in the
certification campaign.
the result of the interlaboratory comparison uinterlab,
the long-time stability ulstab, the short-time stability
usstab and the moisture determination usm (expressed
as standard uncertainties):
2
2
2
2
u = u interlab
+ u lstab
+ u sstab
+ u sm
(2)
uinterlab is estimated as a relative standard deviation
of the overall mean, ulstab – the standard uncertainty
estimated from the long-term stability studies, usstab
– the standard uncertainty estimated from the
short-term stability studies, and usm – the standard
uncertainty estimated from the moisture determination study.
The expanded uncertainty (U) is obtained by multiplying uc by a coverage factor k=2 (corresponds
to a level of confidence of approximately 95%).
Certified values and their uncertainties (X ±U)
established in the course of the present work for
several elements in INCT-CF-3 and INCT-SBF-4
are presented in Tables 1 and 2. Information values
are listed in Table 3.
The relative frequency of using various analytical techniques in this intercomparison is illustrated
Table 3. Information values for Corn Flour (INCT-CF-3)
and Soya Bean Flour (INCT-SBF-4).
89
good cooperation. This work was in part supported
by the State Committee for Scientific Research
(KBN) grant No. 032290/C.PO6-6/2003.
References
[1].
[2].
[3].
[4].
[5].
[6].
[7].
[8].
[9].
[10].
[11].
[12].
[13].
in Fig.3. As can be seen, atomic absorption spectrometry (AAS), neutron activation analysis (NAA),
emission spectroscopy (OES) and mass spectrometry (MS) were the methods most frequently
used. The very significant share of results by NAA,
much greater than could have been expected on
the basis of global contribution of this method to
routine analyses worldwide, is worth emphasizing.
The authors express their thanks to all laboratories participating in this intercomparison for
[14].
[15].
[16].
[17].
[18].
Stoeppler M., Wolf W.R., Jenks P.J.: Reference materials for chemical analysis. Certification, availability
and proper usage. Wiley-VCH, Weinheim 2001.
Reference materials in analytical chemistry. A guide
for selection and use. Ed. A. Zschunke. Springer, Berlin
2000.
Dybczyński R.: Food Addit. Contam., 19, 928 (2002).
ISO/IEC Guide 35: Certification of reference materials
– general and statistical principles. ISO, Geneva 2006.
ISO Guide 30: Terms and definitions used in connection with reference materials. ISO, Geneva 1992.
ISO/IEC Guide 34: Quality system guidelines for the
production of reference materials. ISO, Geneva 2000.
ISO/IEC Guide 33: Uses of certified reference materials. ISO, Geneva 2000.
ISO Guide 31: Contents of certificates of reference
materials. ISO, Geneva 2000.
Linsinger T.P.J., Pauwels J. Lamberty A., Schimmel
H.G., van der Veen A.H.M., Siekmann L.: Fresenius
J. Anal. Chem., 370, 183 (2001).
Dybczyński R., Danko B., Kulisa K., Chajduk-Maleszewska E., Polkowska-Motrenko H., Samczyński Z.,
Szopa Z.: Chem. Anal. (Warsaw), 49, 143 (2004).
Dybczyński R., Danko B, Polkowska-Motrenko H.:
Fresenius J. Anal. Chem., 370, 130 (2001).
Samczyński Z., Dybczyński R.: Chem. Anal. (Warsaw),
41, 873 (1996).
Polkowska-Motrenko H., Danko B., Dybczyński R.,
Becker D.A.: J. Radioanal. Nucl. Chem., 207, 401
(1996).
Danko B., Dybczyński R.: J. Radioanal. Nucl. Chem.,
216 (1), 51 (1997).
Polkowska-Motrenko H., Danko B., Dybczyński R.:
Anal. Bioanal. Chem., 379, 221 (2004).
Polkowska-Motrenko H., Danko B., Dybczyński R.:
Chem. Anal. (Warsaw), 50, 155 (2005).
Polkowska-Motrenko H., Dybczyński R.: J. Radioanal.
Nucl. Chem, 269, 339 (2006).
Dybczyński R., Danko B., Polkowska-Motrenko H.,
Samczyński Z.: Talanta, 71, 529 (2007).
DETERMINATION OF CADMIUM, LEAD AND COPPER
IN FOOD PRODUCTS AND ENVIRONMENTAL SAMPLES
BY ATOMIC ABSORPTION SPECTROMETRY
AFTER SEPARATION BY SOLID PHASE EXTRACTION
Jadwiga Chwastowska, Witold Skwara, Elżbieta Sterlińska, Jakub Dudek, Leon Pszonicki
The growing contamination of environment causes
that many toxic elements are able to form various
organo-metallic compounds. In this form they can
be solubilized and enter soils, sediments, waters
and plants, and, in consequence, they can enter the
food chain. This fact causes the necessity to check
the contamination level of environment by heavy
metals and what their physiological effect is. Therefore, the determination of these metals in soil,
waters, plants and also in food products at very low
concentration levels as μg g–1 and ng g–1 is required.
However, the direct application of suitable analytical instrumental methods is often restricted owing
to interferences caused by the matrices of such
samples and by low concentration of the elements
to be determined. The mentioned difficulties may
be eliminated by the preliminary separation and
preconcentration of the contaminating elements.
From among the methods usually used for this purpose, the solid-phase extraction is applied more and
more frequently because of its simplicity and many
advantages in comparison with other methods
[1-5].
Previously, we elaborated a dithizone sorbent and
applied it for the determination of noble metals in
environmental samples [5], speciation of selenium
90
[6] and the determination of some heavy metals in
highly mineralized waters [7]. In the presented work,
we demonstrate that this sorbent has a versatile
ditions, on the other hand, the toxic elements can
form easy volatile organo-metallic compounds that
may be easy lost. In the proposed method the samples
Table 1. Conditions for sample mineralization and dilution (sample – 0.2-0.5 g, maximum volume of solution – 8 mL).
character and may be applied for the separation and
determination by graphite furnace atomic absorption spectrometry of most toxic elements in various
environmental materials and food products. This
were dried, ground and mineralized in a microwave mineralizer. The mineralization conditions
are presented in Table 1. The obtained solutions
were evaporated to wet residues, dissolved in 0.2 M
Table 2. Results of analysis of certified materials.
* a – certified values.
** b – determined values (mean values of 5 determinations).
fact enables the unification of analytical methods
and, thereby simplification of the work in the laboratories analyzing materials of various types.
The preliminary preparation of samples, their
mineralization and transformation into solution is
a very important step of any analytical procedure.
In the case of environmental and food samples containing mostly organic matter these operations
hydrochloric acid, neutralized by sodium hydroxide to pH 4 and put into a column with the dithizon
sorbent. The adsorbed elements were eluted by 2 M
nitric acid and determined by graphite tube atomic
absorption spectrometry.
The accuracy of the method was checked by the
determination of cadmium, lead and copper in three
various certified reference materials. The obtained
Table 3. Results of copper, cadmium and lead determination in selected food products and environmental materials
(mean values for n=5).
create often serious problems. On the one hand,
some organic compounds are resistant to mineralization and require application of very strong con-
results are established in Table 2. All of them are
inside the confidence intervals what proves that the
tested method is accurate.
The presented method was applied for the analysis of some environmental materials (soil, street dust
and grass) and various food products. The obtained
results and their precision expressed as relative
standard deviations (RSD) are demonstrated in
Table 3. The relative standard deviations vary in the
range from 0.5 to 3% due to the type of sample and
the determined element and indicate that the precision of the applied methods is satisfactory.
References
[1]. Goswami A., Singh A.K.: Anal. Chim. Acta., 454, 229
(2002).
[2]. Osman M.M., Kholeif S.A., Aboul Al.-Mauty N.A.:
Microchim. Acta, 143, 25 (2003).
91
[3]. Pramanik S., Dhara S., Bhattacharyya S.S., Chattopadhyay P.: Anal. Chim. Acta, 556, 430 (2006).
[4]. Burham N., Abel-Azeem S.M., El-Shahat M.F.: Anal.
Chim. Acta, 579, 193 ( 2006).
[5]. Chwastowska J., Skwara W., Sterlińska E., Pszonicki
L.: Talanta, 64, 224 (2004).
[6]. Chwastowska J., Skwara W., Sterlińska E., Dudek J.,
Pszonicki L.: Speciation analysis of selenium in mineral
waters by graphite furnace atomic absorption spectrometry after separation on dithizone sorbent. Chem.
Anal. (Warsaw), in press.
[7]. Chwastowska J., Skwara W., Sterlińska E., Dudek J.,
Pszonicki L.: Determination of cadmium, lead, copper
and bismuth in highly mineralized waters by solid phase
extraction and atomic absorption spectrometry. Chem.
Anal. (Warsaw), in press.
CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS
WITH HETEROCYCLIC CARBOXYLATE LIGANDS.
PART LIX. THE CRYSTAL AND MOLECULAR STRUCTURE
OF A ZINC(II) COMPLEX WITH PYRIDAZINE-3,6-DICARBOXYLATE
AND WATER LIGANDS
Michal Gryz1/, Wojciech Starosta, Janusz Leciejewicz
1/
Office for Registration of Medicinal Products, Medical Devices and Biocides, Warszawa, Poland
The structure of bis(μ-pyridazine-3,6-dicarboxylato- κ 4 N,O:N’,O’)-bis[diaquazinc(II)],
Zn2(C6H2N2O4)2(H2O)4, is composed of isolated
centrosymmetric dinuclear units built up of two
Zn(II) ions bridged by two fully deprotonated
pyridazine-3,4-dicarboxylate ligand molecules.
The Zn1 ion is cheleted by two N,O bonding
groups each donated by a different ligand molecule: Zn1-O1 2.033(2) Å, Zn1-O3 2.045(2) Å,
Zn1-N1 2.160(2) Å, Zn1-N2 2.172(2)Å and two
water oxygen atoms in axial positions (Zn1-O5
2.145(2)Å, Zn1-O6 2.121(2) Å) forming an octahedral enviroment. Figure 1 shows the molecule of
the dimer with atom labelling scheme, Fig.2 – the
packing of dimers in the unit cell. The inversion
centres of the complex molecules coicide with the
the rms deviation of 0.0408(10) Å. Carboxylate
groups deviate from the mean ring plane by 5.4(5)o
(C7O1O2) and 5.0(5)o (C8O3O4). Hydrogen bonds
Fig.1. The asymmetric unit of the title compound with atom
labeling scheme. Displacement ellipsoids are drawn
at the 50% probability level.
inversion centres generated in the unit cell by the
symmetry elements of the space group Pbca. Zn(II)
ions and the pyridazine rings are coplanar with
Fig.2. The alignment of dimeric molecules in the unit cell.
For clarity, only a half of the dimers is shown.
92
with lengths in the range from 2.743(3) to 2.816(3)
Å operate between the coordinated water molecules, and carboxylate oxygen atoms belonging to
adjacent dimers. They are responsible for the cohesion of the structure.
X-ray diffraction data collection was carried out
on a KUMA KM4 four circle diffractometer at the
Structure solution and refinement was performed
using SHELXL-97 program package.
References
[1]. Part LV. Premkumar T., Govindarajan S., Starosta W.,
Leciejewicz J.: Diaquatetrakis(pyrazine-2-carboxylato-κ2O,N)-thorium(IV) trihydrate. Acta Crystallogr.,
E62, m98-m100 (2006).
[2]. Part LVI. Gryz M., Starosta W., Leciejewicz J.: trans-Diaquabis(pyridazine-3-carboxylato- κ2O,N)-magnesium(II) dihydrate. Acta Crystallogr., E62, m123-m124
(2006).
[3]. Part LVII. Starosta W., Leciejewicz J., Premkumar T.,
Govindarajan S.: Crystal structures of two Ca(II) complexes with imidazole-4,5-dicarboxylate and water
ligands. J. Coord. Chem., 59, 557-564 (2006).
[4]. Part LVIII. Starosta W., Leciejewicz J.: catena-Poly[[aquacalcium(II)]bis(μ-1H-imidazole-4-carboxylato)κ4N,O:O,O’; κ3O,O’:O’]. Acta Crystallogr., E62,
m2648-m2650 (2006).
[5]. Part LIX. Gryz M., Starosta W., Leciejewicz J.:
Bis(μ-pyridazine-3,6-dicarboxylato-κ4N,O:N’,O’)-bis[diaquazinc(II)]. Acta Crystallogr., E62, m3470-m3472
(2006).
PART LX. THE CRYSTAL AND MOLECULAR STRUCTURES
OF MAGNESIUM(II) AND ZINC(II) COMPLEXES
WITH IMIDAZOLE-4-CARBOXYLATE AND WATER LIGANDS
1/
Magnesium imidazolate: trans-diaquabis(imidazole-4-carboxylato- κ 2 N,O)-magnesium(II),
Mg(C4H3N2O2)2(H2O)2, crystallizes in the monoclinic system (space group P21/c). The structure is
composed of monomeric molecules, each containing a Mg(II) ion located at the inversion centre
and chelated by two imidazole-4-carboxylate ligand
molecules via their N,O bonding moieties (Mg-N
2.193(2) Å, Mg-O 2.070(2) Å) and two water oxygen atoms (Mg-O 2.063(2) Å). A fairly regular
octahedron with water oxygen atoms at the apical
Fig.2. Packing diagram of Mg(C4H3N2O2)2(H2O)2.
one, the Zn(II) ion is octahedrally coordinated by
two, oriented in trans mode ligand molecules, each
via its N,O bonding moiety and two water oxygen
atoms. In the other, the Zn(II) ion is pentacoordinated by N,O bonding moieties of two ligand
molecules and one water oxygen atom (Fig.3). Six
Fig.1. Mg(C4H3N2O2)2(H2O)2 molecule with atom labeling
scheme. Displacement ellipsoids are drawn at the
50% probability level.
positions is formed (Fig.1). The imidazole rings are
coplanar. The monomers are kept together by hydrogen bonds in which the water molecules and
protonated nitrogen atoms act as donors (Fig.2).
Triclinic unit cell (space group P1) of zinc
imidazolate: [trans-diaquabis(imidazole-4-carboxylato- κ 2 N,O)-zinc(II)][monoaquabis(imidazole-4-carboxylato-N,O)-zinc(II)] trihydrate,
[Zn(C4H3N2O2)2(H2O)2][Zn(C4H3N2O2)2(H2O)]·3H2O,
contains two monomeric complex molecules. In
Fig.3. The molecules of [Zn(C 4 H 3 N 2 O 2 ) 2 (H 2 O) 2 ]
[Zn(C4H3N 2O 2)2(H2O)]·3H2O with atom labeling
scheme. Displacement ellipsoids are drawn at the
50% probability level.
93
solvation water molecules in three symmetry independent sites complete the content of the unit
cell. The octahedron around the Zn(II) ion is
slightly distorted with Zn-O, Zn-N and Zn-OH2
bond distances of 2.152(2) Å, 2.041(3) Å and
2.179(3) Å, respectively. The mean bond distances
in the pentacoordinated Zn(II) polyhedron are:
2.101(2) Å (Zn-O), 2.040(2) Å (Zn-N) and 2.002(3)
Å (Zn-OH2). An extended network of hydrogen
bonds in which solvation water molecules, coordinated water molecules and protonated ring-nitrogen atoms act as donors is responsible for the cohesion of the structure. Hydrogen bond lengths
range from 2.705(2) to 2.950(2) Å (Fig.4).
Fig.4. Packing diagram of [Zn(C 4 H 3 N 2 O 2 ) 2 (H 2 O) 2 ]
[Zn(C4H3N2O2)2(H2O)]·3H2O.
PART LXI. THE CRYSTAL AND MOLECULAR STRUCTURE
OF A MANGANESE(II) COMPLEX
WITH PYRAZOLE-3,5-DICARBOXYLATE AND WATER LIGANDS
Thatan Premkumar1/, Subbian Govindarajan1/, Wojciech Starosta, Janusz Leciejewicz
1/
Department of Chemistry, Bharathiar University, Coimbatore, Tamilnadu, India
The structure of trans-diaquabis(1H-pyrazole-3,5-dicarboxylate-N,O)-manganese(II) dihydrate,
Mn(C5H3N2O4)2·2H2O, is composed of monomeric
molecules in which Mn(II) ions situated at the
inversion centres are chelated, each by two singly
deprotonated pyrazole-3,5-dicarboxylate ligand
molecules and two water oxygen atoms in trans
arrangement. The coordination around the Mn(II)
ion is slightly distorted octahedral. The chelation
of the pyrazole-3,5-dicarboxylate ligand proceeds
via its N,O bonding moiety consisting of the hetero-ring nitrogen atom N2 and the oxygen atom O1
of the nearest carboxylate group: Mn1-O1 2.183(2)
Å, Mn1-N2 2.215(1) Å, Mn1-O5 2.156(2) Å. The
other carboxylate group remains protonated and
participates only in a network of hydrogen bonds.
The pyrazole ring is planar: rms 0.0005 Å. The protonated carboxylic group C7O3O4 deviates from
it only by 1.9(1)o, the carboxylic group C6O1O2 –
by 10.3(1)o. Figure 1 shows the molecule with atom
labelling scheme, Fig.2 – the packing diagram of the
structure. The protonated carboxylic oxygen atoms,
the coordinated water molecules, the solvation
water molecules and the protonated pyrazole ring
nitrogen atoms participate in a network of hydro-
Fig.2. The unit cell of Mn(C5H3N2O4)2·2H2O. Dashed lines
indicate hydrogen bonds.
Fig.1. The molecule of Mn(C5H3N2O4)2·2H2O with atom
gen bonds responsible for the stability of the structure. Their lengths are in the range from 2.509(2)
to 2.916(2) Å.
94
using SHELXL-97 program package
PART LXII. THE CRYSTAL STRUCTURE AND MOLECULAR DYNAMICS
OF 2-AMINOPYRIDINE-3-CARBOXYLIC ACID
Andrzej Pawlukojć, Wojciech Starosta, Janusz Leciejewicz, Ireneusz Natkaniec1,2/,
Dorota Nowak1,3/
1/
2/
Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, Dubna, Russia
The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland
3/
Faculty of Physics, Adam Mickiewicz University, Poznań, Poland
An interesting feature of the 2-aminopyridine-3-carboxylic acid molecule is its zwitterionic structure in
which the carboxylic proton is transferred not to the
amino group but to the hetero-ring nitrogen atom.
Figure 1 shows the molecule with atom labelling
gen bonds are in the range from 2.6472(14) to
2.7951(14) Å. Figure 2 shows the alignment of hydrogen bridged almost flat molecular ribbons. The
pyridine ring of the title molecule is almost planar
(rms 0.0129(1) Å). The dihedral angles between
Fig.2. The unit cell of 2-aminopyridine-3-carboxylic acid.
Dashed lines indicate hydrogen bonds.
Fig.1. The molecule of 2-aminopyridine-3-carboxylic acid
with atom labeling scheme. Displacement ellipsoids
are drawn at the 50% probability level.
scheme. This configuration produces intermolecular hydrogen bonds in which the amino group and
hetero-ring nitrogen atoms act as donors and the
carboxylate oxygen atoms in adjacent acid molecules act as acceptors. The lengths of these hydro-
the hetero-ring plane and the carboxylate and amino
group planes are 5.6(1)o and 2.3(1)o, respectively.
on a KUMA KM4 four circle diffractometer using
an Oxford Cryogenic Cooler to maintain the temperature of the sample at 100 K. Structure solution
and refinement was performed using SHELXL-97
program package. An analysis of inelastic neutron
scattering spectra recorded at the Pulsed Reactor
IBR-2 at Dubna (Russia) using a NERA-PR spectrometer shows a good agreement with those calculated for a crystal.
PART LXIII. THE CRYSTAL AND MOLECULAR STRUCTURE
OF A CALCIUM(II) COMPLEX
WITH PYRAZINE-2,3,5,6-TETRACARBOXYLATE AND WATER LIGANDS
Wojciech Starosta, Janusz Leciejewicz
Centrosymmetric, triclinic unit cell of Ca(II) contains
four (in two symmetry independent sites) Ca(II)
ions, two fully deprotonated pyrazine-2,3,5,6-tetra-
carboxylate (2,3,5,6-PZTC) ligand molecules with
their geometrical centres in the inversion centres
at 0,1/2,1/2 (molecule 1) and 0,1/2,0 (molecule 2)
and two water molecules coordinated to the metal
ions. All potential chelating sites of both ligand
molecules are engagged in bridging the metal ions
giving rise to a three-dimensional molecular network.
95
centre at 0,0,0. The N,O bonding moieties composed of N21, O21 and N21IX, O21IX atoms coordinate the Ca2 and Ca2IX ions, respectively, while
the second carboxylate oxygen atoms O22 and
O22IX acting as bidentate are linked to Ca2IV, Ca1IV
and Ca2VI, Ca1VI ions, respectively. Oxygen atoms
of the carboxylate groups which do not form the
N,O bonding moieties act also as bidentate: O23
chelates Ca2IV and Ca2II ions, while the O23IX atom
– the Ca2VI and Ca2XIV ions. The O24 and O24IX
atoms are bonded to Ca1IV and Ca1XIV ions, respectively. In this way, the ligand molecule 2 bridges
six Ca2 and four Ca1 ions.
Fig.1. The bridging mode of ligand molecule 1.
N,O and NXIII, OXIII bonding moieties of the
ligand molecule 1 chelate the Ca1 and Ca1XIII ions,
while the second oxygen atoms O12 and O12XIII are
coordinated to Ca1VII and Ca1VI ions, respectively.
Belonging to the remaining carboxylate groups
oxygen atoms O13 and O13XIII are bonded to Ca2I
and Ca2IX ions respectively and the O14 and O14XII
oxygen atoms, each acting as bidentate are bonded
to the Ca1VI and Ca1VIII ions (O14) and Ca1II and
Ca1VII ions (O14XIII). Thus, the ligand molecule 1
bridges six Ca1 ions and two Ca2 ions. This bridging pathway with the atom labelling in respect to
the inversion centre at 0,0,0 is shown in Fig.1.
Fig.2. The bridging mode of ligand molecule 2.
Having its geometrical centre at the inversion
centre at 0,1/2,0, the ligand molecule 2 chelates
ten Ca ions. Figure 2 illustrates the bridging pathway with atom labelling in respect to the inversion
Fig.3. The packing of molecules in the unit cell of
Ca2(2,3,5,6-PZTC)(H2O)2.
The bridging pathways via ligand molecules 1
and 2 are interconnected by carboxylate oxygen
atoms O13 and O13IX donated by the ligand molecule 1 to the coordination (Fig.3).
In the third bridging pathway, the coordinated
water oxygen atom O10 joins two adjacent Ca1 and
Ca2 ions. Since the Ca1-O10-Ca2 angle is 94.81(8)o,
a catenated zig-zag motif is observed. The water
molecule O10 acting as a donor provides also an
additional pathway via very weak hydrogen bonds
to carboxylate O14VIII and O12VII atoms.
Symmetry code in respect to the inversion centre at 0,0,0: I x, y, z-1; II x, y-1, z; III -x+1, -y+2, -z+1;
IV
-x+1, -y+1, -z+2; V -x+1, -y+2, -z+2; VI x-1, y, z;
VII
-x+1, -y+1, -z+1; VIII -x, -y+2, -z+1; IX -x, -y+2,
-z+1; X x+1, y, z; XI x, y, z+1; XII x, y+1, z; XIII -x,
-y+1, -z+1; XIV -x, -y+2, -z+2.
96
PART LXIV. THE CRYSTAL AND MOLECULAR STRUCTURE
OF A ZINC(II) COMPLEX WITH PYRAZOLE-4-CARBOXYLATE
AND WATER LIGANDS
1/
The monoclinic structure (space group C2/c) of
trans-tetraquabis(pyrazole-4-carboxylato-N)-zinc(II)
trihydrate, Zn(C4H3N2O2)2·3H2O, contains monomeric molecules in which the central metal ion located at the inversion centre is chelated by two
pyrazole-4-carboxylate ligands via their hetero-ring
nitrogen atoms and by four water oxygen atoms.
The coordination around the Zn(II) ion is octahedral with Zn-N bond distance of 2.078(2) Å and
mean Zn-O bond length of 2.125(3) Å (Fig.1).
Deprotonated carboxylate groups of the ligand
Fig.1. The molecule of Zn(C4H3N2O2)2·3H2O with atom
molecules are not active in coordination but participate in a network of hydrogen bonds responsible
for the cohesion of the crystal (Fig.2).
Fig.2. The unit cell of Zn(C4H3N2O2)2·3H2O. Dashed lines
indicate hydrogen bonds.
RADIOBIOLOGY
RADIOBIOLOGY
99
IRON CHELATORS INHIBIT DNIC FORMATION
TO THE SAME EXTENT, INDEPENDENTLY OF PERMEABILITY
Kamil Brzóska, Hanna Lewandowska, Sylwia Męczyńska, Barbara Sochanowicz,
Jarosław Sadło, Marcin Kruszewski
Dinitrosyl iron complexes (DNIC) are a group of
physiologically important transducers of nitric oxide (NO) [1,2]. The low molecular-weight DNIC
have been shown to modulate redox properties of
the cellular interior through the inhibition of glutathione-dependent enzymes. Previously, we have
shown [3] that depletion of lysosomal LIP (labile
iron pool) by either chelation with deferoxamine
(DFO) or lysis inhibition (by treatment with 10 mM
NH4Cl) in K562, human myelogenous leukemia
cells leads to a considerable decrease (down to 50%,
depending on the incubation time) of DNIC forming in the cells treated with 70 μM nitric oxide donor (DEANO).
We further investigated the nature of the cellular LIP involved in formation of DNIC in K562
cells. The cells were treated with a nitric oxide donor in the presence of a permeable (salicylaldehyde
isonicotinoyl hydrazone – SIH) or a nonpermeable
(DFO) iron chelator. SIH is a highly lipophilic molecule that readily enters cells and firmly chelates
the intracellular pool of redox active iron. Thus, it
was plausible to suppose that it would chelate both
cytosolic and compartmented LIP, including lysosomal LIP. The nonpermeable iron chelator, DFO,
is a hydrophilic molecule that is taken up predomi-
Fig.1. Dose dependent induction of DNIC specific EPR signal in K562 cells incubated for 6 h with different concentrations of SIH or DFO then treated with 100 μM
NO for 15 min at 37oC. Solid bars – mean ±SD, n=3.
Asterix denotes statistically significant difference vs.
samples treated with 100 μM NO alone (a positive
control), p<0.05. Open bars – per cent of initial value
(cells treated with 100 μM NO alone).
nantly via endocytosis and localizes almost exclusively within the lysosomal compartment, where it
seems to remain. Hence, we expected that the effect exerted by DFO would depend on the control
of reactivity of the intralysosomal iron pool.
DNIC formation was recorded using EPR (electron paramagnetic resonance). The EPR spectra
were recorded on Bruker ESP 300 at 77 K, microwave power – 1 mW, microwave frequency – 9.31
Fig.2. Inhibition of EPR signal induction in K562 cells incubated with 100 μM SIH for 0, 1, 3 and 6 h, and then
treated with 100 μM NO for 15 min at 37oC. Solid
bars – mean ±SD, n=3. Asterix denotes statistically
significant difference vs. samples treated with 100 μM
NO alone (a positive control), p<0.05. Open bars –
per cent of initial value (cells treated with 100 μM
NO alone).
GHz, modulation amplitude – 3.027 G and time
constant – 41 ms. In order to estimate the values of
g coefficients computer simulation was performed
on SimFonia 1.25 software (Bruker Analytische
Messtechnik, DE).
The results presented in Figs.1-3 show that DFO
inhibits DNIC formation to the similar extent as
Fig.3. Inhibition of EPR signal induction in K562 cells incubated with 1000 μM DFO for 1, 3 and 6 h, and then
treated with 100 μM NO for 15 min at 37oC. Solid
bars – mean ±SD, n=3. Asterix denotes statistically
significant difference vs. samples treated with 100 μM
NO alone (a positive control), p<0.05. Open bars –
per cent of initial value (cells treated with 100 μM
NO alone).
SIH, indicating that both chelators affect similar
pool of labile iron. Taken together, our present and
previous results support the view that lysosomal
iron considerably contributes to the total LIP in
the cell.
100
RADIOBIOLOGY
of Education and Science statutory grant for the
INCT.
References
J.L. Zweier. Kluwer Academic Publishing, Boston 1999,
pp. 49-82.
[2]. Ueno T., Yoshimura T.: Jpn. J. Pharmacol., 82, 95-101
(2000).
[3]. Męczyńska S., Lewandowska H., Kruszewski M.: Acta
Biochim. Polon., 55, Suppl. 1, 192 (2006).
[1]. Vanin A., Kleschyov A.: In: Nitric oxide in transplant
rejection and anti-tumor defence. Eds. S. Lukiewicz,
GHRELIN, A LIGAND FOR THE GROWTH HORMONE
SECRETAGOGUE RECEPTOR, INCREASES DNA BREAKAGE
IN X-IRRADIATED PIGLET BLOOD MONONUCLEAR CELLS
Marcin Kruszewski, Teresa Iwaneńko, Jarosław Woliński1/, Maria Wojewódzka
1/
The Kielanowski Institute of Animal Physiology and Nutrition, Polish Academy of Sciences,
Jabłonna, Poland
Ghrelin, a recently described endogenous ligand
for the growth hormone secretagogue receptor
(GHS-R), is a 28 amino acid peptide encoded by
GHRL gene and is derived from a 117 amino acid
precursor peptide. It is produced by stomach cells
and is a potent regulator of food intake, energy expenditure, adiposity, and growth hormone secretion (reviewed in [1]). Ghrelin reduces peripheral
energy expenditure and enhances appetite by activating neurons that express Agouti-related peptide and neuropeptide Y. GHS-R and ghrelin are
expressed in human T lymphocytes and monocytes,
where ghrelin inhibits the expression of proinflammatory cytokines. Other functional roles of ghrelin
at the cellular level remain poorly defined.
We investigated the effect of ghrelin addition to
food on the susceptibility of peripheral blood mononuclear cells (BMNC) to DNA damage generated
by X-irradiation. Ghrelin was applied intragastrically to newborn piglets for 7 days at a dose of 15
μg/kg body mass. After treatment, blood was collected by heart puncture and BMNC were isolated
by density gradient centrifugation on Histopaque
1137, resuspended in RPMI1640 medium supplemented with 20% of foetal calf serum. Isolated cells
were exposed to X-radiation (dose range – 0-3 Gy,
200 kV, 5 mA, dose rate – 1.2 Gy/min). The extent
of DNA damage was evaluated by the alkaline comet
assay [2]. To investigate the influence of ghrelin on
cells’ ability to repair DNA damage, BMNC were
irradiated with 2 Gy of X-radiation and disappearance of DNA breaks was monitored 0.5, 1 and 2 h
after irradiation.
We found that ghrelin had a marked effect on
the level of X-ray induced DNA damage: there was
a significant increase in the initial level of DNA
strand breaks in cells from ghrelin treated animals
as compared with untreated controls (Fig.1). However, no effect of ghrelin was observed on the cellular capacity to rejoin DNA strand breaks (Fig.2).
Fig.2. Lack of effect of ghrelin treatment on the capacity of
piglet BMNC to repair DNA damage induced by 2 Gy
of X-radiation.
This is the first observation of the participation
of ghrelin in the cellular response to X-irradiation.
It points to the role of ghrelin in enhancing the
genotoxicity of oxidative stress-inducing factors
generated during inflammation.
The work was supported by the Polish Ministry of Education and Science, project number
PBZ-KBN-093/P06/2003.
References
Fig.1. The effect of ghrelin treatment on the initial X-ray-induced DNA breaks in piglet BMNC evaluated by the
alkaline comet assay.
[1]. Gil-Campos M., Aguilera C.M., Canete R., Gil A.: Br.
J. Nutr., 96, 201-226 (2006).
[2]. Wojewodzka M., Kruszewski M., Iwanenko T., Collins
A.R., Szumiel I.: Mutat. Res., 416, 21-35 (1998).
RADIOBIOLOGY
101
GHRELIN INCREASES
HYDROGEN PEROXIDE-INDUCED DNA BREAKAGE
IN PIGLET BLOOD MONONUCLEAR CELLS
Teresa Bartłomiejczyk, Teresa Iwaneńko, Maria Wojewódzka, Jarosław Woliński1/,
Roman Zabielski2/, Marcin Kruszewski
1/
Jabłonna, Poland
2/
Warsaw Agricultural University, Poland
The recently described endogenous ligand for the
growth hormone secretagogue receptor, ghrelin,
was found to inhibit hydrogen peroxide-induced
cytokine release in human umbilical vein endothelial cells [1]. This suggested that the peptide blocks
redox-mediated cellular signalling. Moreover, ghrelin
inhibited basal and TNF-alpha-induced activation
of nuclear factor-kappaB [1], a process initiated by
DNA damage [2]. However, the effect of ghrelin on
DNA damage induction has not been studied until
now.
We investigated the effect of ghrelin addition
to food on the susceptibility of piglet peripheral
blood mononuclear cells (BMNC) to DNA damage generated by hydrogen peroxide. Ghrelin was
applied intragastrically to newborn piglets for 7 days
at two doses (7.5 and 15 μg/kg body mass). After
treatment, blood was collected by heart puncture
and BMNC were isolated by density gradient centrifugation on Histopaque 1137, resuspended in
RPMI1640 medium supplemented with 20% of
foetal calf serum. Isolated cells were exposed to hydrogen peroxide (0-250 μM) in phosphate buffered
saline for 15 min at 4oC. The extent of DNA damage was evaluated by the alkaline comet assay [3].
Fig.1. The effect of ghrelin treatment on the initial hydrogen peroxide-induced DNA breaks in piglet BMNC
evaluated by the alkaline comet assay.
We found that ghrelin had a marked effect on
the level of hydrogen peroxide-induced DNA damage: there was a significant increase in the initial
level of DNA strand breaks in cells from ghrelin
treated animals as compared with untreated con-
Fig.2. Lack of effect of ghrelin dose on the initial hydrogen peroxide-induced DNA breaks in piglet BMNC
trols (Fig.1). This effect did not depend on ghrelin
dose (Fig.2), supporting the relation of the observed
enhancement of DNA damage to cellular signalling.
Together with the preceding report on the effect of ghrelin on the initial DNA breaks in X-irradiated cells, this observation points to the role
of ghrelin in enhancing the genotoxicity of oxidative stress-inducing factors generated during inflammation. Overproduction of ghrelin may lead
to excessive DNA damage and consequent cytotoxicity, especially under inflammatory conditions,
where DNA damaging agents, such as reactive
oxygen or nitrogen species, are produced. Thus,
the discovered effect of ghrelin may have some
relevance to the pathophysiology of obesity-linked
diseases.
PBZ-KBN-093/P06/2003.
References
[1]. Li W.G., Gavrila D., Liu X., Wang L., Gunnlaugsson S.,
Stoll L.L., McCormick M.L., Sigmund C.D., Tang C.,
Weintraub N.L.: Circulation, 109, 2221-2226 (2004).
[2]. Wu Z.H., Shi Y., Tibbetts R.S., Miyamoto S.: Science,
311, 1141-1146 (2006).
[3]. Wojewódzka M., Kruszewski M., Iwaneńko T., Collins
A.R., Szumiel I.: Mutat. Res., 416, 21-35 (1998).
102
RADIOBIOLOGY
THE EFFECT OF LEPTIN ON DNA BREAKAGE
INDUCED BY GENOTOXIC AGENTS
IN HUMAN PERIPHERAL BLOOD MONONUCLEAR CELLS
Marcin Kruszewski, Teresa Iwaneńko, Maria Wojewódzka, Jarosław Woliński1/,
Roman Zabielski2/
1/
Jabłonna, Poland
2/
Warsaw Agricultural University, Poland
Leptin, an adipose tissue cytokine is known to reduce food intake and to increase energy expenditure. Previous studies in rats indicated that gastric
leptin is involved in cytoprotection in the rat pancreas and gastric mucosa. This protection depends
upon vagal activity and sensory nerves and involves
hyperemia probably mediated by nitric oxide and
mimicking the gastroprotective effect of cholecystokinin (CCK) [1]. On the other hand, long form of
leptin receptor (Ob-Rb) is expressed on the peripheral blood mononuclear cells (BMNC) and the
existence of a reciprocal regulatory network is anticipated, by which leptin may control immune cell
activation and inflammation (reviewed in [2,3]).
Leptin up-regulates growth hormone secretagogue
receptor (GHS-R) expression on human T lymphocytes, modulates the activation of peripheral
BMNC and it is known to have a proinflammatory
action.
We examined the influence of leptin on the susceptibility of human cells to ionizing radiation or
hydrogen peroxide. Human peripheral BMNC
were isolated from whole blood by density gradi-
Fig.2. The effect of leptin treatment on the initial hydrogen peroxide-induced DNA breaks in human BMNC
(20 μg/ml) for 20 h. After pretreatment, cells were
X-irradiated (dose range – 0-8 Gy) in an ANDREX
X-ray machine (Holger Andreasen, Denmark; 200
kV, 5 mA, dose rate – 1.2 Gy/min) or exposed to
H2O2 (0-250 μM) in phosphate buffered saline for
15 min at 4oC. The extent of DNA damage was
evaluated by the alkaline comet assay [3].
Leptin had no effect on BMNC proliferation
after PHA stimulation. Pretreatment with leptin had
no effect on the level of X-radiation- and H2O2-induced DNA breakage (Figs.1 and 2).
The results described here and in the preceding two reports indicate that leptin has different effects on cellular susceptibility to DNA damaging
agents in vivo and in vitro.
PBZ-KBN-093/P06/2003.
References
Fig.1. Lack of effect of leptin treatment on the initial X-ray-induced DNA breaks in human BMNC evaluated
by the alkaline comet assay.
ent centrifugation on Histopaque 1137, resuspended in RPMI1640 medium supplemented with
20% of foetal calf serum, stimulated with phytohemagglutinin (PHA) and pretreated with leptin
[1]. Brzozowski T., Konturek P.C., Pajdo R., Kwiecien S.,
Ptak A., Sliwowski Z., Drozdowicz D., Pawlik M.,
Konturek S.J., Hahn E.G.: J. Physiol. Pharmacol., 52,
583-602 (2001).
[2]. Popovic V., Duntas L.H.: Horm. Metab. Res., 37,
533-537 (2005).
[3]. Broberger C.: J. Intern. Med., 258, 301-327 (2005).
RADIOBIOLOGY
103
CABAS – A FREELY AVAILABLE PC PROGRAM
FOR FITTING CALIBRATION CURVES
IN CHROMOSOME ABERRATION DOSIMETRY
Joanna Deperas1/, Marta Szłuińska2/, Marta Deperas-Kaminska3,4/, Alan Edwards2/,
David Lloyd2/, Carita Lindholm5/, Horst Romm6/, Laurence Roy7/, Raymond Moss8/,
Josselin Morand8/, Andrzej Wójcik1,4,8/
1/
2/
Institute of Nuclear Chemistry and Technology, Warszawa, Poland
Health Protection Agency, Centre for Radiation, Chemical and Environmental Hazards, Chilton,
Didcot, United Kingdom
3/
Joint Institute for Nuclear Research, Dubna, Russia
4/
Świętokrzyska Academy, Kielce, Poland
5/
Radiation and Nuclear Safety Authority (STUK), Helsinki, Finland
6/
Bundesamt für Strahlenschutz, Neuherberg, Germany
7/
Institut de Radioprotection et de Sûreté Nucléaire, Fontenay-aux-Roses Cedex, France
8/
Institute for Energy – JRC European Commission, Petten, the Netherlands
The aim of biological dosimetry is the calculation
of the dose and the range of uncertainty to which
an accident victim was exposed. This process requires the use of the maximum likelihood method
for the proper fitting of an in vitro calibration curve,
a procedure which is not implemented in popular,
commercially available statistical computer programs.
The most specific and sensitive technique of biological dosimetry relies on estimating the frequency
of unstable chromosomal damage in peripheral
blood lymphocytes of the exposed person [1,2]. The
dicentric chromosome aberration assay is the most
Fig. A screenshot of the main menu of the program.
frequently used, sometimes combined with centric
rings, and the cytokinesis blocked micronucleus
(CBMN) assay has also been developed. Numerous
studies, performed both on animals and humans,
have demonstrated a close correspondence between
aberrations or micronuclei induced in peripheral
blood lymphocytes under in vitro and in vivo conditions. This allows one to estimate a radiation dose
absorbed during an accident by reference to an in
vitro calibration curve. This curve is generated by
irradiating blood samples, collected from control
donors, with several doses of radiation. Following
culturing of lymphocytes, microscopic slides are
104
RADIOBIOLOGY
prepared and the frequencies of dicentrics and
rings are estimated in first division metaphases or
micronuclei in binucleate cells. The points of the
dose-response relationship are fitted to an equation which is linear-quadratic for low LET (linear
energy transfer) radiation and linear for high LET
radiation.
The correct fitting procedure is not trivial because it requires an appropriate weighting of data
points. Several laboratories have produced their
own curve fitting programs for internal use but these
are frequently not user-friendly and not available
to outside users. Therefore, a PC-based freely available program called CABAS, for fitting dose-response curves to chromosomal aberration or micronucleus data and for calculating the dose and confidence limit (CL) has been developed and tested.
The program consists of (i) the main curve-fitting
and dose estimating module, (ii) a module for calculating the dose in cases of partial body exposure,
(iii) a module for estimating the minimum number
of cells necessary to detect a given dose of radia-
tion, and (iv) a module for calculating the dose in
the case of a fractionated or protracted exposure
(Fig.).
The program can be downloaded as freeware
from http://www.pu.kielce.pl/ibiol/cabas or obtained
from any of the present authors. The use of the program is straightforward and it can be expected that
its use will improve the precision of dose estimates
by biological dosimetry in cases of radiation accidents. Furthermore, it should facilitate setting up
inter-laboratory dose effect curves.
INCT.
References
[1]. Cytogenetic analysis for radiation dose assessment. A
manual. IAEA, Vienna 2001.
[2]. Voisin P., Barquinero J.F., Blakely B., Lindholm C.,
Lloyd D., Luccioni C., Miller S., Palitti F., Prasanna
P.G., Stephan G., Thierens H., Turai I., Wilkinson D.,
Wojcik A.: Cell. Mol. Biol., 48, 501-504 (2002).
THE TEMPERATURE EFFECT
ON THE FREQUENCY OF RADIATION-INDUCED MICRONUCLEI
IN HUMAN PERIPHERAL BLOOD LYMPHOCYTES
IS ABOLISHED BY DMSO
Kinga Brzozowska, Andrzej Wójcik
The impact of temperature on the frequency of
radiation-induced chromosome aberrations in the
human lymphocytes was first described by Bajerska
and Liniecki [1]. We have previously described [2]
experiments carried out to analyze the impact of
blood temperature at irradiation in vitro on the
level of radiation-induced micronuclei. We found
that temperature of pre-irradiation incubation as
well as that during exposure exerted an effect on
the frequency of radiation-induced micronuclei in
human peripheral blood lymphocytes. The highest
frequency of micronuclei was observed for blood
samples incubated at 37oC before and during irradiation in vitro with doses of 2 and 2.7 Gy, intermediate – at 20oC and the lowest one – at 0oC.
Blood samples were drawn from two healthy
male donors aged 24 and 45 years and irradiated
at 0, 20 and 37oC with X-rays 200 kVp, 5 mA, 3 mm
Cu filter. The doses were: 0, 1 and 2 Gy for the
first donor, and 0, 1.35 and 2.7 Gy for the second
donor. For 20 min before irradiation as well as during irradiation, the blood samples were incubated
at 0, 20 or 37oC. dimethylsulphoxide (DMSO) was
added 5 min before irradiation at the concentration of 0.5 mol/dm3. After irradiation, the samples
were centrifuged in order to discard supernatants
containing DMSO; cells were then transferred into
4.5 ml RPMI 1640 medium supplemented with 25%
calf serum, 2.5% phytohaemagglutinin (PHA),
antibiotic solution and incubated for 72 h at 37oC
and 5% CO2. Lymphocyte preparations for micronuclei analysis were prepared according to the
standard method of Fenech [3].
Whereas temperature of pre-irradiation incubation as well as that during exposure exerted a
distinct effect on the frequency of radiation-induced
micronuclei in human peripheral blood lymphocytes, the presence of DMSO completely abolished
this effect: the dose-effect curves for all three temperatures were identical.
In the interaction of ionizing radiation with
DNA one discerns direct and indirect effect, the
latter produced in the water layer surrounding the
DNA molecule. Since DMSO is a scavenger of the
OH• radical which is produced in the process of
water radiolysis, the presented results indicate
that temperature conditions affect the indirectly
induced damage. At this stage of our research,
we cannot explain which mechanisms are responsible for the effect of temperature on the level of
radiation-induced cytogenetic damage, although
we presume that chromatin conformation may
play a role. It is plausible to assume that accessibility of DNA to the radical attack depends on
the steric relations of the chromatin components
and specifically, on the extent of protection by
proteins. Temperature dependent structural transitions in the protein-DNA complex (e.g. [4]), as
well as temperature dependence of binding of
specific nuclear proteins to DNA (e.g. [5,6]) have
been described but not systematically explored
from the point of view of chromatin radiosensitivity.
INCT.
RADIOBIOLOGY
105
References
[1]. Bajerska A., Liniecki J.: Int. J. Radiat. Biol., 16, 483-493
(1969).
[2]. Brzozowska K., Wójcik A.: The effect of temperature
on the frequency of radiation-induced micronuclei in
human peripheral blood lymphocytes. In: INCT Annual
Report 2005. Institute of Nuclear Chemistry and Technology, Warszawa 2006, pp.102-103.
[3]. Fenech M.: Mutat. Res., 285, 35-44 (1993).
[4]. Peters W.B., Edmondson S.P., Shriver J.W.: J. Mol.
Biol., 343, 339-360 (2004).
[5]. Santilli G., Schwab R., Watson R., Ebert C., Aronow
B.J., Sala A.: J. Biol. Chem., 280, 15628-15634 (2005).
[6]. Ferreira M.E., Hermann S., Prochasson P., Workman
J.L., Berndt K.D., Wright A.P.: J. Biol. Chem., 280,
21779-21784 (2005).
VARIABLE RADIOSENSITIVITY OF CHROMOSOMES 2, 8 AND 14
IN HUMAN PERIPHERAL BLOOD LYMPHOCYTES
EXPOSED TO 480 MeV/n 12C-IONS
Marta Deperas-Kaminska1,2/, Gennady N. Timoshenko1/, Eugene A. Krasavin1/, Andrzej Wójcik2,3/
1/
Joint Institute for Nuclear Research, Dubna, Russia
2/
Świetokrzyska Academy, Kielce, Poland
3/
For a wide variety of biological effects, radiations
of high linear energy transfer (LET) have been
known to have greater biological effectiveness per
unit dose than those of low LET [1]. Little is known
about the extent of individual variability in the
radiosensitivity of human cells to high LET radiation. In all published studies dealing with individual
radiosensitivity, the studied cells (lymphocytes or
fibroblasts) were only exposed to low LET radiation. The purpose of this study was to investigate
by FISH the distribution of radiation-induced
chromosomal aberrations in chromosomes 2, 8 and
14 in lymphocytes of 3 donors.
Irradiation of blood from 3 healthy donors was
performed at the Nuclotron accelerator at the Joint
tions including the complex ones were transformed
into primary breaks. The break frequencies were
scaled to the whole genomic frequencies. The results are presented in Fig.1. For all donors, the lowest frequency of breaks was observed in chromosome 2 and the highest in chromosome 14 in lymphocytes of donor 3, chromosome 8 of donor 2,
and at the same level in chromosomes 8 and 14 of
donor 1 (Fig.1A). The found break frequency is
below the expected values for chromosome 2 and
above the expected values for chromosomes 8 and
14. Only for chromosome 14 of donor 2 the ratio
is close to unity (Fig.1B).
The lowest frequencies of exchanges were
scored in chromosome 2 and the inter-donor vari-
Fig.1. Primary breaks observed in the painted chromosomes of 3 donors. Breaks calculated from aberrations observed
after exposed to 3.5 Gy of 480 MeV/n 12C-ions were summed up and scaled to the whole genomic frequency. The
absolute numbers are shown in Fig.1A and the ratios of found to expected are shown in Fig.1B. Error bars represent
standard deviations from the mean; also, values are shown for the three painted chromosomes of all donors.
Institute for Nuclear Research (Dubna, Russia).
Whole blood samples were irradiated with 1.1, 2.3
and 3.5 Gy of 12C-ions. At the position of the sample
the beam energy was 480 MeV/n and LET=10.6
keV/μm. Chromosomes 2, 8 and 14 were painted
in different colors and aberrations scored with the
help of an image-analysis system, as described in [2].
In order to assess the overall radiosensitivity of
the painted chromosomes, chromosomal aberra-
ability was low. Chromosomes 8 and 14 were involved in exchanges more frequently than expected
on the basis of DNA content. In contrast, the involvement of chromosome 2 was less frequent than
expected.
This is the first study investigating the individual
radiosensitivity of chromosomes of human peripheral blood lymphocytes to heavy ions. Generally,
the sensitivity of chromosome 2 was lower, and that
106
RADIOBIOLOGY
of chromosomes 8 and 14 – higher than expected.
These data suggest that the sensitivity of human
chromosome to heavy ions is individually variable.
The results are in line with those of a recent study
on the sensitivity of chromosomes 2, 8 and 14 to
gamma rays [2].
References
[1]. Goodhead D.T.: J. Radiat. Res., 40 (Suppl.), 1-13
(1999).
[2]. Sommer S., Buraczewska I., Wojewodzka M., Bouzyk
E., Szumiel I., Wojcik A.: Int. J. Radiat. Biol., 81,
741-749 (2005).
EFFICIENT DOUBLE STRAND BREAK REJOINING AND SURVIVAL
IN X-IRRADIATED HUMAN GLIOMA M059 CELLS ARE DEPENDENT
ON EGF RECEPTOR KINASE ACTIVITY
Iwona Grądzka, Barbara Sochanowicz, Irena Szumiel
The epidermal growth factor (EGF) receptor
(EGFR) is a mediator of both proliferative and survival signals in mammalian cells (reviewed in [1]).
Nuclear translocation of EGFR was observed after
X-irradiation and was found to be important for
regulation of DNA repair processes [2,3]. We investigated the effect of EGFR inhibition on various
aspects of the cellular response to X-irradiation
in two related human glioma cell lines M059 K and
M059 J, the latter highly sensitive to X-radiation
due to the lack of a catalytic subunit (DNA-PKcs)
of DNA-dependent protein kinase (DNA-PK) [4].
Tyrphostin AG 1478 was used as a specific inhibitor to block EGFR tyrosine kinase activity.
We have previously found that double strand
break (DSB) rejoining after X-irradiation is faster
in M059 K than in M059 J cells [5] because of a defect in a nonhomologous DNA end-joining (NHEJ)
in the latter cell line [4]. Tyrphostin AG 1478 slowed
down the DSB rejoining in M059 K and has no
effect in M059 J cells. This suggested a direct link
between EGFR kinase activity and DNA-PK-dependent DSB rejoining and was consistent with observation of other authors [3]. Now, we have examined survival of both cell lines after X-irradiation
combined with tyrphostin treatment. The dose
range for each cell line was chosen so that the survival level was comparable (between 90 and 1%).
The survival data were expressed as the ratio of
survival after combined treatment to that after
X-irradiation alone. Ratio equal to unity means a
strictly additive effect, that is, independent effect
of each of the agents tested. A less than additive
effect (protection) or more than additive effect (sensitisation) indicate an interaction of both agents.
As shown in Fig., in M059 K cells there is a more
than additive effect of combined (X+T) treatment,
i.e. radiosensitisation; this effect is absent in M059J
cells (close to additive effect at doses up to 1 Gy
and protective effect at higher doses).
In conclusion, tyrphostin AG 1478 slowes down
the DSB rejoining in M059 K and has no effect in
M059 J cells. This effect corresponds with a decrease
in survival in M059 K but not in M059 J cells subjected to combined (T+X) treatment and suggests
a direct relation between EGFR kinase activity,
DNA-PK-dependent DSB rejoining and survival.
INCT.
References
Fig. Survival ratio after combined (X+T) treatment to that
after X-irradiation alone (see text for explanations).
[1]. Amorino G.P., Hamilton V.M., Valerie K., Dent P.,
Lammering G., Schmidt-Ulrich R.K.: Mol. Biol. Cell,
13, 2233-2244 (2002).
[2]. Harari P.M., Huang S.M.: Semin. Radiat. Oncol., 11,
281-289 (2001).
[3]. Dittmann K., Mayer C., Fehrenbacher B., Schaller M.,
Raju U., Milas L., Chen D.J., Kehlbach R., Rodemann
H.P.: J. Biol. Chem., 280, 31182-31189 (2005).
[4]. Anderson C.W., Dunn J.J., Freimuth P.I., Galloway
A.M., Allalunis-Turner M.J.: Radiat. Res., 156, 2-9
(2001).
[5]. Grądzka I., Buraczewska I., Sochanowicz B., Szumiel
I.: Eur. J. Biochem., 271 (Suppl. 1, Pt1), 1-12 (2004).
RADIOBIOLOGY
107
DECREASED PERSISTENCE OF γH2AX FOCI
IN X-IRRADIATED xrs6 CELLS TREATED WITH SIRTUIN INHIBITOR
Maria Wojewódzka, Marcin Kruszewski, Irena Szumiel
In the preceding reports, we described the effect
of sirtuin inhibitor, GPI 19015 treatment on the
repair of DNA double strand breaks (DSB) and
survival in CHO-K1 and xrs6 cells [1]. In CHO-K1
cells a relatively weak effect was noted (using the
neutral comet assay) at the 15 min repair interval.
In contrast, in the DSB repair (nonhomologous
end-joining – NHEJ) defective mutant cell line, xrs6,
the increase in the rate of DSB repair was more pronounced, especially in G1 phase of the cell cycle.
The cells were treated with sirtuin inhibitor 200 μM
GPI 19015 at 37oC for 1 h and X-irradiated with 10
Gy without medium change. Applying the same experimental schedule, we determined the number of
γH2AX foci in both cell lines, using the foci method
as described in [2].
Control
With the use of an anti-γH2AX antibody with
a fluorescent tag, a pattern of γH2AX foci can be
revealed a few minutes after irradiation. The foci
are markers of DSB and allow to directly count the
DSB number per nucleus (review in [3]). As shown
in Figs.1 and 2, in xsr6 cells GPI 19015 treatment
causes a faster disappearance of foci than in the
inhibitor-untreated cells. In CHO-K1 cells there
is no effect of the inhibitor, in agreement with the
weak effect on DSB rejoining estimated with the
comet assay. As stated previously, the possible reason of this effect may lay in the impaired DNA-PK
(DNA-dependent protein kinase) dependent nonhomologous end-joining (D-NHEJ) in xrs6 cells:
DSB repair in these cells has to rely on the homologous recombination repair or DNA-PK in-
Irradiation 1 Gy
0h
Irradiation 1 Gy
4h
CHO-K1
CHO-K1+GPI
xrs6
xrs6+GPI
Fig.1. Photographs of histone γH2AX foci in control cells and cells irradiated with 1 Gy X-irradiation. Time-dependent
decrease of the histone γH2AX foci number in untreated and inhibitor-treated CHO-K1 and xrs6 cells also is
presented in Fig.2.
108
RADIOBIOLOGY
Fig.2. Time-dependent decrease of the histone γH2AX foci number in untreated and inhibitor-treated CHO-K1 cells
(A) and xrs6 cells (B). The foci numbers are expressed as a percentage of mean initial foci number in irradiated
cells. Number of foci in controls was subtracted. Foci in 100 cells were scored for each time interval.
dependent (backup) nonhomologous end-joining
(B-NHEJ) [4,5]. It can be expected that sirtuin inhibition increases histone acetylation and thus,
facilitates the access of repair enzymes to the damaged DNA sites.
Supported by the Polish Ministry of Education
and Science statutory grant for the INCT.
[2].
[3].
[4].
References
[5].
[1]. Wojewódzka M., Kruszewski M., Szumiel I.: Backup
nonhomologous end-joining is the target of sirtuin
inhibitor. In: INCT Annual Report 2005. Institute of
pp. 107-108.
Cowell I.G., Durkacz B.W., Tilby M.J.: Biochem.
Pharmacol., 71, 13-20 (2005).
Pilch D.R., Sedelnikova O.A., Redon C., Celeste A.,
Nussenzweig A., Bonner W.M.: Biochem. Cell Biol.,
81, 123-129 (2003).
Wang H., Perrault A.R., Takeda Y., Qin W., Wang M.,
Iliakis G.: Nucleic Acids Res., 31, 5377-5388 (2003).
Wang H., Rosidi B., Perrault R., Wang M., Zhang L.,
Windhofer F., Iliakis G.: Cancer Res., 65, 4020-4030
(2005).
TWO p53 BINDING PROTEINS
ARE PRESENT IN LY-R (REPAIR COMPETENT)
AND LY-S (REPAIR DEFICIENT) CELLS
IN DIFFERENT PROPORTIONS
Barbara Sochanowicz, Irena Szumiel
L5178Y-S (LY-S) subline is the longest known
mammalian radiation sensitive cell line. Although
it is clear that the reason for radiation sensitivity
of LY-S cells is an impaired DNA DSB (double
strand break) repair, the molecular defect is unknown. LY-S cells show both phenotypic features
that are characteristic of cells with a defective NHEJ
(nonhomologous end-joining): a pronounced G1
phase radiosensitivity and a slown down DSB repair. Nevertheless, the NHEJ defect in LY-S cells
is not due to DNA-PK (DNA-dependent protein
kinase), Xrcc4 or ligase IV mutation. Another possible defect concerning autophosphorylation in the
so-called ABCDE cluster of serine and threonine
residues in the central part of the catalytic subunit
has also been eliminated as a reason for impaired
repair of DSB (reviewed in [1]).
A recent paper [2] pointed to a role of 53BP1
protein in the NHEJ system. 53BP1 (p53 binding
protein) is a BRCT domain-containing protein that
is rapidly recruited to DSB after X-irradiation. Its
function probably consists in acting as a scaffold
protein and contributing to ligase IV and Artemis
functioning, as shown in Fig.1. Its absence in chicken
DT40 cells was phenotypically manifested as a NHEJ
defect [2] and exactly matched the phenotype of
LY-S cells; hence, there was a possibility that LY-S
cells are deprived of this protein. Therefore, we
examined the total cell extracts from both closely
related LY sublines, LY-R (repair competent) and
Fig.1. Model of NHEJ pathways according to [2]: (A) the
core NHEJ pathway, (B) ATM/Artemis – dependent
pathway, (C) 53BP1 – dependent pathway. The 53BP1
protein contributes to both B and C pathway. Lig IV
– ligase IV.
RADIOBIOLOGY
109
LY-R LY-S LY-R LY-S
60 μg
30 μg
K562
30 μg
Fig.2. Western blot showing one band detected with the
anti-53BP1 antibody in K562 cells and two bands in
LY-R and LY-S cells. Note that in LY cells the two
detected proteins seem to sum up to the same
amount but the ratio of band 1 to 2 differs.
LY-S (repair deficient), for 53BP1 protein, using
a specific antibody (rabbit polyclonal to 53BP1,
ab36823, Abcam) and Western blotting method.
K562 cells served as a positive control.
As shown in Fig.2, we detected one protein
band with the anti-53BP1 antibody in K562 cells
and two bands in LY-R and LY-S cells. In LY cells
the two detected proteins seem to sum up to the
same amount. Nevertheless, the band corresponding to 53BP1 of similar molecular weight as that
in K562 cells is less abundant in LY-S cells than in
LY-R cells.
There are no data on 53BP1 isoforms in the
literature. The antibody was obtained with the use
of a peptide representing a portion of human 53BP1
encoded in part by exons 11 and 12 as immunogen.
It reacts with both the human and murine protein.
Notwithstanding the possible significance of the
presence of two detected proteins expressed in
various proportions in LY sublines, it can be stated
that there is no analogy between this observation
and that concerning DT40 cells with a DSB repair
defect due to lack of 53BP1. Thus, absence of 53BP1
protein is not a reason of defective DSB repair in
LY-S cells.
References
[1]. Szumiel I.: Int. Radiat. Biol., 81 (5), 353-365 (2005).
[2]. Iwabuchi K., Hashimoto M., Matsui T., Kurihara T.,
Shimizu H., Adachi N., Ishiai M., Yamamoto K.,
Tauchi H., Takata M., Koyama H., Date T.: Genes
Cells, 11(8), 935-948 (2006).
PREMATURE CHROMOSOME CONDENSATION
IN BIOLOGICAL DOSIMETRY
AFTER HIGH DOSE GAMMA IRRADIATION
Sylwester Sommer, Iwona Buraczewska, Andrzej Wójcik
Biological dosimetry is necessary in the case of
radiation accidents or accidental exposures to ionizing radiation, especially in the case of lack or failure of physical measurements of the dose [1].
Analysis of Giemsa-stained dicentrics in human
peripheral blood lymphocytes is regarded by the
International Atomic Energy Agency as the most
accurate and reliable assay of biological dosimetry
[1]. In the case of high radiation doses, problems
can occur with obtaining a sufficient number of
mitotic cells for analysis [1,2]. The use of drug-induced PCC (premature chromatin condensation)
was proposed to overcome this problem [2,3].
Therefore, we decided to determine the frequency
of aberrations induced by high doses of radiation
in painted chromosomes 2, 8 and 14, both accumulated in mitotic cells and after PCC induction.
Human lymphocytes of 6 healthy donors, irradiated with 0, 3, 5, 7 and 10 Gy of γ 60Co were cultured in whole blood cultures for 48 h. Twenty four
hours after set-up of cultures, colcemid was added
to the final concentration of 1 μg/ml to arrest cells
in the first mitosis after irradiation. Two hours before the end of cultivation, calyculin A (50 nM) was
applied to induce PCC. Lymphocytes were fixed
according to the standard procedure. FISH staining was performed on 3 pairs of chromosomes: 2,
8, 14, using directly labeled probes from Oncor,
according to the manufacturer’s protocol. At least
150 cells for each dose were analyzed for every do-
nor, to the total number of 10 020 cells. Excess fragments or entities with color junctions, involving 3
painted pairs of chromosomes, were regarded as
aberrations.
Figure presents the dose-effect curve for total
aberrations in chromosomes 2, 8 and 14, scored in
lymphocytes of 6 patients. There was a clear dose
– dependence and no saturation of aberration yields
Fig. Dose response curves for total aberration yields determined with the PCC method combined with FISH
staining after in vitro irradiation of peripheral blood
lymphocytes from 6 donors with 0, 3, 5, 7 and 10 Gy of
gamma rays.
110
up to the dose of 10 Gy. In spite of relatively low
values of the mitotic index (except controls) – lower
than 1% – it was possible – due to PCC – to analyze
more than 150 spreads from each slide; this would
not be possible if only cells arrested in metaphase
by colcemid block were analyzed. Simultaneous
usage of PCC and whole chromosome FISH allowed to score not only excess fragments but also
the exchange type of aberrations, usually not recognizable in PCC-spreads, because of their poor
quality.
We could not see any differences between individual radiosensitivity of donors – there were
only slight differences between curves. Such result
confirms our previous report where we also found
no difference between donors with respect to radiation sensitivity [4].
Our experimental scheme allows to analyze exclusively aberrations in cells in G2/M phase and
mitosis of the first cycle after irradiation; this is
important, since there is a loss of damaged (aberrant) cells during cell division. Also important is
RADIOBIOLOGY
the possibility of analyzing heavily damaged cells
which would be arrested before entering mitosis
e.g. in the G2 phase checkpoint. We conclude that
after establishing suitable calibration curves, simultaneous use of PCC and chromosome painting
could be a very useful tool for biological dosimetry
in the case of high doses of radiation.
of Education and Science – grant No. 6 P05A 11920
and statutory grant for the INCT.
References
[1]. Cytogenetic analysis for radiation dose assessment. A
manual. IAEA, Vienna 2001. Technical Reports Series
No. 405.
[2]. Gotoh E., Durante M.: J. Cell. Physiol., 209, 297-304
(2006).
[3]. Kanda R., Minamihisamatsu M., Hayata I.: Int. J.
Radiat. Biol., 78, 857-862 (2002).
[4]. Sommer S., Buraczewska I., Wojewódzka M., Boużyk E.,
Szumiel I., Wójcik A.: Int. J. Radiat. Biol., 81, 741-749
(2005).
NUCLEAR TECHNOLOGIES
AND
METHODS
113
PROCESS ENGINEERING
METHOD FOR COLLECTION OF NITRATE FROM WATER SAMPLES
AND DETERMINATION OF NITROGEN AND OXYGEN ISOTOPE
COMPOSITION
Małgorzata Derda, Stela Maria Cuna1/, Ryszard Wierzchnicki
1/
National Institute for Research and Development of Isotopic and Molecular Technologies,
Cluj-Napoca, Romania
Problem associated with anthropogenic nitrogen
contributions to the biosphere and hydrosphere are
increasingly being recognized. Nitrate contamination, often related to agricultural activities, is one
of the major problems in surface and groundwater
system.
Nitrogen availability is one of the main controls
on productivity and is an important factor regulating biodiversity. At present, nitrogen input from
human sources, chiefly synthetic fertilizers and
burning of fossil fuels, approximately equals the
input from natural nitrogen fixation. The increased
nitrogen input from anthropogenic sources causes
eutrophication of lakes, streams, and coastal waterways, acidification of environments, and degradation of drinking water quality [1].
Nitrogen in terrestrial and aquatic ecosystem
cycles among oxidized, reduced, organic and inorganic species, of which the nitrate is relatively
abundant and mobile. Nitrogen and oxygen isotope
ratios of nitrates provide a powerful tool to investigate nitrate sources and cycling mechanisms. The
analysis of nitrates for both δ15N and δ18O allows
improved discrimination among potential sources
and reaction mechanisms [2,3].
Our objectives were to develop methods for concentrating dissolved nitrates and to prepare them
for nitrogen and oxygen isotope analysis. We have
developed ion exchange methods because these
methods offer a number of important advantages
over other methods: i) nitrates can be concentrated
from dilute waters, ii) columns can be loaded in
the field, iii) many samples may be processed at
one time. The main disadvantage of this method
is time required for collection and preparation of
samples.
The technical procedure of the method include:
quantitative extraction of nitrates from water
samples, preparation of other nitrogen and oxygen
bearing species for 15N and 18O analysis, and conversion of the nitrate fraction to suitable gases for
nitrogen and oxygen isotopic analysis.
Samples were prepared by an anion exchange
resin method as shown in Fig. [4]. The nitrate fraction was collected by passing the water sample
through pre-filled, disposable, anion exchange resin
columns. Nitrate fraction was then eluted from the
column with 15 ml of 3 M HCl. The nitrate-bearing acid eluent was neutralized with Ag2O and filtered to remove the AgCl precipitate. The sample
containing AgNO3 was split into aliquots in the
ratio 1:2 for δ15N and δ18O analysis.
Fig. Schematic representation of the procedure for collection, elution and processing of δ15N and δ18O analysis.
One portion for δ15N analysis was drying at
55-65oC to evaporate water and to obtain AgNO3
as a solid phase [5]. After drying, the AgNO3 was
redissolved by adding 2 ml of deionized water. The
resulting precipitate was pipetted into 3 silver capsules such that each capsule contained 6-10 μmol
of NO3. The capsules were drying and after adding sucrose, δ15N was measured using an EA-IRMS
(elemental analyzer-isotope ratio mass spectometer) in continuous flow. Nitrogen isotope values
(δ15N) are reported in per mill (‰), relative to the
atmospheric air.
The portion for δ18O determination was dried
and then CO2 was produced by off-line pyrolysis
with graphite in a vacuum line. The δ18O analysis
was carried out using the dual inlet system Delta
plus IRMS. The δ18O values were reported relative
to the standard VSMOW.
The anion exchange resin techniques offer an
efficient and reliable means of collecting, transporting, and storing, water samples for nitrogen and
oxygen isotope analysis for the nitrate. Multiple
samples may be sorbed on columns in field conditions using a common and relatively inexpensive
114
PROCESS ENGINEERING
equipment. The laboratory preparation of samples
for δ15N analysis requires little technician time per
sample (about 30 min) and most of the total time
required for sample preparation is spent for drying and combustion steps.
The preparation of a sample for δ18O analyses
is more time-consuming (about 2 h) because of the
necessity of eliminating non-nitrate, oxygen-bearing anions and finally extraction of CO2.
The presented method will be used for monitoring water systems and investigation of anthropogenic impact on the condition of Polish rivers.
References
[1]. Vitousek P.M., Aber J.D., Howarth R.W., Likens G.E.,
Matson P.A., Schindler D.W., Schlesinger W.H., Tilman
D.G.: Ecol. Appl., 7, 3, 737-750 (1997).
[2]. Amberger A., Schmidt H.L.: Geochim. Cosmochim.
Acta, 51, 2699-2705 (1987).
[3]. Boettcher J., Strebel O., Voerkelius S., Schmidt H.L.:
J. Hydrol., 114, 413-424 (1990).
[4]. Silva S.R., Kendall C., Wilkison D.H., Ziegler A.C., Chang
C.C.Y., Avanzino R.J.: J. Hydrol., 228, 22-36 (2000).
[5]. Fukada T., Hiscock K.M., Dennis P.F., Grischek T.:
Water Res., 37, 3070-3078 (2003).
THE KINETICS OF TRANS-DICHLOROETHYLENE DECOMPOSITION
IN AIR UNDER ELECTRON-BEAM IRRADIATION
Yongxia Sun, Andrzej G. Chmielewski, Sylwester Bułka, Zbigniew Zimek, Henrietta Nichipor1/
1/
Institute of Radiation Physical-Chemical Problems, National Academy of Sciences of Belarus,
Minsk, Belarus
In our previous work [1,2], we have experimentally
studied 1,1-dichloroethylene – 1,1-DCE (H2C=CCl2)
and trans-dichloroethylene – trans-DCE (trans-HClC=CHCl) decomposition in an air mixture
under electron-beam (EB) irradiation. It was found
that the decomposition efficiency of 1,1-DCE in air
under EB irradiation is higher than trans-DCE in
the same range of initial concentration. The degradation organic by-product of 1,1-DCE was identified as chloroacetyl chloride (CH2ClCOCl) by
means of gas chromatography with a flame ionizing detector (GC-FID) analysis, while no organic
compounds were observed as by-products for
trans-DCE degradation in air under EB irradiation using the same analytical method. 1,1-DCE
and trans-DCE are geometric isomers. Whether
their decomposition mechanism in the air mixture
under EB irradiation is the same or not is not clear
to us. In this work, we made a computer simulation of trans-DCE degradation in the air mixture
under EB irradiation, the decomposition mechanism was proposed and compared with 1,1-DCE.
The computer simulation of trans-DCE degradation in air under EB irradiation was carried out
Fig.1. Scheme of reaction pathways of trans-DCE decomposition and by-products formation.
by using the computer code “Kinetic” [3] and GEAR
method, 320 reactions involving 78 species were
considered, five main groups of reactions were included, the rate constants of reactions were mostly
taken from the literatures [4,5]. The rate of Wj of j
type species generated from matrix with k type
molecules was calculated according to equation:
Wj = Σ Gjk I ρk/ρ
where: Gjk – value of j type species from k type
matrix, I – dose rate, ρk – gas phase density of the
matrix, ρ – overall density of the gas phase.
When fast electrons from electron beams are
absorbed in the carrier gas, they cause ionization
and excitation process of the nitrogen, oxygen and
H2O molecules in the carrier gas. Primary species
and secondary electrons are formed. These primary
species and thermalized secondary electrons cause
trans-DCE degradation by complex chemical reactions, a scheme of reaction pathways of trans-DCE
decomposition and organic products formation is
presented in Fig.1. Based on our calculation results, similar to 1,1-DCE degradation in air under
EB irradiation, Cl– dissociated thermalized secondary electron attachment, Cl addition reaction with
trans-DCE followed by peroxyl radical reactions
is a main reaction pathway for trans-DCE degradation. Calculated and experimental results of
trans-DCE degradation in the air mixture vs. dose
under EB irradiation are presented in Fig.2. The
key reactions which cause trans-DCE or 1,1-DCE
decomposition and products formation in air under
EB irradiation can be generally written as follows:
e + C2H2Cl2 = Cl– + C2H2Cl· k1=1.0×10–9
Cl– + A+ = Cl + A
+
(A is any positive ion in the gas phase)
C2H2Cl2 + Cl = C2H2Cl3 (k3)
O2 + C2H2Cl3· = C2H2Cl3(O2)·
2C2H2Cl3(O2)· = C2H2Cl3(O)· + O2
C2H2Cl3(O)· = CH2ClCOCl + Cl (for 1,1-DCE)
or C2H2Cl3(O)· = HCOCl + CHCl2 (for trans-DCE)
The rate constant of Cl addition reaction to
1,1-DCE (k 3a =1.4×10 –10 cm 3·molecule –1 ·s –1 ) is
higher than to trans-DCE (k3b=9.58×10–11 cm3·molecule–1·s–1), this is the main reason why the decomposition efficiency of 1,1-DCE in air under EB irradiation is higher than that of trans-DCE.
115
Fig.2. Concentration of trans-DCE vs. dose under EB irradiation (solid lines – experimental results [2],
dashed lines – calculation results).
Mechanism of trans-DCE degradation in the air
mixture under EB irradiation is similar to 1,1-DCE,
Cl– dissociated thermalized secondary electron
attachment, Cl addition reaction with trans-DCE
followed by peroxyl radical reactions is the main
reaction pathway for trans-DCE degradation.
HCOCl which was not and cannot be detected by
GC-FID analysis was predicted as a main product
of trans-DCE degradation based on modelling
simulation results. OH radical presence increases
decomposition efficiency of trans-DCE less than
10%.
References
[1]. Sun Y. et al.: Radiat. Phys. Chem., 61, 353-360 (2001).
[2]. Sun Y. et al.: Radiat. Phys. Chem., 68, 843-850 (2003).
[3]. Bugaenko W.L. et al.: Program for modeling of chemical
kinetics. Institute of Theoretical and Experimental
Physics, Moscow 1980. Report ITEP No. 50.
[4]. Albritton D.L.: At. Data Nucl. Data, 22, 1-101 (1978).
[5]. http://kinetics.nist.gov/kinetics/index.jsp.
ELECTRON BEAM OF VOCs TREATMENT EMMITTED
FROM OIL COMBUSTION PROCESS
Anna Ostapczuk, Janusz Licki1/, Andrzej G. Chmielewski
1/
Institute of Atomic Energy, Świerk, Poland
Electron beam (EB) processing has been already
applied on industrial scale for the treatment of flue
gas from coal combustion: full-scale EB installations have been put into operation in Poland [1]
and China [2] for the removal of acidic pollutants
like SO2 and NOx. The technology has been investigated for volatile organic compounds (VOCs) removal from flue gases since the late ’80ies and recent research in a pilot plant scale has shown the
possibility to decompose/detoxify of dioxins stream
in waste-incineration [3] and polycyclic aromatic
hydrocarbons (PAHs) in coal combustion flue gases
[4]. It has been observed that the investigated groups
of compound change their distribution profile to
homologues, which are characterized by lower
toxicity factor and, as the consequence, the overall
toxicity of flue gas decreased [3-5]. The change of
concentration and distribution profile observed in
flue gas treated by EB irradiation can be caused
by three processes: (i) destruction in the oxidation
116
processes [6,7], adsorption on the aerosol surface
and (iii) new compound formation in radical process [8]. The experimental work done in the pilot
plant on real flue gas has been concentrated on
the EB influence on the homologues belonging to
one group of compounds. VOCs have been investigated as a single model compound irradiated in
a gaseous mixture and as a main decomposition
pathway OH radicals – initiated oxidation is proposed [9-10]. The process is analogical to atmospheric chemistry, and VOCs are mineralized and
transformed into other organic compounds.
Laboratory scale experiments on EB treatment
have been performed to investigate the change of
the composition of organic fraction of flue gas
emitted from oil combustion process. The flue gas
(v=5 m3/h) passing the irradiation chamber has
been irradiated by EB from an ILU-6 accelerator
through a titanium window with a dose ranging
from 3.5 to 8.8 kGy. The concentration of organic
compounds in flue gas at the inlet and outlet of
the irradiation chamber have been compared with
the aim to find how EB irradiation influences the
composition of organic fraction of flue gas. The
qualitative and quantitative analysis of the concentrated extracts was performed by gas chromatography-mass spectrometry (GC-MS) by a Shimadzu
GC-17A gas chromatograph connected with a
quadropole mass spectrometer Shimadzu QP5050.
Analyzed mixtures were separated on a non-polar
column HP5-MS (Hewlett Packard, 30 m×0.25 mm
ID×0.25 mm film thickness).
The composition of the organic fraction of oil
combustion flue gas has been determined qualitatively and quantitavely in several experimental se-
PROCESS ENGINEERING
Fig. Distribution of PAH, BTX and OAH in the organic
fraction of flue gas at the inlet and the outlet of irradiation chamber; dose D=5.3 kGy, initial VOC concentration ci=72.5 μg/m3.
dividual compounds like PAHs has been lowered
even by two orders of magnitude.
Simultaneously, an increase of oxygen-containing aromatic compounds (OAH) like phenol, benzaldehydes, benzoid acids and others has been
observed. OAH is a dominating group of VOCs
present in flue gas, in contast to the composition
of flue gas before EB treatment (Fig.). The higher
concentration of oxidized compounds and increase
Table. Organic compounds and their concentration level detected in oil combustion gas.
ries with the purpose to establish the key groups
of emitted compounds. The categories of the detected organic compounds and their concentration
level are listed in Table.
The composition of the organic fraction of flue
gas has changed after irradiation: the concentration of PAHs and aromatic compounds (BTX)
decreased after irradiation. The average removal
efficiency for a dose of 5.3 kGy of these compounds
was 60 and 84%, respectively. Decomposition ratio of the investigated compounds increased with
dose absorbed. The initial concentration of the in-
of CO content in irradiated flue gas is effected by
oxidative decomposition of aromatic compounds.
The work has been partially co-finansed by the
International Atomic Energy Agency (IAEA research contract No. POL 13136) and the Ministry
of Science and Higher Education (agreement No.
7/IAEA/2006/0).
References
[1].
Tymiński, B.; Pawelec, A.: Economic evaluation of
electron beam flue gas treatment. In: Radiation treatment of gaseous and liquid effluents for contaminant
removal. Proceedings of a technical meeting held in
Sofia, Bulgaria, 07-10.09.2005. IAEA, Vienna 2005,
pp. 25-34, IAEA-TECDOC-1473.
[2]. Mao B.: Process of flue gas desulphuration with electron beam irradiation in China. In: Radiation treatment of gaseous and liquid effluents for contaminant
removal. Proceedings of a technical meeting held in
Sofia, Bulgaria, 07-10.09.2005. IAEA, Vienna 2005,
pp. 45-51, IAEA-TECDOC-1473.
[3]. Hirota K., Hakoda T., Taguchi M., Takigami M., Kim
H.-H., Kojima T.: Environ. Sci. Technol., 37, 3164
(2003).
[4]. Chmielewski A.G., Ostapczuk A., Zimek Z., Licki J.,
Kubica K.: Radiat. Phys. Chem., 63, 653-655 (2002).
[5]. Chmielewski A.G., Ostapczuk A., Licki J.: Polycyclic
aromatic hydrocarbons removal from flue gas by electron beam treatment – pilot plant tests. In: Radiation
117
[6].
[7].
[8].
[9].
[10].
treatment of gaseous and liquid effluents for contaminant removal. Proceedings of a technical meeting
held in Sofia, Bulgaria, 07-10.09.2005. IAEA, Vienna
2005, pp. 63-68, IAEA-TECDOC-1473.
Biermann H.W., Mac Leod H., Atkinson R., Winer
A.M., Pitts J.N.: Environ. Sci. Technol., 19, 1115
(1985).
Atkinson R., Arey J., Zielinska B., Aschmann S.M.:
Int. J. Chem. Kinet., 22, 1071 (1990).
Gerasimov G.Ya.: High Energ. Chem., 39, 60 (2005).
Prager L., Mark G., Mätzing H., Paur H.-R., Schubert
J., Frimmel F.H., Hesse S., Schuchmann H.-P.,
Schuchmann M.N., Sonntag C.V.: Environ. Sci.
Technol., 37, 379-385 (2003).
Hirota K., Mätzing H., Paur H.-R., Woletz K.:
Radiat. Phys. Chem., 45, 649-655 (1995).
ELECTRON BEAM TREATMENT OF FLUE GAS
FROM FUEL OIL COMBUSTION
Andrzej G. Chmielewski, Andrzej Pawelec, Bogdan Tymiński, Zbigniew Zimek, Janusz Licki1/,
Ahmed A. Basfar2/
1/
2/
King Abdulaziz City for Science and Technology, Riyadh, Saudi Arabia
During operation of the plant installed at the Pomorzany Electric Power Station, the electron beam
flue gas treatment technology has proved its usability for industrial applications. The technology
allows for simultaneous removal of both sulphur
dioxide (SO2) and nitrogen oxides (NOx) with high
efficiency. Beside of this the process is wasteless
and economically competitive to the conventional
emission control methods. One of the important
advantages is the possibility of application of this
method for cleaning of flue gas from various, not
only coal combustion based, technological processes. Research on the purification of flue gas
from the fuels different than coal was undertaken
in the Institute of Nuclear Chemistry and Technology.
The process of treatment of flue gas from fuel
oil combustion was studied. Three types of oil containing various amounts of sulphur (oil I – 2.81%,
oil II – 2.9% and oil III – 3.1%) were taken for laboratory experiments. The composition of the flue
gas depends on burning conditions and oil itself.
Generally, the basic flue gas parameters were as
follows:
- volume flow rate – 5 Nm3/h,
- SO2 concentration – 800-1850 ppmv,
- NOx concentration – 80-190 ppmv,
- gas temperature at process vessel – 60-120oC.
The influence of such factors as irradiation dose,
gas temperature at the inlet to process vessel, ammonia stoichiometry, gas humidity and oxygen concentration on the process efficiency was studied.
High SO2 and NOx removal efficiency up to 99%
for SO2 and 90% for NOx (respectively, 98% and
85% in optimal conditions) was achieved. Results
of the parametric tests indicate that, with the exception of dose, SO2 and NOx removals depend on
the different process conditions. By controlling these
conditions it is possible to obtain maximum removal
efficiencies. NOx removal is mostly energy-consuming, while SO2 removal is sensitive to temperature,
humidity and ammonia stoichiometry. The proper
selection of the process conditions (gas humidity
– 10-15 vol.%, ammonia stoichiometry – 0.90-0.95
and gas temperature – 60-700C) guarantees high SO2
removal efficiency at low energy consumption. A
dose of 6-9 kGy is sufficient to achieve over 90%
SO2 and 70% NOx simultaneous removal from flue
gas under optimum operating conditions. Higher
NOx removal efficiencies require higher energy
consumption. No impact of oxygen concentration,
in the analyzed range, on the process efficiency was
observed. The optimal parameters were very similar for all three grades of oil. This means that the
electron beam flue gas treatment technology may
be applied for any grade of oil.
The by-product is almost a pure mixture of
ammonium sulphate and ammonium nitrate, that
makes it a valuable fertilizer. The combination of
these two compounds provides a suitable quality
material for direct soil application or as a blending component in the standard manufacture of
commercial fertilizer (NPK type).
The obtained results correspond with those
previously obtained for the experiments conducted
with coal combustion flue gases. The above results
prove the possibility of electron beam flue gas
treatment technology to be applied for the purification of flue gases from different fuel combustion process.
118
PROCESS ENGINEERING
DOSIMETRY FOR COMBUSTION FLUE GAS TREATMENT
WITH ELECTRON BEAM
Kishor Mehta1/, Sylwester Bułka
1/
Vienna, Austria
The most widely applied systems for coal fired
boilers are wet flue gas desulphurization (FGD) using lime or limestone as reagent and selective catalytic reduction for NOx reduction. Therefore, it is
still important to develop new treatment methods
that do not have these problems. The electron beam
treatment of flue gas is one of the new technologies.
Its success in significantly reducing SO2 and NOx
has already been demonstrated in many pilot plants
and a few full commercial plants.
There are several advantages in employing ionizing radiation (electrons) for this purpose, including [1]:
- several polluting gases are removed simultaneously with high efficiency;
- dry system without any wastewater treatment;
- simple system with easy operation;
- compact plant, thus easy for retrofitting in an
existing power station;
- high energy efficiency, and by-product can be
used as fertilizer.
This process requires beam power of 300 kW
or more, and electron energy in the range of 0.8 to
1 MeV. Accelerators suitable to fulfill such requirements are based on high-power, high-voltage transformers according to the present state-of-the-art
accelerator technology. Industrial linac technology,
which was developed for military applications, is
being demonstrated now as an appropriate technical and cost-effective competitive alternative [2].
The electron beam technology is relatively flexible
and adaptable to local conditions. The process can
be easily adapted for different removal efficiency
levels and adjusted for use with different fuels.
Also, retrofitting of existing facilities to reduce NOx
and SO2 concentrations to meet low-space requirements is an attractive option.
Dose and dose distribution in the reaction
vessel of a flue gas treatment facility very strongly
influence the removal efficiency of NOx, and to a
smaller degree of SO2. Thus, it is essential that
these two parameters are measured and optimized
for better economy of the process.
The recent dosimetry related work carried out
by the authors at the Institute of Nuclear Chemistry and Technology (INCT) lead to conclusion that
the best method for measuring average dose to the
gas is through a dosimetry system that relies on
the reaction in the gas phase. Such measurements
will truly represent the dose absorbed by the flue
gas. Thus, it is a matter of selecting a most suitable system whose G value is known fairly accurately and the product(s) is easily measurable.
The second best choice would be calorimetry
of flue gas for the determination of average dose.
However, there are uncertainties using this method;
mainly how adiabatic is the system. The main source
of uncertainty arises from the contribution of the
walls of the reaction vessel to the temperature rise
of the flue gas since it is unavoidable that radiation (electrons) will deposit part of its energy in
the walls. However, by judiciously matching the
size of the reaction vessel to the beam energy, this
uncertainty can be minimized.
The third method, measurement with solid
dosimeters, is still less reliable. One can measure
dose using several dosimeters and calculate some
kind of average dose for the entire reaction vessel.
There are two difficulties in this method. First, to
be very accurate, dose should be measured at a
very large number of locations. Second, this is the
measurement of dose rate, and not dose to gas. One
needs then to assume that the residence time of the
gas is the same through each part of the vessel;
that will be true if it were a plug (segregated) flow.
On the other hand, it would be irrelevant if the
gas flow were turbulent. But that is hardly the case.
The only method to measure non-uniformity of
dose absorbed in gas is to measure the dose rate at
various locations in the vessel with fixed dosimeters,
such as cellulose tri-acetate (CTA). This information then can be used to calculate dose absorbed
by different portion of gas as it travels through the
vessel. However, as mentioned above, one then
assumes that there is a plug (segregated) flow. On
the other hand, if the flow were completely turbulent, the dose would be uniform to all the gas. Yet
another method is to carry out a detailed Monte
Carlo simulation of the system. The reliability of
the results of such a calculation of course depends
on the quality of the input data. Thus, we have to
know the type of flow of the gas through the vessel:
plug or turbulent and extent of each. And it is
always prudent then to validate the results with
measurements.
References
[1]. Chmielewski A.G., Zimek Z.: Nuclear technology for
cleaning coal emissions. In: The environmental challenges of nuclear disarmament. Eds. T.E. Baca, T. Florkowski. Kluwer Academic Publishers, The Netherlands
2000, pp. 139-148.
[2]. Chmielewski A.G., Ostapczuk, Namba H., Tokunaga
O., Hashimoto S., Tanaka T., Ogura Y., Doi Y., Aoki
S., Izutsu M.: Radiat. Phys. Chem., 46, 1103-1106
(1995).
119
CATALYTIC CRACKING OF POLYOLEFINE WASTES
IN A LARGE LABORATORY INSTALLATION
Bogdan Tymiński, Krzysztof Zwoliński, Renata Jurczyk
Recycling of polyolefine wastes by thermal degradation into liquid hydrocarbons is being intensivly
studied. Several plants producing a wide hydrocarbon fraction, similar to heavy crude petrol oil
from polyolefine wastes, exist in Poland. Previous
investigations showed that it is possible, without
additional energy consumption, to receive more
valuable gasoline and light oil fractions from the
same plastic wastes. Lately, we concentrated on
checking of quality of wastes on final products.
There were made five experiments with the use of
different wastes. Experiments were made in a large
laboratory installation shown in Fig. Products were
withdrawn from five levels at the distillation column and were analyzed in the same way as reported
in paper [1,2]. The main results are presented in
Table. In the first three experiments the wastes were
prepared in our laboratory from relatively clean
materials. The next two experiments were made
with wastes from a company selecting the wastes.
The wastes were in the form of flakes of unknown
composition. From Table, it follows that the distillates from these wastes (experiments Nos.4 and 5)
contain more heavy fraction and its temperature
of freezing point is higher. In one case, not shown
in Table, the wastes contained a component with
a high melting temperature which caused plugging
the melter. To avoid this design of the melter was
improved. After improvement, the temperature in
Fig. Scheme of a large laboratory installation for catalytic
cracking of polyolefine wastes.
carbons, these temperatures were lower. In the
batch distillation it was easy to separate fractions
with a demanded range of boiling points. Both
Table. Main results of decomposition of plastic wastes (PP – polypropylene, PE – polyethylene).
the melter significantly increased and there was
no more problems with plugging of the melter.
The distillates from the distillation column contain some heavy oil which makes worse the properties of the gasoline and light oil fraction. For the
separation of gasoline and light oil fractions with
higher purity, the distillates were purified in a batch
and continuous distillation process. In the continuous distillation process, the temperature in the
boiler was 360oC and the gasoline fraction collected
at temperatures 230 to 170oC and the light oil fraction – at temperatures 200 to 270oC. During distillation of the fractions containing more light hydro-
methods of distillation give more pure and stable
products [2].
References
[1]. Tymiński B., Zwoliński K., Jurczyk R., Darkowski A.:
Investigation of catalysts for cracking of polyethylene
wastes into liquid hydrocarbons. In: INCT Annual
Report 2005. Institute of Nuclear Chemistry and Technology, Warszawa 2006, pp. 113-114.
[2]. Tymiński B., Zwoliński K., Jurczyk R.: Prace Naukowe
Instytutu Inżynierii Ochrony Środowiska Politechniki
Wrocławskiej, 81, Seria konferencje 12, 263-268 (2006),
in Polish.
120
PROCESS ENGINEERING
ECONOMICAL COMPARISON OF ABSORPTION
AND MEMBRANE METHODS APPLIED
FOR THE ENRICHMENT OF METHANE IN BIOGAS
Marian Harasimowicz1/, Grażyna Zakrzewska-Trznadel1/, Weronika Ziółkowska2/,
Andrzej G. Chmielewski1,2/
1/
2/
Faculty of Chemical and Process Engineering, Warsaw University of Technology, Poland
Raw biogas contains about 55-65% methane (CH4),
30-45% carbon dioxide (CO2), traces of hydrogen
sulphide (H2S) and fractions of water vapour. Enrichment of methane in biogas from anaerobic digestion in fermentation tanks or landfills to obtain
fuel of higher calorific value can be achieved by removing carbon dioxide and other gaseous impurities like hydrogen sulphide. Elimination of carbon
dioxide from the flue gas helps in increasing its calo-
Laboratory experiments with the use of gas separation membranes from polyimide showed a great
potential for membrane permeation as a separation method of gaseous components of biogas [2,3].
At common concentration of methane, a single
stage unit seems sufficient to achieve 94% enrichment, and multistage systems are not required. For
lower methane concentrations (<60%), the standard gas GZ-50 can be produced by a multistage
Table 1. The comparison of the capabilities of absorption and membrane methods.
rific value as well as in eliminating the greenhouse
gas, CO2. Carbon dioxide thus generated can be
utilized as an effective refrigerant.
Current technologies to purify off-gas and increase its caloric value have been primarily limited
to physicochemical methods such as chemical separation, membrane separation, cryogenic separation
as well as adsorption. Chemical methods are based
on absorption under elevated pressure (in water,
30% solution of potassium carbonate (K2CO3),
solution of monoethyloamine, etc.). Other methods
are based on adsorption in which a vital role plays
a suitable adsorbent material [1].
separation. The high permeability of the polyimide
membranes to water vapour and hydrogen sulphide,
common impurities of gas produced in biomass
fermentation process, makes them useful for biogas
processing without special pretreatment.
Preliminary economic evaluations proved that
the application of membranes is reasonable. Table
1 performs the production abilities of the absorption method carried in a Benfield type apparatus.
At the same flow rate of biogas, the absorption
method produces 40% more of methane than
membrane permeation. The productivity of the
membrane system is reduced by methane losses
Table 2. A comparison of energy and reagents consumption in two methods: absorption and membrane separation.
that are equal ca. to 84 000 Nm3 per year. However,
the expenses related to methane losses are compensated by the lower costs of materials consumption.
The chemical method is more energy-consuming,
uses more reagents like potassium carbonate, activator (DEA) and corrosion inhibitor (KVO3). In
this method, in some parts of installation waste
heat can be utilized, that reduces the total energy
consumption.
In Table 2, the consumption of energy and reagents is presented. The energy consumption for
absorption is reduced by waste energy utilized in
some parts of installation.
The investment costs of both methods are listed
in Table 3. The tentative cost evaluation showed
Table 3. Economy of two processes: absorption and membrane separation for methane enrichment – a comparison.
121
the membrane installation is simple, compact and
does not need complex control equipment like
chemical methods. Despite of high costs of the
membrane modules for gas separation, the total
capital costs of the membrane installation are
lower than for the Benfield installation.
Comparison of the operational costs is also
favourable for membrane permeation. Even
though the membrane method consumes much
energy for gas compression, it does not use the
expensive reagents, which are necessary for chemical process.
The work proved that the absorption method
can be superseded by membrane separation. Thanks
to the development of material science that produces modern high selective materials and new
achievements in process engineering, separation
of gaseous components of biogas are reliable. Both
selectivity and efficiency of membranes are sufficient to produce gas of appropriate parameters of
standard gas GZ-50.
References
that the membrane method is more economical
than the absorption method. Both capital and operational costs are lower for the membrane process than for chemical absorption. Additionally,
[1]. Sarkar S.C., Bose A.: Energ. Convers. Manage., 38,
Suppl. 1, 105-110 (1997).
[2]. Harasimowicz M., Orluk P., Zakrzewska-Trznadel G.,
Chmielewski A.G.: Application of polyimide membrane from biogas purification and enrichment. In:
Proceedings of the 5th European Meeting on Chemical
Industry and Environment, EMChIE 2006, Vienna,
Austria, 03-05.05.2006, pp. 617-622.
[3]. Harasimowicz M., Ziółkowska W., Zakrzewska-Trznadel G., Chmielewski A.G.: Economical comparison of
absorption and membrane methods applied for enrichment of methane biogas. In: Proceedings of the XXI
ARS SEPARATORIA, Toruń, Poland, 03-06.07.2006,
pp. 52-54.
STUDY OF BOUNDARY-LAYER PHENOMENA
IN MEMBRANE PROCESSES
Grażyna Zakrzewska-Trznadel, Agnieszka Miśkiewicz, Marian Harasimowicz, Ewa Dłuska1/,
Stanisław Wroński1/, Agnieszka Jaworska1/, Cornel Cojocaru2/
1/
Faculty of Chemical and Process Engineering, Warsaw University of Technology, Poland
2/
”Gh.Asachi” Technical University of Iaºi, Romania
Pressure-driven membrane filtration is an important process for separation of colloids and particulate matter from liquid suspensions in many fields
of engineering and applied science. There are many
examples of application of pressure-driven membrane processes in nuclear technology. Such processes like reverse osmosis, ultrafiltration or microfiltration can be used for liquid radioactive waste
processing, cleaning reactor waters, boric acid recovery and separation of isotopes. The pressure-driven membrane filtration process can operate
at either cross-flow or dead-end flow mode. In case
of dead-end filtration the resistance increases with
formation of the cake on the membrane surface,
while in cross-flow process the deposition continues
until the cake adhesion is balanced by shearing
forces of the liquid passing over the membrane. It
is important to keep appropriate hydrodynamic
conditions in the apparatus that avoid continuous
building-up of the cake layer which results in increase of the resistance and reduction of the permeate flux. The term of concentration polarization
describes the tendency of the solute to accumulate in the membrane-liquid interface. It is important to suppress the concentration polarization by
adjusting the flux on the level that avoid the boundary level development or by promoting the turbulence by all available means. For understanding of
permeate flux decline mechanisms and predicting
of the permeate flow rate, the development of
mathematical models and tools for simulations and
optimization are of great importance.
The hybrid membrane process for removal of
cobalt ions, the main components of the liquid
122
PROCESS ENGINEERING
radioactive wastes produced in Poland, was run in
the ultrafiltration unit equipped with a membrane
contactor with a central rotor. Helical CouetteTaylor flow was expected to promote the turbulence and vortices in the apparatus that resulted
in good transport parameters. Before filtration,
Fig.1. Permeate flux vs. time. Cobalt removal in hybrid process: sorption on activated carbon (AC)-ultrafiltration.
cobalt ions were complexed by soluble chelating
polymers like polyacrylic acid derivatives or
adsorbed on activated carbon seeds dispersed in
the solution. In both cases the improvement of filtration conditions and increase of permeate flux
through the membrane were observed when dynamic conditions were applied (Figs.1-2). There
Jv =
ΔP K
μ δ
(2)
where: K – cake permeability, δ – thickness of the
cake layer.
From comparison of eqations (1) and (2), the thickness of the residual deposit layer can be estimated.
The cake thickness determined for different process conditions, assuming K=10–17 m2, was in a
0.035-0.186 mm range for dynamic conditions.
The thickness showed a marked influence of rotation: the δ values decreased with increasing rotation frequency in the helical-flow membrane apparatus. The influence of rotation on the separation
efficiency was not observed. In experimental
conditions at rotation frequency W=1000-1500
rpm and for ion to polymer concentration ratio
CCo2+/Cpolymer=1/4, the retention factors higher than
90% were achieved.
The models for simulation and optimization
of cross-flow filtration developed from theory of
concentration polarization and response surface
methodology (RSM) were elaborated. The regression analysis in order to find empirical models for
fitting the experimental data of flux decline was
employed. The models were determined by minimization of the residual variance S2res:
2
Sres
=
2
1 n
J (t j ) − J exper
→ min
(
)
∑
j
n − 2 j =1
(3)
The experimental data of the kinetics of flux decline were fitted well by polynomial equation of
type:
J (t ) = a0 + a1 t + a2t + a3t −1 + a4t 2 + a5t 3 (4)
Two responses derived from kinetic curves of flux
decline were used: the average permeate flux calculated by integration of J(t) function from t1=1
min up to tn=180 min as follows:
t
Fig.2. Permeate flux vs. time. Cobalt removal in hybrid process: complexation by polyacrylic acid (PAA)-ultrafiltation.
was evidence that by promoting the turbulence the
resistance of boundary layer and the resistance of
the deposit accumulated on the membrane surface
were reduced. Permeate flux, Jv, can be expressed
as a function of total membrane-cake resistance
by the equation:
Jv =
ΔP
μ ( Rm + Rδ )
1 n
< J >= ∫ J (t )dt
tn t1
(5)
n ⎛
J ( t1 ) − J ( ti ) ⎞
S FD = ∑ ⎜⎜
⎟⎟
J ( t1 )
i =2 ⎝
⎠
(6)
where J(t) means the regression functions determined by regression analysis, and the cumulative
flux decline defined as
(1)
where: ΔP – transmembrane pressure, μ – viscosity
of the liquid.
Membrane resistance, Rm, was estimated from
water permeability and cake layer resistance Rδ –
from the total resistance determined in experiments. On the other hand, permeate flux can be
described by the relationship analogical to the
equation of the filtration through the sediments:
Fig.3. Permeate flux vs. time for optimal conditions:
ΔP*=0.19 bar, QR*=54 L/m2h and W*=2480 rpm.
The cumulative flux decline defined by equation
(6) gives information about all experimental points
in flux decline curve for the time interval studied,
i.e. 1 min≤t≤180 min. By means of the multiple
linear regression method, the empirical models of
cross-flow filtration, which gave the information
about the influence of hydrodynamic parameters
upon J and SFD were developed. The cumulative
flux decline and average permeate flux were used
as the objective functions in optimization by the
Lagrange multiplier method using MathCAD software. The calculated optimal values in terms of actual operating variables were ΔP*=0.19 bar, QR*=54
L/m2h and W*=2480 rpm. For these operation con-
123
ditions, the check out experiment was carried out
to determine the permeate flux vs. time (Fig.3). The
initial flux decline was observed in the time interval
1 min≤t≤60 min; after that a slight increase of flux
was recognized for t>60 min. This means that in
optimal operating conditions the vortices created
by Taylor flow led to self-cleaning effect of the
membrane surface for t>60 min. For all experiments concerning the polymer-assisted cross-flow
ultrafiltration process carried out in the helical
membrane module, the average value of the rejection coefficient was 91.54% with a standard deviation of 4.06%.
A STUDY OF STABLE ISOTOPE COMPOSITION IN MILK
Ryszard Wierzchnicki, Małgorzata Derda
Isotope ratio mass spectrometry (IRMS) methods
play a very important role in food authenticity and
origin control. The measurements of bioelements
(hydrogen, nitrogen, carbon, oxygen, and sulfur)
composition provide a very sensitive tool to food
control. The isotopic methods of origin and authenticity control were recently implemented in European Union for wine, juice, and honey.
The aim of our study is to explore the relationship between isotopic composition of milk and its
origin (regional, seasonal). The stable isotope composition of food is strictly connected with environmental conditions (climate, geographical position
and included pollutants).
The bases for this study are isotopic effects (biological, physical and chemical) which are responsible for different isotopic composition in nature:
soil, air and water. The effect of differentiation of
isotope composition is connected with different
composition of cow diet (maize, grass etc.) and
different composition of drinking water for cows
[1-3]. Seasonal and regional variations of cow diet
composition cause seasonal and regional variations
of isotopic composition of milk and finally dairy
products (Table).
Correlation between the stable isotope composition 18O/16O, 13C/12C, 15N/14N and δD in milk components was analyzed. The variability of the parameters related to environmental factors like:
geology, climate and anthropogenic factors was
studied (Fig.).
Fig. Factors determining the water isotopic composition
of dairy products – a schematic way from the farm to
the consumer.
Finally, on the basis of the collected results a
map of isotopic parameters distribution will be
drawn. The information about the relation between the isotopic compositions and the regional
and seasonal factors will be an important research
Table. Chemical components of milk and their important isotopic composition.
In the frame of the project, many samples of
milk and dairy products from main regions of milk
production were gained. The collected samples
were measured by the use of IRMS DELTAplus
(Finnigan, Germany), connected with peripheral
units as: GasBench, H/Device and Elementar
Analizer (ThermoFinnigan).
result of this project. In the future, on the data
base of authentic value of stable isotope composition, the method for origin control of milk and
dairy products will be proposed.
The study was supported by the Polish Ministry of Science and Higher Education in the frame
of project No. 2P06T03928.
124
PROCESS ENGINEERING
References
[1]. Rossmann A., Haberhauer G., Hölzl S., Horn P., Pichlmayer F., Voerkelius S.: Eur. Food Res. Technol., 211,
32-40 (2000).
[2]. Knobe N., Vogl J., Pritzkow W., Panne U., Fry H.,
Lochotzke H.M., Preiss-Weigert A.: Anal. Bioanal.
Chem., 386, 104-108 (2006).
[3]. Renou J.P., Deponge Ch., Gachon P., Bonnefoy J.C.,
Coulon J.B., Garel J.P., Verite R., Ritz P.: Food Chem.,
85, 63-66 (2004).
INTERLABORATORY TESTS FOR 3H MEASUREMENTS
IN WATER SAMPLES
Wojciech Sołtyk, Jolanta Walendziak, Jacek Palige
Successive observation and measurements of 3H
contents in water samples has been realized in
Poland in a few laboratories starting since 1967. The
measurement of this kind is being performed in
the Institute of Nuclear Chemistry and Technology
(INCT) since 1999 and is connected with the observations of 3H concentration changes in surface
samples of water with 3H concentration in an interval of 0-20 TU.
In test VI participated 86 laboratories and 6
samples of water with 3H concentration in an interval of 0-25 TU and with one unknown sample
with a concentration of about 500 TU were measured.
Table 1. Results of test V.
and underground waters in the surrounding of the
coal mine “Bełchatów”. About 240 3H measurements are realized each year.
The results of these measurements are used for the
diagnosis of environmental processes occurring in
the open lignite mine area.
The International Atomic Energy Agency
(IAEA) organizes from time to time (every 5 years)
The results of tests are presented in Tables 1
and 2.
The real concentration, Cr, is defined as the
mean value – the result of averaging all data obtained by the test participants whose result Ci fulfilled the condition |Ci – Cr|<2δ.
The measured concentration is the result obtained
in the INCT laboratory with an error of ±0.5 TU.
Table 2. Results of test VI.
interlaboratory tests for checking the correctness
of data obtained in the laboratories which are registered in the IAEA – laboratories net.
The INCT laboratory participated in the tests
organized in 1994 (test V), 2000 (test VI) and 2005.
In test V participated 91 laboratories from numerous countries which measured the same 4
The results of the test realized by the IAEA in
2005, for the moment, were not published.
The data obtained in the INCT laboratory indicate sufficient agreement with the interlaboratory
results especially with those for higher 3H concentration.
MODELLING FOR GROUNDWATER FLOW
IN THE OPENCAST BEŁCHATÓW AREA
Robert Zimnicki
The groundwater flow modelling is one of the most
important steps in characterizing transport and
properties of contaminants in industrial area like
coal-mine. The majority of processes based on natural raw material exploitation causes a significiant
environment destruction. The majority of problems
concerning water quality like salinity or organic pollutant contents, water interchange and their resi-
dence time in ground could be forecasted by computer simulation of flow processes.
Modelling for the Bełchatów opencast area
started in 2006. Simulation was done using Modflow
software based on the application of the finite element method for the solution of appropriate 3D
flow equation system for porous media. The Darcy
law was applied for filtration velocity description.
125
Fig. Scheme of exploitation area.
At the beginning, data concerning porosity of the
materials, boundary conditions for a certain part of
opencast, like salt dome, outer dump, first driving
area, were collected. The applied model consist of
six layer describing three principal geological plies
(Mesozoic, Quaternary and Cenozoic). The scheme
of exploitation area is presented in Fig., where the
principal mine objects are indicated.
The Bełchatów model consist of 680x360x6 cells,
in reality, the dimensions are 34 000 m length and
18 000 m width. Step size between bend is 50 m.
The porosity for sand is equal to 45%, granite –
0.7% and total as 10% were sets. The transmissi-
vity for all area 5 m2/day were preset. Rain parameter is equal to 0.0016 m/day.
Actually the model is being verified. The sensitivities of applied procedures on boundary conditions changing is tested [1].
References
[1]. Zimnicki R., Owczarczyk A., Chmielewski A.G.: Obserwacja zmian hydrochemicznych wód podziemnych w rejonie powstającej odkrywki węgla brunatnego. In: Materiały z IV Ogólnopolskiej Konferencji Naukowo-Technicznej “Postęp w inżynierii środowiska”, Bystre near
Baligród, Poland, 21-23.09.2006, pp. 521-529 (in Polish).
TRACER AND CFD INVESTIGATIONS
OF SEDIMENTATION PROCESSES IN RECTANGULAR SETTLER
Jacek Palige, Andrzej Dobrowolski, Sylwia Ptaszek, Andrzej G. Chmielewski
Wastewater treatment process is realized in different apparatus such as equalizers, aeration tanks,
settlers and final sedimentation basins. The treatment efficiency strongly depends on the work of a
secondary settler.
Many researches concerning the sludge sedimentation process were carried out [1-3]. Actually,
few methods are used for investigations of settlers.
The tracer method is used for the determination
of residence time distribution (RTD) function and
Fig.1. Scheme of a secondary settler and experimental results of spatial sludge ceoncentration distribution: A – in profiles at 8, 24 and 37 m from the wastewater input as a function of depth; B – 1 and 2 m below the water table in the
axis of the settler.
126
PROCESS ENGINEERING
Fig.2. Distribution of axial velocity component in planes orthogonal to the settler axis at distances: 6, 15, 25, 30 and 38 m
from the wastewater input.
computational fluid dynamics (CFD) [4-6] for obtaining the water flow structure inside a settler
tank.
In this work, the results of tracer investigations
and CFD simulations for an industrial rectangular
settler with immersed input (width 10 cm in all
settler width) are presented. Volume of unit under
investigation was V=1050 m3 (length L=41.5 m,
height H=3÷4 m), flow rate of wastewater q=160
m3/h, output of sewage in the settler was realized
by overflow. For this inflow structure, the sediment
concentrations have been measured 1 and 2 m
below the water table in the axis of the settler and
in profiles at 8, 24, 37 m from the wastewater input as a function of depth. The scheme of the settler and the distribution of sediment inside the
settler are presented in Fig.1.
The velocity of sludge sedimentation was determined in laboratory tests. The value of this vel-
ocity was 3 cm/min. Using the CFD codes, the sedimentation process of monodisperse sludge with
input concentration 2 kg/m3 and flow rate of fluid
0.041 m3/s was simulated. Numerical 3D simulations
of the sedimentation process with numerical code
of FLUENT software application were carried out
using the Euler-granular scheme and standard k-ε
model of flow turbulence for a mixture of water
and sludge.
The characteristic backflow, up to 30 m in settler
(Fig.2) for this construction of inflow, was observed
near the surface and bottom of the tank.
Numerical sludge concentration distribution as a
function of depth in the axis of the settler are presented in Fig.3.
A satisfactory agreement of numerical and experimental curves of concentration sludge distribution
was observed in profiles 1 and 2. In profile 3, a
large decrease of sludge concentration obtained
in numerical simulation is connected with the fact
that, for example, the sludge drift in the bottom
and scrapper movement in real settler tank is not
taken into account.
References
Fig.3. Profiles of sludge concentration in the axis of the settler as a function of depth (8, 24, 37 m from the wastewater input).
[1]. White D.A., Verdone N.: Chem. Eng. Sci., 55, 2213-2222
(2000).
[2]. Berres S., Buger R., Tory E.M.: Chem. Eng. J., 111,
105-117 (2005).
[3]. Burger R., Karlsen K.H., Towers J.D.: Chem. Eng. J.,
111, 119-134 (2005).
[4]. Krebs P., Armbruster M., Rodi W.: Gaz, Woda Tech.
Sanit., 11 (2000), in Polish.
[5]. Palige J., Dobrowolski A., Owczarczyk A., Chmielewski A.G., Ptaszek S.: Inż. Ap. Chem., 42, 72-75 (2003),
in Polish.
[6]. Palige J., Owczarczyk A., Ptaszek S.: Inż. Ap. Chem.,
44, 24-26 (2005), in Polish.
NATIVE AND TRANSPLANTED Pleurozium schreberi (Brid.) Mitt.
AS BIOINDICATOR OF NITROGEN DEPOSITION
IN A HEAVY INDUSTRY AREA OF UPPER SILESIA
Grzegorz Kosior1/, Aleksandra Samecka-Cymerman1/, Andrzej G. Chmielewski,
Ryszard Wierzchnicki, Małgorzata Derda, Alexander J. Kempers2/
1/
2/
Department of Ecology and Nature Protection, Wrocław University, Poland
Department of Environmental Sciences, Radboud University of Nijmegen, the Netherlands
During the period of 90 days, an assay was carried
out with the moss Pleurozium schreberi transplanted from an uncontaminated control site to
the most polluted industrial region of Poland in the
Upper Silesia (Poland). Within the same period also
samples of native Pleurozium schreberi growing in
the industrial region were collected together with
the same species from an unpolluted control site.
Concentrations of total nitrogen in soil, nitrate and
ammonia in rainfall, nitrogen in mosses as well as
lead and zinc as pollution markers in mosses were
measured. The natural abundance of 15N was determined in transplanted, native and control Pleurozium schreberi. The examined soils from the polluted sites were contaminated with high levels of
nitrogen and also the concentrations of lead and
zinc in mosses seriously exceeded the levels of these
elements in plants from the control sites. The input of atmospheric ammonium nitrogen by deposition significantly exceeded that of the nitrate nitrogen at all sites. Established correlations confirmed
a general suitability of the examined moss species
for at least a rough estimation of the nitrogen input. The transplanted Pleurozium schreberi was a
127
better nitrogen accumulator in the less polluted
parts of the area showing a relation between the
δ15N signature and the tissue nitrogen concentration to the ratio NH4+N/NO3–N after 45 days of exposure. The same species transplanted into the
more polluted sites of the industrial area did not
reach the level of nitrogen of native species within
90 days of exposure and showed a relation to atmospheric nitrogen deposition only after 90 days
of exposure. Therefore, it may be concluded that
the transplanted moss needs at least 90 days in its
new environment to give indications for polluting
nitrogen compared to the indications obtained
from the native mosses. Therefore, the transplants
were worse indicators of nitrogen deposition in
heavy polluted areas compared to those in less
polluted areas.
128
MATERIAL ENGINEERING, STRUCTURAL STUDIES,
DIAGNOSTICS
IDENTIFICATION OF LEAD WHITE
OF THE 15th CENTURY GDAŃSK PANEL PAINTINGS
BY MEANS OF INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS
Ewa Pańczyk, Justyna Olszewska-Świetlik1/, Lech Waliś
1/
Faculty of Fine Arts, Nicolaus Copernicus University, Toruń, Poland
Connection between the content of trace elements
in lead white and the place, time and technology of
Table. Description of the analyzed samples.
its production can be determined on the way of extensive studies carried out on sample paintings rep-
resenting different periods in history and various
countries [1-5]. More sensitive detection methods
currently applied in neutron activation analysis
(NAA), and first of all, high-resolution gamma
spectrometry allow to increase the number of detectable elements and to more accurately determine their concentrations in the lead white [2]. A
more complete distribution pattern of trace elements permits also to take into account the elements that were not present in original paints in a
given period of history. This is particularly important for elimination of the impurities accidentally
introduced into paint during creation of a painting. The objective of the work are systematic studies on the lead white in Polish painting. The presented results of analyses constitute merely a part
of broader studies on lead white produced in 15th
and 16th centuries. The following work contains
the results of researches of the chosen set of panel
paintings of Gdańsk from the second half of the
15th century. A set of 16 pieces of panel painting,
most of which were taken from the important shrine
of Gdańsk – the Church of the Blessed Virgin Mary
– were the object of the research. Additionally, the
study of the retable from the Parish Church at
Wróblewo, an altar from the St. Peter and St. Paul
church at Hel and Grudziądz Polyptych from the
Castle of the Teutonic Knights at Grudziądz were
taken. The workshop of these three panel paintings is closely connected to Gdańsk painting tradition. Only a part of works of art remained until our
times [6]. Those that were preserved, in most cases
constitute only a part of retables (panels of polyptychs, predellas).
All the samples were taken from paintings subjected to a routine maintenance work after reveal-
129
ing their structure and state of preservation of the
original layers, After removal of protective coating with a scalpel under a microscope, a sample of
the white was taken directly to a quartz ampoule.
The sampling spots were selected so that they had
not shown admixtures of other pigments as indicated by UV luminescence tests. Detailed description of the paintings is presented in Table. 1-6
samples from each object, with a mass from 0.1 to
1 mg were collected.
The analysis of lead white samples was carried
out using the instrumental neutron activation
analysis (INAA) method without chemical separation, using standards of analyzed elements. The
samples were packed together with standards of
such elements as Na, K, Sc, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Ga ,Ge, As, Se, Br, Rb, Sr, Zr, Mo, Ru,
Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu,
Tb, Dy, Ho, Er, Yb, Lu, Hf, Ta, W, Ir, Au, Hg, Th
and 238U. Also attached were the standards of gold
and scandium evaporated onto a piece of aluminium foil. They played the role of the thermal
neutron flux monitor.
Irradiation of the samples was carried out in the
MARIA reactor at Świerk, in a channel with 8*1013
n/cm2s thermal neutron flux. The irradiation time
was 24 h with subsequent 8-hour cooling. Then,
the irradiated samples were unpacked and washed
in 1:1 hydrochloric acid solution and rinsed in alcohol to remove surface contaminations.
Measurements of activity of samples and standards prepared in such a way were carried out using an HP germanium detector with an active volume of 80 cm3 and an energy resolving power of
1.95 keV for the 1333 keV peak from 60Co. The
detector cooperates with a S100 Canberra analyzer,
Fig. Dendrogram of 56 lead white samples taking from 19 panel paintings (number of features is 28) – standardized
variables.
130
controlled by IBM/PS-2. The analysis of complex
gamma radiation spectra was carried out using
micro-SAMPO and Gene 2000 programs. The
measurements were repeated six times within three
months after irradiation. The measurement time
varied between 300 and 10 000 s. Thirty two elements were identified and determined in the analyzed samples.
Ultimately, 28 elements were selected for
multiparameter statistical analysis aimed at identifying the degree of similarity of analyzed paintings.
The clustering analysis using STATISTICA
(StatSoft) program was carried out to identify the
similarity degree of analyzed objects. The clustering analysis was carried out for standardized variables.
The results of clustering analysis for all the
tested 19 panel paintings (56 samples of lead white)
are presented in Fig., which clearly shows division
into four groups. Based on to date quantitative
analysis of the trace elements in lead white collected from paintings from the 15th-19th century,
it can be concluded that lead white from the studied panel paintings shows a lower content of cop-
per and manganese and a higher content of sliver
and antimony than lead white from regions south
to Alps and is more similar to lead white applied
in Northern Europe [4,5,7]. The results of the conducted analyses revealed features characteristic of
painting technique of Gdańsk of the second half
of 15th century.
References
[1]. Perlman I., Asaro F., Michel H.V.: Annu. Rev. Nucl.
Sci., 22 (1972).
[2]. Sayre E.V.: Advan. Activ. Anal., 2 (1972).
[3]. Fleming S.J.: Authenticity in art. London 1975.
[4]. Houtman J.P., Turkstra J.: Neutron activation analysis
and its possible application for age determination of
paintings. In: Proceedings of the Conference on Radiochemical Methods of Analysis, Salzburg, Austria 1964.
IAEA, Vienna 1965, vol.1.
[5]. Lux F., Braunstein L.: Z. Anal. Chem., 221 (1966), in
German.
[6]. Olszewska-Świetlik J.: Technologia i technika gdańskiego malarstwa tablicowego drugiej połowy XV wieku. Toruń 2005, in Polish.
[7]. Pańczyk E., Ligęza M., Waliś L.: Nukleonika, 37, 29
(1992).
ELEMENTAL COMPOSITION AND PARTICLE MORPHOLOGY
OF LEAD WHITE PIGMENTS
Bożena Sartowska, Ewa Pańczyk, Lech Waliś
The analysis of pigments on artworks is of major
significance in art conservation as it leads to detailed
characterization of materials and is thus important
for dating and authentication, as well as for possible conservation or restoration of artwork. Pigment
analysis can be a challenging problem due to the
complexity of materials analyzed because one may
have to identify several different pigments used in
multicomponent mixtures and in different paint
layers. The problem becomes even more demanding for artworks in which sampling is either extremely limited or even forbidden. Several analytical techniques for identification of pigments have
been in use for many years such as scanning electron microscopy (SEM), energy-dispersive X-ray
(EDX), X-ray diffraction (XRD), X-ray fluorescence (XRF), Fourier-transform infrared spectroscopy (FT-IR), UV-visible absorption, particle-induced X-ray emission (PIXE), proton-induced
gamma-ray emission (PIGE), Rutherford backscattering spectroscopy (RBS), instrumental neutron activation analysis (INAA) and prompt gamma
activation analysis (PGAA) [1-3].
Natural and synthetic pigments are subject to
various geological, mining and manufacturing processes, which are unique to each manufacturer.
Understanding of the manufacturing process of
common pigments allows the forensic scientist to
understand how trace elements may become incorporated into the final product, and validity of
the concept of using their association pattern in
the paint as a provenance establishment techniques.
For the last twenty centuries, lead white has
been one of the most frequently used pigment. Its
purity is directly related with the development of
methods of production and purification of lead.
Owing to this fact, it is possible to distinguish the
groups of the artists by whom the painting has been
created by determining trace elements present in
the lead white used. In addition, it is possible to
identify repainted fragments and conservation
steps made which is of great importance to art historians. The variation seen in trace element compositions according to region and time, proper
authentication would require compiling a library
of analyses of carefully documented paintings to
compare statistically the painting in question. Such
work can confidently contribute to the reassignment of dates and the placement of objects in their
correct historical context [1-4].
The lead white of commerce that has been used
in painting is the basic carbonate 2PbCO3·Pb(OH)2.
Lead carbonate hydroxide is chemically equivalent
to the naturally occurring hydrocerrusite, however,
the mineral equivalent is extremely rare and consequently rarely used as a pigment source. During
the Roman period, lead white was well-known historically as a synthetic pigment that is made from
metallic lead and vinegar. Lead white was commonly adulterated with other white pigments, particularly chalk, baryte and kaolinite to cut cost [4].
The goal of the described work is the comparison of trace element patterns and particle morphology of contemporary lead white pigments and
Bologna chalk which was used very often as an
admixture to lead white specially in grounding of
paints, with lead white pigment taken from the
panel painting of Crucifixion Triptych (Gać Śląska,
dating on 1440/1450) which belongs to the so-called
Silesian Painting School. We used two methods:
INAA for determination of trace elements and SEM
for revealed morphology of investigated pigments.
The activation analysis is one of the modern
instrumental analytical methods. Since 1950 it has
been an important technique used to analyze trace
Table. Composition of lead white and chalk samples [ppm].
131
elements at a level of ppb or even better in a wide
range of materials. In the 1950’s there was no technique that could compete with this method. At
present, though there are other methods with comparable sensitivity, neutron activation analysis
(NAA) still offers new capabilities thanks to the
development of electronics and availability of increasingly technologically advanced instruments.
This results in enhanced precision, accuracy and
repeatability [1,3].
132
A
B
Fig.1. Pigments: A – calcite CaCO3, B – lead white 2PbCO3·Pb(OH)2.
The analysis of lead white samples was carried
out using the INAA method without chemical
separation, using standards of analyzed elements.
The samples were packed together with standards
[3]. Also attached were the standards of gold and
scandium evaporated onto a piece of aluminium
foil. They played the role of the thermal neutron
flux monitor.
Irradiation of the samples was carried out in
the MARIA reactor at Świerk, in a channel with
8x1013 n/cm2s thermal neutron flux. The irradiation
time was 24 h with subsequent 8-hour cooling. Measurements of radioactivity of samples and standards
were carried out using an HP germanium detector
with an active volume of 80 cm3 and an energy resolving power of 1.95 keV for the 1333 keV peak
from 60Co. The detector cooperates with a S100
Canberra analyzer, controlled by IBM/PS-2. The
analysis of complex gamma radiation spectra was
carried out using micro-SAMPO and Gene 2000
programs. The measurements were repeated six
times within three months after irradiation. The
measurement time varied between 300 and 10 000
s. Thirty two elements were identified and determined in the analyzed samples. The results of this
analysis are presented in Table.
It follows from the comparison of the data sets
obtained for the investigated samples that the oil
colour from Grumbacher N.Y. firm characterized
a very high concentration of zinc which is an ad-
A
mixture in this contemporary paint. In original,
lead white taken from the Crucifixion Triptych contained a higher concentration of copper and lower
of silver than in contemporary pigments.
The same four different kinds of pigments were
investigated by means of SEM: powder of CaCO3
– calcite, powder of 2PbCO3·Pb(OH)2 – lead white
pure pigment (Poland), oil colour form Grumbacher
N.Y. and original lead white pigment taken from
the panel painting of the Crucifixion Triptych with
linseed oil binder.
Powders of pigments and small pieces of paints
were fixed at the microscopic tables using the conductive glue (Quick Drying Silver Paint, Agar Scientific Ltd.). The surfaces of the samples were coated
with a thin layer of metal to reduce the charging
which takes place during SEM observations [5].
They were covered with a thin layer (less than 10
nm) of gold using a vacuum evaporator JEE-4X
(JEOL, Japan). Observations were carried out using scanning electron microscope DSM 942 (Zeiss,
Germany).
Powder of CaCO3 consists of agglomerates of
needle-shape grains (Fig.1A). Needles-grains with
different sizes are in the shape according to the
theoretical calcite orthorhombic crystal system [6].
Powder of lead white consists of agglomerates
of hexahedron plate-shape grains (Fig.1B). The
sizes of these plates are: the diagonal – about 2.4
μm and the thickness – about 0.3 μm. The shape
B
Fig.2. Oil colour (Grumbacher N.Y.): A – surface, B – brittle fracture.
A
133
B
C
Fig.3. Lead white from the panel painting Crucifixion Triptych with linseed oil binder: A – bulk sample, B – dispersed
particles x20 000, C – dispersed particles x5000.
of the observed plates are in good agreement with
the theoretical hexagonal crystallographic lattice
of 2PbCO3·Pb(OH)2 [6].
The Grumbacher N.Y. oil colour was in the dried
form as a bulk material. Pieces of this paint have
the smooth surface without cracks and inclusions.
Visible grains are fixed in the matrix. Diameter of
the single grain is less than 1.1 mm (Fig.2A). Surface of brittle fracture shows a lot of cracks and
voids, free pieces of material could be distinguished.
Much smaller particles (about 0.3 μm) fixed in the
matrix are visible at the fracture (Fig.2B).
The sample of lead white from the Crucifixion
Triptych was in the form of some small particles of
dried paint. Their surfaces are rough with voids
and inclusions (Fig.3A). The interesting objects –
groups of the spherical particles are also observed.
The spheres are in different sizes: from less than
0.3 μm in diameter (Fig.3B) to rather big – 17.6
μm in diameter (Fig.3C). This shape is the result
of the pigment formation: the particles of solid
phase of 2PbCO3·Pb(OH)2 are dispersed in the
liquid phase of used oil [7].
Scanning electron microscopy is a useful tool
for investigations of the morphology of pigments
and paints. The investigated pigments consist of
small particles with the shape in accordance with
the theoretical shape of crystallized CaCO3 and
2PbCO3·Pb(OH)2. The investigated paints show
the pigment particles fixed in the oil matrix. The
oil paint from Gać Śląska shows a spherical shape
of the pigment particles dispersed in used oil.
In this work, it was demonstrated that a combined method approach, performed directly on the
artwork and small samples, is able to identify the
materials that were used to manufacture artefacts.
The consequence of these findings, in relation to
dating and authenticating the investigated artefact,
are consistent with the art historical observations.
According to our experience, the NAA and
SEM methods are a powerful tool to identify and
characterize the pigments.
References
[1]. Houtman J.P., Turkstra J.: Neutron activation analysis
and its possible application for age determination of
paintings. In: Proceedings of the Conference on
Radiochemical Methods of Analysis, Salzburg 1964.
IAEA, Vienna 1965, vol.1.
[2]. Lux F., Braunstein L.: Z. Anal. Chem., 221 (1966), in
German.
[3]. Pańczyk E., Ligęza M., Waliś L.: Nukleonika, 37, 29 (1992).
[4]. Eastugh N., Walsh E., Chaplin T., Siddall R.: Pigment
compendium. Elsevier 2004.
[5]. Goldstein I.J.: Electron microscopy and X-ray microanalysis. A text for biologist, material scientists and
geologists. Plenum Press, New York 1992, 820 p.
[6]. Poradnik fizykochemiczny. Praca zbiorowa. WNT,
Warszawa 1974, 1985 p. (in Polish).
[7]. Spychaj T., Spychaj S.: Farby i kleje wodorozcieńczalne.
WNT, Warszawa 1996, 323 p. (in Polish).
134
ULTRAVIOLET BLUE FLUORESCENCE
OF CENTRAL EUROPEAN BAROQUE GLASS (FURTHER RESULTS)
Jerzy Kunicki-Goldfinger, Joachim Kierzek, Piotr Dzierżanowski1/
1/
Faculty of Geology, Warsaw University, Poland
About 1200 colourless glass vessels originated
mainly from central European areas and dated to
17th and 18th centuries were analyzed by the use
of energy dispersive X-ray fluorescence (EDXRF)
analysis and examined under UV-C radiation.
These observations were carried out to distinguish
the items that show blue fluorescence, which is
associated with the presence of lead in glass. The
colour of fluorescence was determined with the
naked eye. Also, small samples were taken from
the 88 examined objects. They were analyzed by
the use of electron probe microanalysis (EPMA).
The project constitutes a continuation of our
previous paper [1].
A band with the dominant line of 253.7 nm
(usually denoted as UV-C) was applied. Commercially available sources of the UV-C radiation were
used (two low pressure TUV 15 V mercury lamps,
manufactured by Philips). They were installed in a
special chamber for safe observation of the phenomenon. The total radiation intensity in the
chamber amounted to 8.257x10–4 W/cm2 (for the
wavelength range of 200-398 nm), with a single
dominant peak of 2.503x10–4 W/cm2 for a wavelength of 254 nm.
Energy dispersive X-ray fluorescence was used
in a surface manner. The 109Cd and 241Am radioisotope annular sources were applied to excite the
elements in the glass. X-ray spectra were measured
using Si(Li) and a planar HPGe detectors. The live
time of the measurements was 600 s. The analyzed
Analyses by wavelength dispersive spectrometry
in the EPMA system were carried out using
Cameca SX-100 at the Electron Microprobe Laboratory, Faculty of Geology, Warsaw University.
Standards were oxides and minerals. Corning B,
C, D, and NIST 610, 612, among others, were used
as secondary standards.
The obtained results have confirmed that blue
fluorescence of baroque central European vessel
glass is connected to the presence of lead in glass.
There is no border PbO concentration that cause
the phenomenon. The PbO concentration even
below 0.2% can cause the bright blue fluorescence.
On the other hand, in this range slightly below
0.5% of PbO, a few examined glasses did not show
the fluorescence at all. These vessels are attributed
to unknown Polish and/or Russian factories run
by the end of the 18th century.
The presence or absence of blue fluorescence
does not seem to depend on the concentration of
Mn and Fe, thought the relative ratios of Pb, Mn
and Fe influence the changes of glass fluorescence
under UV-C in the case of such small lead concentrations.
When the PbO content is higher (over 0.5%),
glass shows this fluorescence independently of the
kind of glass matrix composition. There is one exception found and it concerns a few vessels attributed to Zechlin (or Potsdam), Brandenburgia
(Fig.1). It should be underlined that not all glasses
from this glass centre behave in this way; other
Fig.1. Triangular diagrams for the variables Pb, Mn, and Fe. The variables have been transformed in such a way that the
sum of their values is constant for each case.
area of glass amounted to approximately 2 cm2.
No quantitative chemical analysis was carried out
by the use of EDXRF. Only PbO contents were estimated.
examples also containing lead show the blue fluorescence. We do not know the reason of it.
Three groups of leaded central European glass,
which show blue fluorescence under UV-C radia-
< – below detection limit.
For all samples: P2O5<0.4.
Table. Chemical composition of 21 glasses analyzed by the use of EPMA [wt%].
135
136
tion, have been distinguished (tentatively marked
A, B, and C) (Fig.2). “A” is white (chalk) glass with
highest PbO concentration reaching c. 2%. “B” is
crystal glass. The PbO content did not exceed 6%.
“C” is also crystal glass, but with the PbO content
over 6%. These groups differ from one another
in the chemical composition as a consequence of
the application of determined recipes and raw materials.
Chemical composition of 21 glasses with the
highest PbO concentration analyzed by the use of
EPMA (in wt%) are presented in Table. The items
have been sorted according to their lead content
and the presence of blue colour of their fluorescence
is indicated. The PbO level in the remaining 67
glasses, also examined by the use of EPMA, remains below 0.04% and they did not show blue
fluorescence. It can be seen that the glasses with
PbO content over about 0.2-0.3% show this distinct
blue fluorescence. Though, there are two exceptions and both vessels were produced in Zechlin.
According to our previously published results,
we can now divide leaded crystal central European
glass from the 18th century into two groups, B and
C. The further conclusion is that all glasses that
belong to group C showed blue fluorescence.
Among the glasses from group B, we have found a
few exceptions.
We have also found a few examples with very
low lead content (or with its concentration below
the detection limit) that exhibit weak pale-blue
fluorescence. This phenomenon is caused probably
by the presence of other kind of fluorescent centre
in glass than lead.
Spectroscopy seems to be undoubtedly needed
for further studies on this phenomenon.
The project has been carried out at the Institute
of Nuclear Chemistry and Technology in Warsaw
within the frameworks of a few separated projects
since 1998.
The following museums made the vessels available for examination: the National Museums
(Gdańsk, Cracow, Poznań, Warsaw, Wrocław), the
Royal Castle in Warsaw, the Wawel State Art Collection, the Czartoryski Museum and the Jagiellonian University Museum (Cracow), the District Museums (Jelenia Góra, Rzeszów, Tarnów), the Łańcut Castle Museum, Museum in Nieborów and
Arkadia, the Museum-Palace in Wilanów, the Historical Museum of Warsaw and private collectors.
Fig.2. The scatter plots for PbO [wt%] and, respectively
Rb, Y and Zr. Rb, Y and Zr contents are expressed
in arbitrary units. Three groups of leaded glass have
been distinguished.
References
[1]. Kunicki-Goldfinger J.J., Kierzek J.: Glass Technol.,
43C, 111-113 (2002).
LATE 17th CENTURY GLASS VESSELS FROM EILAND
– TECHNOLOGICAL APPROACH
Jerzy Kunicki-Goldfinger, Martin Mádl1/, Piotr Dzierżanowski2/
1/
National Museum & Institute of Art History, Academy of Sciences of Czech Republic, Prague,
Czech Republic
2/
Faculty of Geology, Warsaw University, Poland
We know relatively little about glass production
in the second half of the 17th century, when vari-
ous technologies and manufacturing processes that
would later become commonplace were still being
developed and tested. In the catalogs of European
glass collections, we find only a few objects that can
be reliably dated between the 1650s and the 1690s,
with the exception of enameled glass that derives
from the Renaissance tradition.
This article draws attention to several luxury
objects that are intriguing because of their crizzled
glass and forming and finishing techniques. We have
managed to date these objects with considerable
precision. At the same time, we have attempted to
situate them in the broader context of European
glass production, and specifically to link them with
the important Hessian glassmaker Georg Gundelach and his heretofore little-known work in Bohemia.
Our primary method for the identification of
objects has been art-historical analysis, augmented
by chemical analysis of the selected samples. Three
objects attracted our special attention. One of them
is a goblet of Matthias Helfried von Plönstein decorated with a prelate’s coat of arms in the glass collection of the Prague City Museum (inv. no. 137 969).
The next object that deserves our attention is a goblet of Christoph Lodron and Catharina von Spaur
bearing the coat of arms of the Lodrons in the collection of the Museum of Applied Arts in Prague
(inv. no. 4 462). Another vessel that can be linked
with the Thun court and perhaps also with the glassworks in Eiland is a small jug of Marie Adelheid,
Countess Thun with the motif of the Virgin and
Child in the collection of the Department of Czech
History of the National Museum in Prague (inv. no.
H2 – 6 579).
The main goal of this part of our study was to
identify the technology used in the manufacture of
the three glass vessels. We assumed that this would
contribute important complementary information
to the study of the provenance and dating of the
objects.
Two preliminary assumptions have been made
in writing this section. First, we use the term “glass”
to mean only the material, not the object, and we
characterize this “glass” exclusively in terms of its
chemical composition. Second, when interpreting
the chemical composition, we consider only the
likely intention of the glassmaker, assuming that
this composition reflects, at least to some extent,
the recipe used. This method of analysis differs
from an assessment of the optical quality of the
glass that is made with the naked eye, since the
latter involves an examination of the final product, which does not always reflect the glassmaker’s
intention. In some instances, glass that was intended
to be of particularly fine quality emerged from the
manufacturing process as an inferior material, and
the reverse also happened.
We use the terms “crystal glass”, “white glass”
(also referred to as “chalk glass”), and “ordinary
glass” in referring to the chemical composition of
the glass. These terms correspond to the three types
of glass compositions developed by the Venetians:
cristallo, vitrum blanchum, and vetro commune [1].
These three basic formulas for colorless glass were
used during the period under discussion, and they
are known from documentary sources. Their char-
137
acteristics and distinct properties have been discussed elsewhere [2].
We took small samples of glass from the three
vessels and analyzed them by wavelength-dispersive spectrometry with electron-probe microanalysis (EPMA). The samples for analysis were collected with a diamond point. They came from the
pontil mark of the goblet of Matthias Helfried von
Plönstein; from the bowl of the jug of Marie Adelheid, Countess Thun; and from the stem of the goblet with the coat of arms of the Lodron family. The
samples were mounted in blocks of epoxy resin,
polished to 0.25 μm, and coated with a layer of
carbon. The analyses were carried out using a
Cameca SX-100 equipped with three simultaneously working spectrometers (PET, LIF, TAP
crystals, and PC2 for boron) at the Electron Microprobe Laboratory (Faculty of Geology, Warsaw
University). The measurement conditions were as
follows: (i) for main constituents – 15 kV, 6 nA, 20
μm beam diameter, counting time 20 s for each
element; (ii) for minor and trace constituents (with
fixed concentration of main constituents) – 20 kV,
100 nA, 80 μm beam diameter, counting time 20-60
s; and (iii) for boron (with fixed concentration of
main and minor constituents) – 5 kV, 100 nA, 20
μm beam diameter, counting time 20 s. The standards were oxides and minerals. Corning reference
glass D, CRM-glasses 4001 and 4002 (Glass Institute, Hradec Králové, Czech Republic), and NIST
CRM-glasses 610 and 612 were used as secondary
standards.
The results are presented in Table (Nos.1, 2,
and 11). For comparison, we include the results of
chemical analyses of luxury glasses manufactured
in central Europe from the late 17th through the
18th centuries. Because there are almost no published chemical analyses of central European luxury
baroque glasses from the late 17th century, we have
relied mainly on examples from the first half of
the 18th century and on two vessels from about
1700 that were specially examined for our study.
They are shown in Table as Nos.3 and 4. Both
glasses are crizzled. The analyses were also carried out using EPMA, under the same conditions.
The presence of certain chemical components
and their concentrations in all of the glasses in
Table provide clues to their provenance and dating. The near absence of MgO and P2O5, as well as
the presence of As2O3, suggests that the glass was
melted from batches containing potash (and/or
saltpeter) as a flux, arsenic, and other ingredients.
Saltpeter and arsenic began to be used in the production of certain types of colorless vessel glass in
central Europe probably not earlier than in the
second half of the 17th century.
The glasses in Table are grouped into three sets
according to composition. The first set consists of
six examples of central European crystal glass dating from the late 17th century and about 1700. It
includes the goblet of Matthias Helfried von Plönstein and the goblet with the coat of arms of the
Lodron family. These examples are distinguished
by their uniquely low concentration of CaO, which
is significantly below one weight percent (<1%),
All results are for colorless glasses. Nos.1-4, 6, 8, and 10 are crizzled.
+ – found but not quantified; < – below detection limit.
For all samples: P2O5<0.4, SO3<0.4, Rb2O<0.07, ZrO2<0.01, Y2O3<0.03, ZnO<0.03.
Column 3: NM – National Museum, MAA – Museum of Applied Arts, MP – Museum Palace.
Table. Chemical composition of luxury vessel glass from central Europe, late 17th and 18th centuries [wt%].
138
and five of these vessels have relatively high levels
of B2O3. The EPMA system used for the analyses
allowed us to quantify boron oxide only when its
concentration exceeded about 0.7-1%, depending
on the glass matrix. Because of this, in certain cases,
boron could be found but not quantified.
The low CaO content suggests that calcium
could have been introduced to the glass as contamination or as a minor constituent of certain raw
materials (possibly potash or wine stone). If this
type of crystal glass was made without adding calcium as a raw material, it may be considered a successor to Venetian cristallo. Another possible explanation is that chalk was added as an ingredient
in very small quantities. Chalk appears in lists of
raw materials used during this period, but we do
not know if it was used in the production of this
particular type of glass. The higher concentration
of B2O3 seems to be a characteristic only of crystal
glass, and documentary sources from the period
confirm that borax was used in the production of
crystal glass. Five of these six early examples of crys-
139
The second set contains four objects from the
first half of the 18th century. They were made in
Dresden, Zechlin, Naliboki, and an unidentified
German glasshouse. The composition of this later
crystal glass is distinguished by a higher CaO content (which does not go much above 5% in any of
the discussed examples). The other characteristic
features of the chemical composition of this glass
are its significant PbO content and the lack of, or
markedly lower concentration of, B2O3.
The four examples of white glass in the third
set, which date from the late 17th century to the
end of the 18th century, originated in Bohemia,
Germany, and Poland. Their composition is characterized by a lack of B2O3 and a significantly
higher CaO concentration (ranging from 7.5 to
9.5%).
White glass and crystal glass may generally be
distinguished by calculating variables from the
alkaline and alkaline earth oxide concentrations,
as shown in Fig.1. This plot clearly shows that
baroque crystal glass and white glass followed the
Fig.1. Venetian soda-ash glass (vitrum blanchum and cristallo) and the late 17th and 18th century central European
potassium glass (white glass and crystal) shown in a scatter plot for the variables calculated from the alkaline and
alkaline earth oxide concentrations. The three vessels that are considered to be Eiland products are indicated by
arrows [2,4].
tal glass are known to have been manufactured in
Bohemian and German centers. The vessel from
Altmünden is dated to about 1710, and it differs
from the other glasses in this set in its possible lack
of B2O3 and its high PbO content. It may thus be
seen as a later variation of this early crystal glass
formula. It appears that lead compounds were
introduced as separate raw materials in central
European colorless vessel glass formulas not earlier than about 1700 [3].
tradition of Venetian cristallo and vitrum blanchum,
respectively.
In Figure 1, we can also observe the division of
baroque crystal glass into the earliest formulation,
which is characterized by a virtual lack of CaO (a
group of points in the lower right corner of the plot),
and later formulations. The same division can be
seen even more distinctly in Fig.2, which is a plot
of As2O3 and CaO concentrations. Based on this
plot, we can tentatively conclude that levels of these
140
Fig.2. Crystal and white glass from various central European glasshouses (late 17th and 18th centuries). The three vessels
that are considered to be Eiland products are marked as black squares. Scatter plot for As2O3 and CaO concentrations.
oxides gradually increased in crystal glass from the
time its manufacture in this part of Europe began
in the late 17th century.
We conclude that the goblet of Matthias Helfried von Plönstein and that with the coat of arms
of the Lodron family are made of crystal glass from
the earliest known phase of its development in
central Europe, while the jug of Marie Adelheid,
Countess Thun is an example of white glass. Both
of the goblets are crizzled, and it is well known that
crystal glass is particularly susceptible to crizzling
[5,6].
The glasses from which these two goblets were
made have very similar chemical compositions, and
they may therefore be considered as products of the
same glasshouse and made during the same period.
In this article, these glasses are tentatively attributed
to the Eiland glassworks. However, we can neither
exclude nor confirm the same attribution for the
jug of Marie Adelheid, Countess Thun. Moreover,
the chemical composition of this glass affords no
clues to its dating.
Because of the lack of published chemical analyses of Bohemian luxury vessel glasses from the late
17th century, as well as any known object that can
be securely attributed to the Eiland glasshouse, all
conclusions concerning the dating and attribution
of the three vessels discussed in this article must
remain a working hypothesis.
It is very encouraging that the art-historical and
technological studies we conducted produced such
similar results. On some points, our findings were
complementary, enabling us to offer bolder hypotheses. However, a consistently wide margin of uncertainty has to be taken into account, as is usual
for this type of research.
Two of the objects discussed in this article – the
goblet of Matthias Helfried von Plönstein and the
Lodron goblet – show many similarities in typol-
ogy, stylistic features, iconography, and the technology used in their manufacture. Both vessels are
exceptional in their decorative features and the
quality of their glass. Their chemical composition
represents an early phase in the development of
crystal glass in central Europe. Based on historical research, we can date the goblets quite securely
about 1675, while chemical analysis confirms that
they were probably produced in the late 17th century. We can be fairly sure that the goblets were
made with the same technology, in the same factory, and by the same glassmaker. The Eiland glassworks and Georg Gundelach are the strongest candidates, although the lack of comparative material
makes this attribution uncertain.
As for the jug of Marie Adelheid, Countess
Thun, we can say only that it was made of white
glass after 1688. This dating, unlike that of the
goblets, is based solely on stylistic analysis and historical research. The jug differs from the two goblets both technologically and stylistically.
We cannot rule out the same attribution for all
three vessels. However, we did not find any clear
evidence indicating that the jug was manufactured
in the same glasshouse as the goblets. This remains
an open question [7].
References
[1]. Moretti C., Toninato T.: Rivista della Stazione Sperimentale del Vetro, 1, 31-40 (1987), in Italian.
[2]. Kunicki-Goldfinger J., Kierzek J., Dzierżanowski P.,
Kasprzak A.J.: Central European crystal glass of the
first half of the eighteenth century. In: Annales du 16e
Congres de l’Association Internationale pour l’Histoire
du Verre (London 2003). AIHV, Nottingham 2005, pp.
258-262.
[3]. Kunicki-Goldfinger J., Kierzek J., Kasprzak A.J.,
Dzierżanowski P., Małożewska-Bućko B.: Lead in
Central European 18th-century colorless vessel glass.
In: Archäometrie und Denkmalpflege – Kurzberichte
2003 (Berlin). Etnologischen Museum Staatliche
Museen zu Berlin, Berlin 2003, pp. 56-58.
[4]. Verità M.: Rivista della Stazione Sperimentale del
Vetro, 15, 1, 17-29 (1985), in Italian.
[5]. Kunicki-Goldfinger J., Kierzek J., Małożewska-Bućko
B., Kasprzak A.: Glass Technol., 43C, 364-368 (2002).
[6]. Kunicki-Goldfinger J.: Preventive conservation
strategy for glass collections: identification of glasses
susceptible to crizzling. In: Proceedings of the 5th EC
141
Conference “Cultural Heritage Research: A Pan-European Challenge”, Cracow, Poland, 16-18.05.2002. Ed.
R. Kozłowski. Institute of Catalysis and Surface
Chemistry, Polish Academy of Sciences and European
Communities, Cracow 2003, pp. 301-304.
[7]. Mádl M., Kunicki-Goldfinger J.: J. Glass Stud., 48,
255-277 (2006), (the full text of the article, which comprises both historical and technological approaches).
WATER SOLUBLE SILICA BIOCIDES
CONTAINING QUATERNARY AMMONIUM SALTS
Andrzej Łukasiewicz, Dagmara K. Chmielewska, Lech Waliś
Silica biocides insoluble in water obtained by coating a carrier (TiO2, dolomite etc.) with an ammonium salt (QAC – quaternary N-alkylammonium
compound) and water glass (WG) stabilized by
sulphuric acid have been described previously [1-3].
Many scientific papers on the synthesis of silica
materials with the application of acid or basic
hydrolysis of alcoholic solution of tetraethoxysilan
(Si(OEt)4) have been published [4,5]. Nanosol, which
can be connected with other materials creating
nanogel, can be obtained by this procedure.
On the basis of the earlier developed technologies, we have elaborated a method for the synthesis of water soluble silica materials containing
quaternary alkylammonium salts (s-SiO2-QAC).
Example: 20 ml of 50% aqueous solution of
benzalkonium chloride (Aldrich) was dissolved in
20 ml of Si(OEt)4 (Aldrich), then 100 ml of isopropanol was added and the mixture was stirred. Next,
10 ml of 0.04% HCl or 0.02% H2SO4 was added
and the mixture stayed at room temperature until
the next day. Properties of the hydrolyzate indicate
complete hydrolysis of Si(OEt)4 and binding of
silica with QAC. The hydrolyzate is bound quantitatively with carrier C (e.g. TiO2, dolomite) and
the product indicates properties characteristic of
insoluble in water materials C(SiO2-QAC): binds
acid dyes effectively, binds Ag+ from water and
zero-valent silver atoms obtained due to UV irradiation.
s-SiO2-QAC can be also incorporated into fabrics
and similar materials.
Investigations of biocidal properties of soluble
materials s-SiO2-QAC and their binding with different carriers as well as structural investigation
are being continued.
References
[1]. Łukasiewicz A., Krajewski K.J., Gajewska J., Chmielewska D.: Właściwości biocydowe nowych materiałów
dla budownictwa modyfikowanych IV-rzędową solą
N-alkiloamoniową związaną z krzemionką. In: Czwartorzędowe sole amoniowe. Wydawnictwo Instytutu Technologii Drewna, Poznań 2005, pp. 432-437 (in Polish).
[2]. Łukasiewicz A., Chmielewska D., Waliś L., Krajewski
K.: Ekologia, 29, 3, 36-37 (2005), in Polish.
[3]. Chmielewska D.K, Łukasiewicz A., Michalik J., Sartowska B.: Nukleonika, 51, Suppl. 1, 69-72 (2006).
[4]. Mahltig B., Haufe H., Bottcher H.: J. Mater. Chem.,
41, 15, 4385-4398 (2005).
[5]. Haufe H., Thron A., Fiedler D., Mahltig B., Bottcher
H.: Surf. Coat. Int. B: Coat. Trans., 88, 1, 55-60 (2005).
THE ROLE OF CARBON, CHROMIUM AND NITROGEN
IN AUSTENITIZATION OF UNALLOYED AND ALLOYED STEELS
BY INTENSE PLASMA PULSES
Jerzy Piekoszewski1,2/, Ludwik Dąbrowski3/, Bożena Sartowska1/, Lech Waliś1/,
Michał Kopcewicz4/, Justyna Kalinowska4/, Marek Barlak2/, Jacek Stanisławski2/,
Zbigniew Werner2/, Adam Barcz5/
1/
The Andrzej Sołtan Institute for Nuclear Studies, Świerk, Poland
3/
4/
Institute of Electronic Materials Technology, Warszawa, Poland
5/
Institute of Physics, Polish Academy of Sciences, Warszawa, Poland
2/
In our previous works it was shown that normal
and so-called expanded austenite phases (γN , γC)
can be formed not only in the stainless steel but
also in carbon steels and even in the pure α-iron if
they are treated with high intensity nitrogen plasma
pulses [1,2]. The purpose of the present work was
to study how the alloying elements such as carbon,
chromium and nitrogen influence the efficiency of
austenitization of steels treated by argon and nitrogen plasma pulses [3]. The steel samples contained initially 2.5-4.2 at.% C, 0.12-14 at.% Cr and
about 1 at.% N after the nitrogen plasma treatment
142
were used in the investigations. The pulses were
generated by rod plasma injector type of generator described in detail in [4].
The energy density of plasma pulses was about
5 Jcm-2, pulse duration – about 1 μs and numer of
pulses – 3. The energy was high enough to melt the
near surface layer, so the used element was doped
to the liquid metal. The samples were examined
by conversion electron Mössbauer spectroscopy
(CEMS), X-ray diffraction (XRD) and secondary-ion mass spectroscopy (SIMS) techniques. The
main results of the detailed analysis of the experimental data can be summarized as follows:
- Both nitrogen and carbon alone are capable of
forming normal and expanded austenite phases
γN and γC.
- Of all three alloying elements: carbon, chromium
and nitrogen, nitrogen is most effective in austenitization of both carbon and alloyed steels.
- Presence of nitrogen weakens the efficacy of
carbon and chromium in austenite formation.
- Presence of carbon strengthens the efficacy of
chromium in austenite formation.
This work was financed by the Polish Ministry
of Education and Science for scientific projects
under contract No. 1147/T08/2005/29.
References
[1]. Sartowska B., Piekoszewski J., Waliś L., Szymczyk W.,
Stanisławski J., Nowicki L., Ratajczak R., Kopcewicz
M., Kalinowska J., Barcz A., Prokert M.: Vacuum, 78,
181-186 (2005).
[2]. Piekoszewski J., Sartowska B., Waliś L., Werner Z.,
Kopcewicz M., Prokert F., Stanisławski J., Kalinowska
J., Szymczyk W.: Nukleonika 49, 2, 57-60 (2004).
[3]. Gavriljuk V.G., Berns H.: High nitrogen steels. Structure, properties, manufacture, applications. Springer-Verlag, Berlin Heilderberg 1999, 376 p.
[4]. Werner Z., Piekoszewski J., Szymczyk W.: Vacuum, 63,
701-708 (2000).
THERMAL STABILITY OF THE PHASES FORMED
IN THE NEAR SURFACE LAYERS OF CARBON STEEL
BY NITROGEN PULSED PLASMA TREATMENT
Bożena Sartowska1/, Jerzy Piekoszewski1,2/, Lech Waliś1/, Jacek Stanisławski2/, Lech Nowicki2/,
Renata Ratajczak2/, Michał Kopcewicz3/
1/
The Andrzej Sołtan Institute for Nuclear Studies, Świerk, Poland
3/
Institute of Electronic Materials, Warszawa, Poland
2/
The intense pulsed plasma beams were used for
carbon steel surface modification. The energy density of the pulse was high enough to melt the near
surface region of the substrate and nitrogen was introduced into the liquid alloy. The nitrogen expanded
austenite – γN (austenite in which iron atoms have
one or more nitrogen atoms in the nearest neighbourhood) was found in the near-surface region of
carbon steel and significant increase of hardness
and tribological properties were observed [1]. The
formation of nitrogen expanded austenite does not
follow the equilibrium phase Fe-N diagram [2,3].
At elevated temperature, the interstitial atoms can
be released from the lattice and diffuse. Therefore,
the stability under maximum operating temperatures must be determined and it must be known
how long a component can be used under specific
thermal load before undesirable properties occur.
Carbon steel 1C45 with 0.52 wt% C and heat
treated with the standard procedures was used for
investigations. The plasma pulses were generated
in a rod plasma injector (RPI) [4]. The samples were
irradiated with five nitrogen plasma pulses at an
energy density of about 5 J cm–2. The samples were
characterized by: nuclear reaction analysis (NRA)
14
N(d,α)12C for the determination of retained nitrogen dose and conversion electron Mössbauer
spectroscopy (CEMS) for quantitative analysis of
the identified phases. The annealing processes
were carried out using a tube furnace, with con-
trolled temperature and flow of the ambient gas –
argon. The heat treatment parameters were: temperature between 100 to 300oC with a step of 50oC
for 1 h. In the investigating samples nitrogen retained a dose of 1.2x1017 cm–2. The standard deviation σ=2x1016 cm–2.
Relative changes of the determined parameters
characterizing properties of the material are defined
as:
[(AM – IM)/IM] x 100%
where AM and IM are the values of the investigated
parameter for annealed and initial material, respectively.
After annealing, the relative surface nitrogen
concentration changes depending on the annealing temperature (Fig.1). The surface nitrogen concentration increased up to temperature of about
Fig.1. Changes of surface nitrogen concentration as a result of annealing the modified samples.
150oC and decreased for annealing at higher temperatures. The main reason for this fact could be
releasing of the interstitial nitrogen atoms from
the nitrogen expanded austenite lattice at elevated
temperature. It is likely that up to 150oC, nitrogen
diffuses towards the surface. At a temperature
higher than 150oC, the nitrogen atoms have higher
energy and can diffuse to the bulk of the sample
as well [5].
As a result of surface modification process, we
obtained thin (about 1.5 μm) layers with the presence of the identified phases α-Fe (ferrite and/or
martensite), γ0 (austenite in which iron atoms have
no nitrogen or carbon atoms in the nearest neighbourhood), expanded austenities γC, γN (austenities
in which iron atoms have one or more carbon or
nitrogen atoms in the nearest neighbourhood) and
nitrides. CEMS results obtained for the heat-treated
samples are presented in Fig.2. The phases transformation process started at annealing at 150oC.
The content of all austenities (γ0, γC and γN) decreases with temperature, while the contents of
α-Fe phases and nitrides increase. Decrease of the
austenitic phases content above 150oC has a rapid
Fig.2. Changes of the identified phases contents as the result of annealing modified samples.
character and these phases are no more present
above 250oC. The content of α-Fe phases increases
by a factor of 2 at 300oC annealing. It is obvious
that this increase is of the expense of austenitic
phases decomposition. For the same reason, we
observed also an increase of nitrides content by a
factor of about 2. Released interstitial nitrogen
atoms become available for the nitrogen phases
formation [5].
The presence and stability of nitrogen expanded
austenite determined in our experiments in steel
1C45 are compared with the data reported in the
literature describing the alloyed steels: austenitic
X6 (0.08% C, 17-19% Cr, 9-12% Ni) and ferritic
X10 (0.12% C, 17-19% Cr) [6] (Fig.3). As it is seen,
the γN phase is the most stable in X6 steel containing both chromium and nickel alloying elements.
It is less stable in chromium containing X10 steel
with the onset temperature of 250oC. As it could
have been expected, our sample which does not
143
contain any of austenite stabilizing element shows
the lowest (150oC) onset temperature of nitrogen
expanded austenite decomposition.
Fig.3. Changes of the nitrogen expanded austenite presence in the modified surface layer of different kinds
of steels as the result of annealing the samples.
In conclusions: The surface nitrogen concentration in the top layer of modified carbon steel
started its decreasing from 150oC due to releasing
the interstitial nitrogen atoms from fcc (face centered cubic) nitrogen expanded austenite lattice
and their diffusion into the surface and bulk of the
samples. The significant changes of the content of
identified phases started at 150oC. The austenities
transformed to the α-Fe phases. The nitrides are
formed at the expense of nitrogen released from
the fcc expanded austenite lattice. The modification effects in unalloyed steel 1C45 induced by the
intense nitrogen plasma pulses are stable to the
temperature of about 150oC. This is the application limit, but below this temperature a material
can be used without losing its required properties.
This work was financed by the Polish Ministry
of Education and Science for scientific projects
under contract No. 1147/T08/2005/29.
References
[1]. Sartowska B., Piekoszewski J., Waliś L., Szymczyk W.,
Stanisławski J., Nowicki L., Ratajczak R., Kopcewicz
M., Kalinowska J., Barcz A., Prokert F.: Vacuum, 78,
181-186 (2005).
[2]. Williamson D.L., Oztruk O., Glick S., Wei R., Wilbur
P.J.: Nucl. Instrum. Meth. Phys. Res. B, 59/60, 737-741
(1991).
[3]. Gavriljuk V.G., Berns H.: High nitrogen steels. Structure, properties, manufacture, applications. Springer-Verlag, Berlin Heilderberg 1999, 376 p.
[4]. Werner Z., Piekoszewski J., Szymczyk W.: Vacuum, 63,
701-708 (2000).
[5]. Briglia Th., Terwagne G., Bodart F., Quaeyhaegenes
C., D’Haen J., Stals L.M.: Surf. Coat. Technol., 80,
105-108 (1999).
[6]. Jirásková Y., Blawert C., Schneeweiss O.: Phys. Status
Solidi A, 175, 537-548 (1999).
144
ELECTRON-BEAM IRRADIATION OF PVDF MEMBRANES
AS A METHOD FOR OBTAINING BRITTLE FRACTURES
FOR SEM OBSERVATIONS
Bożena Sartowska, Oleg Orelovitch1/, Andrzej Nowicki
1/
Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, Dubna, Russia
Specific template – track membranes can be used
to obtain the nano- and microstructures [1]. It is important for these applications to know geometry
parameters of the pores like sizes, shape and their
inner surface morphology [2]. A scanning electron
microscopy technique (SEM) was used for the investigations of surface and fracture of membrane.
The proper preparation of samples for SEM observations is very important in order to prevent destruction the structure of the membrane during fracture preparation. The breaking membrane samples
at the liquid nitrogen temperature (77 K) did not
A
highest purity, strength, and resistance to solvents,
acids, alkalies and heat. It is commonly used in the
chemical, semiconductor, medical and defense industries. A fine powder grade is also used as the
principal ingredient of high-end paints for metals.
PVDF is exhibiting efficient piezoelectric and pyroelectric properties. These characteristics make it
useful in sensor and battery applications [6,7].
The samples of PVDF membranes were irradiated with electron beam at the Institute of Nuclear
Chemistry and Technology (INCT) using different
doses. The mechanical properties: tensile strength
B
Fig.1. The fractures of PVDF membrane: A – initial, fractured in liquid nitrogen; B – irradiated with electron beam up
to a dose of 603 kGy.
allow us to obtain undistorted cross-section. The
use of other methods of sample preparation as electron beam, gamma rays or UV irradiation allows
us to make them more brittle [3-5]. Preliminary
results of investigations of polyvinylidene fluoride
(PVDF) membranes after electron-beam irradiation are presented here.
Polyvinylidene fluoride is a highly non-reactive
and thermoplastic fluoropolymer. This is the reason to find new methods of destruction of this type
of polymer foils or membranes for the cleavage
production for SEM fracture investigations. Its use
is generally reserved for applications requiring the
and elongation at break of the initial and irradiated
materials were tested using a universal testing machine Instron 5565 (Instron Co., England) in the
INCT. Membranes surface and fracture observations
were made using SEMs: JSM 840 (Jeol, Japan) and
DSM 942 (Zeiss, Germany). The samples were fixed
using a conductive glue and then coated with a thin
layer of gold to reduce the charging which takes a
place during SEM observation.
Figure 1A presents the fractures of the investigated PVDF membrane produced using the method
with liquid nitrogen. The deformation of polymeric
material is clearly seen, so the observation of the
Fig.2. Results of mechanical strength measurements of PVDF membrane: A – initial, B – after electron-beam irradiation up to a dose of 603 kGy.
shape and inner geometry of the channels is difficult or even impossible. Figure 1B presents the fractures of a PVDF membrane subjected to the electron-beam irradiation up to a dose of 603 kGy. The
plastically deformed parts of the material are not
visible. The shape and sizes of channels are clearly
seen, so the pores can be observed, measured and
characterized.
Figure 2 presents the results of mechanical
strength measurements. According to these diagrams, we can determine the main parameters of
material tensile properties: elongation at breake
[%] and tensile stress [MPa]. The strength of the
membrane decreases significantly after electron-beam irradiation. The elongation at breake (tensile strain) of irradiated membrane was only about
1% at the 13 MPa of tensile stress, while for the
initial material these parameters were 25% at the
35 MPa, respectively. This means that the investigated material became more brittle and the membrane breaks without distortion of its channel structure and we obtain the cleavage without plastic
deformations.
145
In conclusion: using the irradiation with electron beams, we can obtain a better SEM image of
polymeric membrane fractures than obtained with
liquid nitrogen.
References
[1]. Sartowska B., Wawszczak D., Buczkowski M., Starosta
W.: Radiat. Meas., 40, 2-6, 790-793 (2005).
[2]. Apel P.Yu.: Radiat. Meas., 34, 559-566 (2001).
[3]. Orelovitch O.L., Apel P.Yu., Sartowska B.: Mater.
Chem. Phys., 81, 349-351 (2003).
[4]. Orelovitch O.L., Apel P.Yu.: Microsc. Anal., 82, 11-13
(2003).
[5]. Orelovitch O.L., Apel P.Yu., Sartowska B.: J. Microsc.,
224, 100-102 (2006).
[6]. Zhang Q.M., Bharti V., Kavarnos G., Schwartz M.:
Poly(vinylidene fluoride) (PVDF) and its copolymers.
In: Encyclopedia of smart materials. John Wiley & Sons,
2002, pp. 807-825.
[7]. Vinogradov A., Schwartz M.: Piezoelectricity in polymers. In: Encyclopedia of smart materials. John Wiley
& Sons, 2002, pp. 780-792.
SELECTED PROPERTIES OF POLYPYRROLE NANOSTRUCTURES
DEPOSITED IN TRACK-ETCHED MEMBRANE TEMPLATES
Marek Buczkowski, Wojciech Starosta, Bożena Sartowska, Danuta Wawszczak
Polypyrrole (PPy) belongs to conducting polymers
which are the most stable in typical environmental
conditions and seems to be very interesting material for nanotechnology [1-4]. Presented results
are a continuation of investigations carried out earlier. The first subject was connected with: deposition of PPy nanotubules on track-etched membranes
(TMs) and determination of the kinetics of their
wall thickness growth for time of deposition longer
than 7 min [4]. The second subject was connected
with measurements of electrical parameters of PPy
nanotubules deposited into TMs [5].
In this work, the results are connected with: PPy
nanotubules formed in TM templates for times
of polymerization shorter than 5 min, determination of permeability of deposited nanotubules and
covering of such structures with a thin copper layer.
The template-based synthesis of PPy was carried out into pores of TMs made of 10 μm thick
Fig.1. A scheme of the mould for PPy nanotubules deposition in TMs membranes.
poly(ethylene terephthalate) (PET) films [4]. In order to prepare samples for measurements, proper
A
B
Fig.2. Nanotubules formed in pores of TM membrane (0.2
μm pore size) after 2 min (A) and 3 min (B) of polymerization process.
146
Table 1. Dependence of PPy layer thickness on TM vs. time
of polymerization for both sides of a membrane
sample (pore size – 1.3 μm).
Fig.3. Kinetic curve of PPy nanotubules growth into pores
of the TM (initial pore size – 1.3 μm).
solutions were introduced to both sides of a membrane disc (for certain period of time) that had
been mounted in a plexiglas mould (Fig.1). As a
allowed to determine nanotubules wall thickness
and thickness of the PPy layer on membrane surfaces. Selected SEM photographs (Fig.2) show
fractures of the samples in liquid nitrogen in case
of time of polymerization, respectively 2 and 3 min.
Dependence of nanotubule wall thickness vs. time
of polymerization is shown in Fig.3 (for times equal
to or longer than 7 min; results are taken from previous work). It is seen that the first stage of the
speed of nanotubules formation is higher than in
the next stage. This speed is equal to 20.3 nm/min
and is 1.7 times higher than in the next stage. Thickness of PPy layers on the template surfaces for different times of polymerization is given in Table 1.
Table 2. Permeability of nanotubules deposited on pores of TMs 0.2 μm at an air pressure of 0.5 bar.
result of such procedure, discs 20 mm in diameter
covered with PPy have been obtained (outer diameter of samples was 30 mm).
The value of permeability is an important parameter in some applications, for instance, in microfiltration devices. Permeability for samples with
Table 3. Permeability of nanotubules deposited on pores of TMs 1.3 μm at an air pressure of 0.5 bar.
Scanning electron microscopy (SEM) measurements by using a Zeiss-Leo DS942 microscope
A
different wall thickness of nanotubules in TMs with
pore diameters 0.2 and 1.3 μm was determined at
B
Fig.4. The copper layer sputtered on the membrane surface by using a glow vacuum discharge: (A) membrane pore size
– 0.2 μm, (B) membrane pore size – 1.3 μm.
an air pressure of 0.5 bar. For TMs with a pore size
of 0.2 μm, the initial permeability was equal to 0.70
l/(min·cm2). Values of the permeability for different wall thickness of PPy nanotubules deposited
in such pores are given in Table 2. It was calculated
that by decreasing the internal pore diameter 6.3
times (from 200 to 32 nm), the permeability decreased 2.9 times.
For TMs with a pore size of 1.3 μm, the initial
permeability was equal to 14.8 l/(min· cm2). For different wall thickness of PPy nanotubules deposited
in pores, the permeability is given in Table 3. In
this case, decreasing of the internal pore diameter
6.6 times (from 1300 to 198 nm) caused decreasing of the permeability 10.4 times.
Attempts were taken up concerning the covering of samples with deposited PPy nanotubules by
thin metallic layer. This is important matter because samples with deposited PPy can be applied
as sensors and in such case it is necessary to introduce electrical connection with an outer circuit.
Introductory experiments were carried out with
glowing sputtering of copper (in the “Surftec” s.c.,
Warszawa). SEM photographs (Fig.4) show the
sputtered copper layer in case of two types of samples
147
with PPy nanotubules: TM membrane with pores
0.2 μm (Fig.4A) and 1.3 μm (Fig.4B). The thickness of copper layers was similar in both cases: 0.7
and 1.2 μm, respectively, but the structure of these
layers was different. In case of smaller size of the
pores in template, the surface of the copper layer
was smoother.
The authors would like to thank Mr Adam Leciejewicz – head of the “Surftec” s.c. for the copper
sputtering of membrane samples by using glow
vacuum discharge.
References
[1]. Nakata M., Kise H.: Polym. J., 25, 91 (1993).
[2]. Kohli P., Martin C.R.: Curr. Pharm. Biotechnol., 15,
441-450 (2004).
[3]. Zhitariuk N.J. et al.: Nucl. Instrum. Meth. Phys. Res.
B, 105, 204-7 (1995).
[4]. Starosta W., Buczkowski M., Sartowska B., Wawszczak
D.: Nukleonika, 51, Suppl. 1, S35-S39 (2006).
[5]. Buczkowski M., Wawszczak D., Starosta W.: Electrical
parameters of polypyrrole nanotubules deposited inside
track-etched membrane templates. In: INCT Annual
Report 2004. Institute of Nuclear Chemistry and Technology, Warszawa 2005, pp. 93-94.
SOL-GEL-DERIVED HYDROXYAPATITE AND ITS APPLICATION
TO SORPTION OF HEAVY METALS
Andrzej Deptuła, Jadwiga Chwastowska, Wiesława Łada, Tadeusz Olczak,
Danuta Wawszczak, Elżbieta Sterlińska, Bożena Sartowska, Marcin Brykała,
Kenneth C. Goretta1/
1/
Argonne National Laboratory, USA
Hydroxyapatite (HA, Ca10(PO4)6(OH)2) is the major inorganic constituent of biological hard tissues
such as bones and teeth. Owing to its structure and
chemical composition this material also shows a
high capacity for ion exchange. The properties of
synthetic hydroxyapatites depend greatly on the
method of their preparation. In most published
work, hydroxyapatites obtained by precipitation
methods have been studied. These hydroxyapatites
have been examined as new inorganic cation exchangers [1-6] and anion exchangers [7,8]. Teams
from Argonne National Laboratory have studied
engineering aspects of HA and use of various
phosphates for containment of radioactive waste
[9-11].
The principal goal of this work was a study of
adsorption of heavy metal ions on HA microspheres
and monolithic ceramics to address the possibility
of application to separation of various metal ions
from water and liquid wastes. Hydroxyapatite in the
form of microspheres was prepared by a proprietary
sol-gel method [12,13]. For fabrication of HA monoliths, we applied a second proprietary method. The
synthesis processes consisted of preparation of sols
with the use of a very strong complexing agent –
ascorbic acid (ASC) [14,15].
Synthesis
Starting sols were prepared by ultrasonic mixing of concentrated solutions of calcium acetate
(1.7 M) with 85% H3PO4, followed by emulsification in dehydrated 2-ethyl-1-hexanol. Drops of
emulsion were gelled by extraction of water with
this solvent. Details of the laboratory equipment
(50 g/h) and microspheres formation have been
described [12,16,17]. For synthesis of the powder
for the monoliths, we modified the sol-gel process
described in [15], using inexpensive CaO and H3PO4
as starting ingredients. In brief, 28.054 g of CaO
was dissolved in 150 mL of deionized water and
44 g of ASC was dissolved in 500 mL of deionized
water. The solutions were blended with 20 mL of
concentrated H3PO4 and 150 mL of deionized
water. The pH was adjusted to 7 by addition of
NH4OH. Evaporation was followed by drying at
room temperature (RT) and final heating of monoliths in air for 2 h soak at 900oC. The sedimentation rate of the spherical powders of HA was approximately 20 times greater than for irregularly
shaped powders of similar size distribution. The
resulting spherical powders and monoliths are
shown in Fig.1.
On the basis of published information [16], we
estimate the cost of producing HA microspheres
by our method for a projected scale of 1 kg h–1 to
be approximately 170 USD/kg. This price is comparable to those for irregularly shaped commercial HA powders (Sigma Chemical Company (art.
C 4507) = 180 USD/kg; Merck (index 11.1701) =
148
A
B
------3cm -----Fig.1. Sol-gel-derived HA produced in the forms of microspheres (A) and fired monolith (B).
150 USD/kg). Merck also offers microspheres (diameter 75-100 μm) at approximately 1700 USD/kg.
For column-based sorption experiments, powder
fractions of approximately 200 mesh were separated
by sedimentation. The concentrations of stock solutions of metals were 1 mg cm–1. The solutions were
prepared by dissolving metallic compounds in 1 M
HCl. A test water solution of the following composition [mg dm–3] was used: Na+ – 15; K+ – 4; Mg2+
– 20; Ca2+ – 55; Cl– – 125; SO42– – 80; Zn2+ – 0.2;
Cd2+, Pb2+, Ni2+, Co2+, Cu2+, and Mn2+ – 0.1.
Solubility of hydroxyapatite
Solubility was estimated under conditions similar to those of metal sorption: 0.2 g of HA was
shaken with 20 mL of solution of suitable pH for
30 min at 20oC. The solution was then filtered off.
Ca was measured by atomic absorption spectrometry (AAS) and P by spectrophotometry, as
phosphoromolybdate with reduction to blue. Measurements of the Ca and P eluted by solutions of
pH within the range of 0-9 revealed that the solubility of HA increased with decreasing pH (Fig.2).
The amount of Ca eluted by 1 M HCl from 1 g of
HA was ca. 0.5 mg Ca, which corresponds to 12
mmole per one mole HA. The solubility decreased
with increasing pH, e.g. from 2.7 to 0.8 mmole Ca
per one mole HA for pH=5-9. The concentration
of P in the solutions was much lower than that of
Ca: the P eluted by 1 M HCl was equal to ca. 0.067
mg g–1 HA (2.2 mmole per mole).
It may be concluded that a greater number of
Ca cations than P anions release into solution when
pH decreases, which results in a decrease in the
Ca/P mole ratio in the solid phase. These results
correspond with measurements of the solubility of
HA reported elsewhere [5,18].
Batch sorption experiments
The influence of pH on the sorption of the selected elements, and the sorption kinetics for Cu(II)
and Ni(II), were studied by the batch method. A
solution for each element, containing 100 μg of the
element, was adjusted to a suitable pH by addition
of HCl or NaOH and transferred into a 50 cm3
separatory funnel. The final volume of the solution
was 20 cm3. Then 0.5 g of the HA was added and
mechanically shaken for 30 min. The solution was
filtered then and the sorbent was washed twice with
2 cm3 portions of a solution of the same pH. The
washings were combined with the filtrate. The concentration of each element studied was determined
by AAS with flame atomization or by spectrophotometry. The amount of the element retained on the
sorbent was calculated from the difference between
the amounts in the original solution and in the filtrate.
For kinetic studies, similar experiments were
performed for two elements – Cu(II) and Ni(II) –
at a suitable pH and a shaking time within a 5-30
min interval. The retention capacities for Cu(II)
and Pb(II) were also determined by the batch
method. Detailed conditions of these experiments
are shown in Table; amount of sorbent – 0.5 g,
Table. Estimations of retention capacity of elements on
HA.
Fig.2. Solubility (as concentration, c) of HA at various pH
levels.
volume of liquid phase – 20 cm3, original concentration of metal – 0.5 mg cm–3.
Column sorption experiments
A glass column, 4 mm inner diameter, was filled
with 0.5 or 1 g HA and conditioned with a solution
of a suitable pH. A sample containing 100 μg of
the element studied, adjusted to a suitable acidity,
was passed through the column under pressure at
a flow rate of 0.3-2.2 cm3 min–1. The column was
149
then washed with 10 cm3 of solution of the same
pH. The washings were combined with the effluent. The element studied was determined in the
combined solution.
The test water samples, 100 or 200 cm3 each,
were adjusted to pH=5. The solution was then
passed at the flow rate of 0.5 cm3 min–1 through
the column filled with 1.0 g of HA (previously
washed with water, pH=5). The efficiency of sorp-
Fig.3. Retention of elements in solutions of various pH (pH measured before sorption); monolithic HA was used in only
three sets of experiments (top three plots).
150
tion was checked by determining the metal concentration in the elutant, with the use of the AAS
method with flame atomization.
The kinetic sorption was rapid: equilibrium was
attained within a few minutes. The effect of shaking time was established for Cu(II) and Ni(II).
Obtained data indicated that the equilibrium of
sorption process is attained in 5 min. This rapid
equilibration is in contrast to the previously reported
work with HA, for which the times for attaining
the equilibrium were much longer (1-48 h) [4,5] and
even 20 days [3].
The main results of our experiments are shown
in Fig.3, as the dependence of sorption upon the
pH of the original solution. The pH of the solution
after sorption increased, probably owing to a partial dissolution of HA. The retention of most elements studied was approximately 94-100%, in the
most suitable acidity ranges. Only the MnO4– ions
exhibited low retention; the maximum was 47% in
a 1 M H2SO4 solution. The sorption of Cr(VI),
which was present in solution as anions, and that
of Sb(V), As(V), and Mo(VI), which have amphoteric character with a predominance of acidic properties, probably followed anion exchange between
the hydroxyl ions of the lattice and the metal anions in the solution.
The optimum conditions for the column process were established for Cu(II). The influences
of flow rate and sample volume on the sorption
efficiency were determined. The process of sorption was carried out under pressure in the glass
column filled with 0.5-1 g of HA. It was found that
flow rates to 2.5 mL min–1 and sample volumes to
200 mL did not deteriorate the efficiency of Cu
sorption.
The sorption responses of the group of divalent metal ions (Cu, Cd, Pb, Ni, Co, and Mn) from
the artificially prepared test water were also studied
by a dynamic method. Under the conditions established (pH – 5, flow rate – 0.5 cm3 min–1, sample
volume – 100 cm3, 1 g of HA), all of the metals
studied were quantitatively adsorbed.
Retention capacity of hydroxyapatite
The conditions and the results of determination of the retention capacity for Cu(II), Pb(II),
and U(VI) are show in Table. It can be concluded
that the capacities of HA materials that were
studied were rather low, equal to 3 mg of Cu2+, 10
mg of Pb2+, and 12 mg of U(VI) per 1 g of HA.
The retention capacity of the monolithic HA was
significantly higher: for U(VI) it was approximately
three times higher than the values that were obtained for spherical HA.
Discussion – mechanism of sorption
The sorption of metal cations can be achieved
mainly in two ways: ion exchange and ion adsorption. The ion exchange mechanism is generally
believed to take place in the case of sorption of
heavy metals on HAs [2,3,5]. Moreover, Xu et al.
[19] proposed that the most important sorption
mechanism may be surface complexation and coprecipitation, possibly accompanied by ion exchange
and solid-state diffusion. Furthermore, in the work
by Reichert and Binner [4], ion adsorption was pro-
posed as a mechanism for ion removal; ion exchange
was not observed, but it could not be completely
ruled out.
The amount of Ca2+ released during the sorption can be used as an indicator of either ion exchange or ion adsorption. If ion exchange takes
place, the molar ratio between the divalent metal
cation retained in the solid phase and Ca released
into the solution must be close to one. If this ratio
is less than one, then some adsorption must have
taken place.
In the present work, for both Ca/Cu and Ca/Ni,
the molar ratio was equal to 0.3. These results suggest that for the HA materials studied the predominant process in the sorption of metal cations was
surface adsorption, possibly accompanied by ion
exchange.
Synthetic HA synthesized by sol-gel methods
and produced in the form of microspheres or irregularly shaped powders that were processed into
monoliths offered the possibility for separation of
various metal cations and anions. In contrast to HAs
previously reported upon, the sorption kinetics was
fast; equilibrium of sorption was attained within a
few minutes.
The cost to produce these materials in irregularly shaped powders (monoliths) was estimated to
be more than 10 times lower than spherical powders
and HA powders now offered commercially.
The mechanism of cation sorption on the HA
was determined to be primarily ion adsorption,
possibly accompanied by ion exchange. The HA
studied is a suitable material for the separation of
the group of metals studied from natural waters.
However, retention capacity was not high (3 mg
of Cu and 10 mg of Pb per 1 g of HA), which would
be a disadvantage for possible applications of the
HA as, for example, a filter material to sewage treatment. The retention capacity for U(VI) of monolithic HA was much better for spherical HA, approximately 3 times higher. We recommend that
the monolithic form HA should be examined for
immobilization of U from nuclear wastes.
References
[1].
[2].
[3].
[4].
[5].
[6].
[7].
[8].
[9].
[10].
Suzuki T., Hatsushika T., Hayakawa Y.: J. Chem.
Soc., Faraday Trans., 77, 1059 (1981).
Suzuki T., Hatsushika T., Miyake M.: J. Chem. Soc.,
Faraday Trans., 78, 3605 (1982).
Suzuki T., Ishigaki K., Miyake M.: J. Chem. Soc.,
Faraday Trans., 80, 3157 (1984).
Reichert J., Binner J.G.P.: J. Mater. Sci., 31, 1231
(1996).
Jeanjean J., Fedoroff M., Faverjon F., Vincent U.,
Corset J.: J. Mater. Sci., 31, 6156 (1996).
Jeanjean J., Vincent U., Fedoroff M.: J. Solid State
Chem., 108, 68 (1994).
Wright G.: Ann. Chim. Fr., 5, 39 (1970).
Young R.A.: In: Proceedings of the 2nd International
Congress on Phosphorus Compounds (IMPHOS).
Paris 1980, p. 73.
Singh D.,. Wagh A.S, Cunnane J., Mayberry J.: J.
Environ. Sci. Health A, 32, 527 (1997).
Singh D., de la Cinta Lorenzo-Martin M., Routbort
J.L, Gutiérrez-Mora F., Case E.D.: Int. J. Appl.
Ceram. Technol., 2, 247 (2005).
[11]. Goretta K.C., Singh D., Tlustochowicz M., Cuber
M.M., Burdt M.L., Jeong S.Y., Smith T.L.,. Wagh A.S.,
Routbort J.L.: Mater. Res. Soc. Symp. Proc., 556, 1253
(1999).
[12]. Deptuła A., Łada W., Olczak T., Borello A., Alvani
C., Di Bartolomeo A.: J. Non-Cryst. Solids, 147&148,
537 (1992).
[13]. Alvani C., Borello A., Deptula A., Lorenzini L., Orru’
L.: Method for preparing of irregularly shaped and
spherical powders of calcium phosphates, especially
Ca-hydroxyapatite. Italian Patent 01245400 (1994).
[14]. Deptuła A, Łada W., Olczak T., LeGeros R.Z.,
LeGeros J.P.: Method for preparing of calcium phosphates layers, especially hydroxyapatites. Polish Patent
No. 180602 (2000).
[15]. Deptuła A., Łada W., Olczak T., Lanagan M.T.,
Dorris S.E., Goretta K.C., Poeppel R.B.: Method for
151
[16].
[17].
[18].
[19].
preparing of high temperature superconductors. Polish
Patent No. 172618 (1997).
Deptuła A, Łada W., Olczak T., Sartowska B.,
LeGeros R.Z., LeGeros J.P.: Complex sol-gel process
(CSGP) preparation of calcium phosphate biomaterials (powders, monoliths, fibres). In: Bioceramics
11. Eds. R.Z. LeGeros, J.P. LeGeros. World Scientific,
Singapore 1998, p. 743.
Deptula A., Chmielewski A.G.,. Wood T.E.: Sol-gel
ceramic beads and bubbles – a historical perspective,
modern fabrication and cost analysis. In: 9th CIMTEC
Proceedings. Part D. Ed. P. Vincenzini. Techna, Faenza
1999, p. 771.
Verbeek R.M.H., Steyaer H., Thun H.P., Verbeek F.:
J. Chem. Soc., Faraday Trans., 76, 209 (1980).
Xu Y., Schwartz F., Traina S.J.: Environ. Sci. Technol.,
28, 1472 (1994).
PHYSICAL AND CHEMICAL PROPERTIES OF YTTERBIUM
DOPED KY(WO4)2 NANOCRYSTALS
Andrzej Deptuła, Mieczysław T. Borowiec1/, Vladimir P. Dyakonov1/, Wiesława Łada,
Tadeusz Olczak, Danuta Wawszczak, Pavlo Aleshkevych1/, Wiktor Domuchowski1/,
Tetyana Zayarnyuk1/, Marek Barański1/, Henryk Szymczak1/, Marcin Brykała
1/
Institute of Physics, Polish Academy of Sciences, Warszawa, Poland
Nanocrystalline materials can offer several alternatives to the classic bulk laser crystals. Sol-gel
methods are used for producing homogeneous
samples at low temperatures.
The mechanism of selfignition
Sol-gel methods are used for producing homogeneous samples at low temperatures. Novel synthesis of carbon-free nanocomposites of KYW and
KYW:Yb (1 mol%) was elaborated by introducing a selfignition (SI) step. The SI mechanism is
very complex and strongly related to the drying and
heating conditions. Obviously the SI step can be
easily obtained without a drying step. However, a
controlled drying step is necessary in order to avoid
the foaming effect which causes a 10-20 fold in-
drying takes place under vacuum conditions. The
drawback of the prolonged drying time is related
to the risk that the SI process might disappear. As
can be seen in the upper part of Fig.1, sample
B6Pw-1 extracted from the running furnace at
230oC is black in colour. Further heating to 300oC
produced a white powder with only small gray inclusions, indicating that SI has occurred. After a
final treatment at 550oC, sample B6Pw-2 is snow-white. In contrast, sample B6Pw-4 heated slowly
(lower part of Fig.1) does not exhibit SI and, under
the same firing conditions, became deep gray indicating high carbon content.
Final thermal treatment parameters have been
selected on the basis of differential thermal analy-
Fig.1. Samples of KY(WO4)2 gels is various stages of the
thermal treatment.
crease of the powder volume. This effect can be
suppressed if the drying time is increased and the
Fig.2. The representative TG (thermogravimetry) and DTA
traces of the gel samples B27 (650oC, 5 h, 2oC/min,
SI) and KY(WO4)2+Yb3+, 650oC, 5 h, 2oC/min, SI).
152
sis – DTA (Fig.2). As can be seen (line a) at 230oC,
the samples extracted from the running furnace
are black. But farther heating results in selfignition.
The sample taken out immediately after SI is white,
only with small gray inclusions. However, after
final treatment the sample is snow-white. In contrast, a sample heated slowly (line b) does not exhibit SI and, after the same firing conditions is
deeply gray, indicating a high carbon content.
XRD and ESR investigations of nanocrystals
The expected monoclinic phase C2/c of the
KYW nanocomposites was confirmed using X-ray
resonance lines, meaning the absence of paramagnetic centra in this sample (very high “spectral”
purity). On the other hand, the spectrum of the
B8Yb sample exposes wide resonance absorption.
This absorption is a result of the superposition of
the single resonance lines of the Yb ions averaging
on angles (Fig.4).
IR spectra of KY(WO4)2 nanocomposites
The infrared (IR) spectra of the synthesized
samples were obtained from a KBr pellet using a
Fig.5. The IR spectra of B6Pw-2 sample (KY(WO4)2, SI –
550oC, 10 h).
Fig.3. X-ray spectrum for samples B27.
diffraction (XRD) technique (Fig.3). Unit cell
parameters and size of grain L for various samples
BRUKER-EQUINOX 55 spectrometer. For semi-quantitative evaluation of the carbonate content
in the synthesized materials it was necessary to use
admixtures of Na2CO3 powder.
Table. Lattice parameters of decarbonized nanocomposites.
are presented in Table. The electron spin resonance
(ESR) spectrum of the B6Pw-2 sample shows no
Fig.4. The EPR spectra for samples B6Pw-2 (KY(WO4)2,
SI – 550oC, 10 h) and B8Yb (KY(WO4)2+1%mol
Yb, SI – 550oC, 10 h).
In the gels dried at 230oC (B6Pw-1 and B6Pw-3),
only a very weak and broad -Me-(=)O band was
observed in the range 600-1000 cm–1. A very strong
band near 1400 cm–1 (assigned to σOH) indicates the
presence of (Me)-OH groups. These, together with
molecular H2O bonds (σ, 1600 cm–1; ν, 2900-3600
cm–1) form a gel network (hydrogen bonds and -Obridging bonds). Nitrate and carbonate bands were
not observed. The absence of bands characteristic
of organic substances (e.g. C-H bands at 2800-3000
cm–1 related to ascorbic acid, ASC, and products
of its decomposition), indicated that the ASC decomposition at this temperature is complete. This
is a very important result if compared to other systems (e.g. LiNixCo1-xO2), where carbonates remained
after ASC decomposition and strongly hydrated
the final compounds. The lack of organic compounds
(no –C-H bands) in the KYW and KYW:Yb
samples clearly indicates that the morphology of
the dried gels is responsible for the occurrence of
the SI process. From the IR spectra (Fig.5), it
seems that high-purity double tungstate structures
can be easily obtained by introducing an SI step.
The best example is sample B6Pw-2.
The good quality nanocomposites of KY(WO4)2
and KY(WO4)2+1%mol Yb have been synthesized.
Electron spin resonance studies in the X band have
been performed on KYW and KYW:Yb nanocrys-
153
tals. The IR spectra of synthesized samples were
obtained.
This work was supported by the Eueopean Union
(project DT-CRYS, NMP3-CT-2003-505580) and
the Polish State Committee of Scientific Research
(KBN) (decision of project No. 72/E-67/SPB/6
PR/DIE 430/2004-2006).
SAXS STUDY OF XERO- AND AERO-GELS
FORMED FROM MONOSACCHARIDE GELATORS
Helena Grigoriew, Dagmara K. Chmielewska
The processes of gel drying produce xero- or aero-gels, depending on the method used. The method
of xero-gel production is lyophilization or frozen-drying, i.e. evaporation of the solvent at low pressure, from the frozen gelator skeleton. If there is no
collapse, the gelator structure, with an enormous
surface area and a very small pore size, is maintained. But such drying process is accompanied
with unhindered shrinkage that can lead to structural collapse of the gelator network structure, resulting in formation great, compact, surface-type
clusters. The aero-gel is produced by careful drying
a wet gel in various environments, often in super-critical conditions, and/or with solvent exchange.
The gel does not shrink, so the fragile gelator net-
work does not collapse and the aero-gel is highly
porous. Both processes can be complex and many-staged [1].
The weak, physical gels, as it is known, can disintegrate upon touching. So, the process of drying
can be expected as having a more essential influence on their structure.
The main goal of this work was to check, using
the small angle X-ray scattering (SAXS) method,
the influence of drying on monosaccharide gel
structure and to consider the rightness of application of microscopic results to the description of
wet monosaccharide gels structure.
The gel, formed from a methyl-4,6-O-benzylidene-α-D-glucopyranoside gelator with diphenyl
Fig.1. Fractal curves for weaker apolar gels: A – wet, B – xero, C – aero. The straight-line parts of the curves are marked
by lines with their slopes.
154
ether as a solvent, was prepared [2]. The gelator is
an example of one of the smallest monosaccharide
molecule, which is apolar as well as the solvent is.
So, very weak mutual interactions in the gel structure can be expected. The next gel was built of methyl-4,6-O-(p-nitrobenzelidene)-α-D-glucopyranoside gelator with water as a solvent. Both materials
are polar and the gelator molecule size is not very
small among monosaccharides. This gel structure
is expected to be stronger than the first one. Both
gelators were prepared by us according to [2,3]. The
gels were prepared in the same way, as used in our
earlier works [4,5]: a mixture composed of a gelator
and a solvent was heated in a closed, capped tube
until the gelator dissolved. The gelator concentration was in the range 1-1.5% [g/mL]. Aero-gels
were produced by leaving the obtained gels in open
vessels till they become dry. Xero-gels were produced by frozen-drying of the gels in a Labconco
lyph.lock 1l apparatus at about -50oC and 10 mm
Hg.
The wet gel samples for SAXS measurements
were prepared by putting them in thin-walled capillaries ( Hilgenberg, 2 mm diameter, 0.01 mm wall
thickness), then sealed.
The measurements were carried out at the
ULTRA-SAXS BW-4 wiggler beamline, Hasylab-DESY synchrotron, BW4 beamline. The collected ultra small angle X-ray scattering (USAXS)
measurements were subjected to pie integration,
and, after normalization, to subtraction of the
background which was the USAXS signal due to
the solvent in the capillary. To obtain a wide range
of scattering angles (USAXS-SAXS), each sample
was measured at two different sample-detector distances (4 and 12 m), and both measurements were
joined, using OTOKO program, to get one curve
over the whole range.
For weak glucose gel, G, the first slope of log-log
curve (Fig.1A), of dm=1.6 is generated by loose,
mass fractal built according to DLCA (diffraction
limited cluster aggregation) mechanism. The surface fractal slope of ds=2.9, (ds=6 – slope) means
very uneven and developed surface. From the
fractal curve, also two sizes, typical of fractal structure can be evaluated: at Guinier crossover – radius
of gyration of fractal aggregate, Rg=109 nm and
at Porod crossover – size of primary particle, a=10
nm.
The essential change of fractal curve for xero-gel (Fig.1B) seems to be caused by drying-induced
stress that results in collapse and formation of
large-scale morphological features. Their size is too
large to be visible by X-rays, and small-s scattering is related to surface fractal with dimension ds≈2,
characteristic of smooth, sharp interface. After this
surface fractal range, for bigger angles, the crossover is showed, at 17 nm, and then mass fractal
range, of dm=2.45. The same run of aero-gel fractal
curve (Fig.1C) is observed, also with crossover at
Fig.2. Fractal curves for stronger polar gels: A – wet, B – xero, C – aero. The straight-line parts of the curves are marked
by lines with their slopes.
17 nm. Only the followed mass range slope is
smaller and is equal to dm=1.8, i.e. there is more
loose structure.
So, in our case, the collapse takes place not only
at the xero-gel formation, where it is due to a strong
shrinkage during emptying fractal structure from
maintaining it solvent molecules, but also at aero-gel formation, where the evaporated solvent molecules are replaced by their vapor and finally by
air, so stresses should be much smaller. These observation confirmed a big weakness of monosaccharide gel structure.
Whereas, for a stronger para-glucose gel with
water, P, the fractal curve (Fig.2A) begins, the part
generated by mass fractal of dm=2.9 is much denser
than for G gel, built according to another, RLCA
(reaction limited cluster aggregation) mechanism.
The Porod bend at 160 nm and then surface fractal
of ds=2.05 means that the primary particle is much
greater, than for G gel, and of smooth surface. This
can be expected, because the polarity of both gel
constituents can activate enthalpic forces that favor
a large scale phase separation [1].
The log-log curve of related P xero-gel (Fig.2B)
is close to the curve, obtained for G xero-gel with
long, straight-line segment of surface fractal with
close interface. This run of the curve suggest a similar collapse as caused by G-xero-gel formation.
But for the P aero-gel there is no similarity with
the G aero-gel structure. No collapse is observed.
155
Visible three ranges of the fractal curve (Fig.2C)
are related to a small primary particle, smaller than
in the wet P gel (a=63 nm in comparison with
a=160 nm), of very uneven surface (in comparison with very smooth one). The particles form
loose fractal generated by DLCA mechanism, and
not dense by RLCA mechanism. Such structure is
not a modification of the previous wet gel structure and must be formed during drying from the
beginning. This behavior could be explained by the
Ostwald ripening [1] including dissolutions and
precipitations, and the resulting structure is formed
by these competing interactions.
All dried gels, xero-gels and aero-gels, obtained
by us from the monosaccharide gels, are of essentially changeable structures in comparison with the
related wet gels.
References
[1]. Brinker C.J., Scherer G.W.: Sol-gel science: The
physics and chemistry of sol-gel processing. Academic
Press, Boston 1990.
[2]. Sakurai K., Jeong Y., Koumoto K., Friggeri A.,
Okamoto S., Inoue K., Shinkai S.: Langmuir, 19, 8211
(2003).
[3]. Gronwald O., Sakurai K., Luboradzki R., Kimura T.,
Shinkai S.: Carboch. Res., 331, 307 (2001).
[4]. Grigoriew H., Luboradzki R., Cunis S.: Langmuir, 20,
7374 (2004).
[5]. Grigoriew H., Luboradzki R., Gronkowski J.: J. Non-Cryst. Solids, 352, 3052 (2006).
156
MEASUREMENT OF 222Rn AND 220Rn
WITH SINGLE SCINTILLATION CELL
Bronisław Machaj, Piotr Urbański, Jakub Bartak
Quite often there exists a need for measurement
of radon 222Rn and thoron 220Rn concentration in air.
Such continuous measurements can be done with
two scintillation cells (Lucas cells) [1] connected
in series and air flow forced through the cells. Between the first and the second cell a delay of air
flow is so placed that thoron with its 55 s half-life
disintegrates. The first cell detects radon and thoron,
the second radon only. From these two readings,
concentration of radon and thoron can be determined. Another method of measurement of radon
and thoron is spectrometry of alpha radiation of
decay products [2]. The alpha radiation of 218Po
(6.0 MeV) is used for measurement of 222Rn, and
216
Po (6.78 MeV) alpha radiation for measurement
of 220Rn.
The aim of the presented investigations was the
development of a gauge model for measurement
of radon and thoron with a single Lucas cell. A
gauge for measurement of radon concentration in
air, MR-1, employing the Lucas cell as alpha radiation detector was developed earlier. Additional
function for measuring thoron concentration in air
should widen its applications.
Thoron laden and radon laden air are forced
to flow at a rate of 1 dm3/min through the Lucas
cell for a period of 10 min, simultaneously count
rate from the Lucas cell is measured. After 10 min,
Fig.1. Simulated alpha activity deposited on the walls of
Lucas cell when 1 dis/min of radon is flowing through
the cell during 10 min. The curve in the period 1-10
min is disturbed due to air flow (lower deposition of
218
Po inside the cell). Decay series of 222Rn →218Po→
214
Pb→214Bi (214Po) was simulated. Alpha activity of
222
Rn+218Po+214Po against time is shown in this Fig.
Fig.2. Simulated alpha activity deposited on the walls of
Lucas cell when 1 dis/min of 220Rn is flowing through
the cell during 10 min. Decay series of 220Rn→
216
Po→212Pb→212Bi was simulated. Alpha activity of
220
Rn+216Po+212Bi(212Po) against time is shown in
this Fig.
the air flow is switched off. Count rate is measured
at two time intervals from 1 to 10 min and from 20
to 30 min. The time intervals are a compromise
between the length of measuring cycle and the
random errors that are made smaller with increasing counting time. The relation between the count
Fig.3. Measured count rate against time (broken line)
and simulated count rate corresponding to real
(reference) radon concentration – 53.09 dis/min
(continuous line). n1=sum(r(1:10))=683 counts,
n 2 =sum(r(20:20))=1287 counts, from y=m\n:
222
Rn=56.0 dis/min, 220Rn=-1.85 dis/min.
157
y = m·ε\n = |A| [dis/min]
(3)
|B|
where n = |n1|
|n2|
Employing Cramer rules, concentration of radon
and thoron can be given in a more convenient form
for microprocessor processing:
A = (-0.000049·n1 + 0.0435·n2)/ε [dis/min]
(4)
B = (0.0548·n1 – 0.0305·n2)/e
Fig.4. Measuring arrangement for thoron: AP – air pump
1 dm3/min, TS – thoron source, AF – air filter, LC –
Lucas cell, MR-1 – radon radiometer, pgc – black
rubber pipe.
numbers n1 and n2 at the two time intervals and
the alpha activity deposited inside on the walls of
the cell are given by:
n1=(m11·A+m12·B)·ε
(1)
n2=(m21·A+m22·B)·ε
where: A – radon alpha activity, B – thoron alpha
activity, ε – deposition and detection efficiency.
The coefficients m11...m22 are determined from the
simulated activity of alpha radiation [3-5] (Figs.1
and 2). The coefficients m11, m12 are equal to the
total (sum) alpha activity at 1-10 min interval from
radon and thoron, respectively, and m21, m22 to the
total alpha activity at an interval of 20-30 min from
radon and thoron. After computation of the coefficients, the m matrix of coefficients is equal to:
m = |12.80 18.25|
|22.98 0.0218|
and equation (1) can be rewritten as:
n1 = (12.80·A + 18.25·B)·ε
(2)
n2 = (22.98·A + 0.0218·B)·ε
Concentration of radon A and thoron B computed
from equations (2) is given by matlab function:
Fig.5. Measured count rate against time (broken line) and
simulated alpha count rate corresponding to reference thoron concentration – 1323 dis/min (continuous line). n1=25635 counts, n2=48.6 counts; from
y=m\n: 222Rn=0.8 dis/min, 220Rn=1404 dis/min.
Random error due to fluctuations of count number
calculated from the relation for propagation of
errors:
s 2 (y) = (
∂y 2 2
∂y 2 2
) s (n 1 ) + (
) s (n 2 ) (5)
∂n 1
∂n 2
Table. Results of radon and thoron measurement.
The mean ratio of columns 4/6, for measurements mr62...mr65, is 1.003, which means that the computed concentration
y=m\n of radon is correct. The ratio of columns 5/7, for measured mr53, mr147, mr150 is 1.04, which means that the
computed concentration y=m\n of thoron is too high by 4%. This error can be corrected by dividing the thoron concentration from y=m\n by 1.04.
Negative values of “cross talk” from radon concentration into thoron concentration for measurements of mr62...mr65
can be neglected (no negative concentration exists). “Cross talk” from the thoron concentration into radon concentration is <1.5% of the indicated radon concentration.
158
is equal to 0.209 dis/min for 222Rn and 0.234 dis/min
for 220Rn at ε=1 and radon and thoron concentration equal to 1 dis/min.
Radon laden air was forced to flow 1 dm3/min,
within 10 min, across an air filter through the Lucas
cell φ54x74 mm (0.17 dm3) that was installed in an
MR-1 radon monitor and was placed inside a radon
chamber with known radon concentration. Simultaneously, pulse count rate of the Lucas cell was
measured in the time period up to 220 min. The
measured count rate (broken curve) is shown in
Fig.3. The simulated count rate (smooth curve)
corresponds to the reference radon concentration
which is equal to 53.09 dis/min at ε=1. Computed
radon concentration from y=m\n is 56.0 dis/min.
Similarly, thoron was forced to flow through the
Lucas cell (Fig.4), and count rate was measured.
Thoron source was ventilated until radiation equilibrium was reached and the outlet of thoron source
was connected to an air filter at the moment of starting count rate measurement. The 232U source is an
old source and is in radiation equilibrium with 228Th
and 224Ra.
The measured and simulated count of thoron is
given in Fig.5. The reference concentration at ε=1
is equal to 1323 dis/min. Computed thoron concentration from y=m\n is equal to 1404 dis/min.
Results of a series of measurements are given in
Table.
Measurements and computations carried out
confirm that radon and thoron concentration in
air can be measured with a single Lucas cell. Although the investigations were done on the assumption of detection efficiency ε=1, however, the
method is valid also for ε different from 1.
References
[1]. Coleman R.L.: A method for concurrent and continuous measurement of Rn-222 and Rn-220 using scintillation cell. Oak Ridge National Laboratory Report
No. ORNL/TM-2002/37.
[2]. Rad7. Electronic radon detector. Durridge Company.
www.durridge.com.
[3]. Machaj B., Bartak J.: Nukleonika, 43, 2, 175-184
(1996).
[4]. Machaj B., Urbanski P.: Nukleonika, 47, 1, 39-42
(2002).
[5]. Machaj B., Urbanski P.: Nukleonika, 49, 3, 123-129
(2004).
DOSIMETRIC GATE DSP-15
Edward Świstowski, Jan Mirowicz, Piotr Urbański, Jan Pieńkos
A common procedure of checking if personnel
involved in handling open radioisotopes is not
contaminated is installment of a dosimetric gate
[1-3] and obligatory checkup of all the employees.
A new dosimetric gate DSP-15 was developed in
the Department of Radioisotope Instruments and
Methods, Institute of Nuclear Chemistry and Technology. The gate is designed for fast radioactive
contamination measurement of the personnel leaving the area under dosimetric control where open
radioisotope sources are handled. The contamination is measured by proportional counters for beta
and gamma radiation located in the gate. Additionally, the gate is equipped with a local monitor displaying the state of the gate and measuring results
of the last measurement. In case contamination of
a person or a passage of an unauthorized person
through the gate takes place, this incident is detected
by an acoustic alarm. The gate is also equipped
with relays (contacts closed or open) that can, e.g.
block the exit of a contaminated person.
Automatic registration of staff is accomplished
by means of a proximity card presented against a
card reader of the gate. The gate is prepared for
operation in the monitoring system. Each measuring result is sent immediately to an external computer of the monitoring network, and is stored is
the gate memory. Three modes of operation can be
programmed: a) obligatory contamination measurements of persons entering and leaving the area
under control, b) no obligatory contamination measurement of persons entering and leaving the area
under control, c) obligatory contamination checkup
of persons leaving the area under control. The soft-
ware allows for programming parameters of the
gate such as permissible contamination level, time
of measurement, date and time setting etc. The
gauge program allows also for quick checkup of
proper operation of the gate.
The principle of operation of the gate is illustrated in a block diagram in Fig.1. Fifteen propor-
Fig.1. Block diagram of DSP-15: S1-S15 – proportional
counter LND 49741, W1-W15 – charge preamplifier,
E1-E15 – pulse discriminator, PLI1-PLI15 – programmable pulse counter, CZK – card reader, RS232
– serial port RS232, RS485 – serial port RS485, USB
– universal series bus, GL – loudspeaker, M – gate
monitor, uP – microprocessor system, IR bra – IR
control of a person presence in the gate, IR in – IR
control at the input to the gate, IR out – IR control
at the exit from the gate, IR S1 – IR control of S1
(left hand), IR S4 – IR control of S4 (right leg).
tional counters for measurement of beta and gamma
radiation are used in the gate. Four counters S1...S4
serve for measurement of contamination of legs
and hands. Five counters S6...S10 located at the
front column are used for measurement of contamination of front clothes of a person, and another five
counters S11...S15 placed at the rear column are
used for measurement of back clothes of a person.
Each measuring channel contains charge preamplifier, pulse discriminator and pulse counter under
the control of microprocessor system. The gate card
reader CZK serves for reading identification number of the person and for reading two special cards
SETTINGS and DOSIMETRY. When SETTING
card is read out a menu is displayed allowing for
setting measuring parameters of the gate. Presenting DOSIMETRY card against card reader mode
of operation of the gate is selected and the gate is
made ready for contamination measurements.
Measurement of contamination starts when identification card of a person is presented against the
card reader. Measuring results are stored in the
memory of the gate, are displayed on the screen
of a local monitor M, and are sent to an external
computer through a serial port RS485. A universal
series bus USB connects a laptop to the gate that
enables to read out measuring results stored in the
gate memory.
Number of registered pulses by the probes
S1...S15, that are proportional to the contamination, are compared with the permissible (programmed) level of contamination. In case when
excessive contamination is detected, the counter
that detected the contamination is shown, alarm
in sounded and the exit from the area under control is blocked.
The gate is equipped with IR (infrared) controls
to check if a person the contamination of whom is
to be measured is present inside the gate, and if his
legs and hands are in correct position. Additionally there are two other IR controls at the entrance
and exit from the gate (entrance and exit from the
area under control). The gate is also equipped with
movement and dusk sensors for automatic switching on light. A general view of the gate is shown in
Fig.2.
159
Fig.2. A general view of the gate.
The main parameters of the gate are following:
- contamination detected – beta and gamma radiation;
- radiation detector – LND 49741, proportional
counter, xenon filled, 3 mg/cm2 window, 115 cm2
area;
- sensitivity for 60Co – 600 cps/mR/h;
- background measuring time – 1 s;
- contamination measuring time – 1...9 s programmable;
- memory capacity – 500 measurements stored in
memory.
References
[1]. Sirius-4 serries. Hand and foot surface contamination
monitors. www.canberra.com/products/575.asp.
[2]. Argos-2. Whole body beta or alpha + beta surface contamination moniotor. Hand and foot surface contamination monitors. www.canberra.com/products/566.asp.
[3]. Dosimetric stand SD-50B. http://www.zami.com.pl.
GAMMA THIN LAYER CHROMATOGRAPHY ANALYZER SC-05
Edward Świstowski, Bronisław Machaj, Ewa Kowalska, Jan Pieńkos, Ewa Gniazdowska
Thin layer chromatography (TLC) is a technique
very often used in chemistry for identifying compounds, determining their purity, and following the
progress of reactions. It is also a good method for
optimization of the solvent system for a given separation problem [1]. TLC technique is faster and
simpler than column chromatography and requires
samples of much lower volume. Analysis of compounds that are labelled with isotopes emitting
gamma or beta radiation can be measured with
analyzers equipped with sensitive radiation detectors [2]. Such analyzers enables fast and accurate
scanning of prepared strips with investigated com-
pounds and the result of analysis can be shown in
the form of diagrams.
A gamma TLC analyzer, type SC-05, was developed and was constructed in the Department
of Radioisotope Instruments and Methods, Institute
of Nuclear Chemistry and Technology (INCT). A
general view of the analyzer is shown in Fig.1. It is
a laboratory instrument, with small dimensions
whose parameters allow for its wide application in
chemical and pharmaceutical laboratories, employing radioactive isotopes, and in nuclear medicine.
The analyzer can analyze strips 20 cm long with an
isotope labelled compound deposited on the strip.
160
Gamma isotopes: 125I, 131I, 111In, 188Re, 99mTc and
others with radiation energy 15-510 keV can be
analyzed. The radiation is collimated with a Pb slot
collimator 2.5x25 mm, 20 mm thick. An NaI(Tl)
φ25x25 mm scintillator is used as radiation detector. Linear stage with the strip analyzed is moved
in relation to the detector in 1 mm steps by a step
motor. Counting time of one step is programmed
in the range: 0.5, 1, 3, 6 s. The measuring result of
each step is displayed on the analyzer display, and
is stored in the analyzer memory. The measuring
Fig.1. A general view of gamma TLC analyzer SC-05.
results stored in the memory are sent through a
serial port to an external computer. Up to 50 diagrams can be stored in the memory. Three fixed
windows for 125I, 131I, 99mTc and one programmable
window in the range 15-510 keV are accessible for
the user. The measuring results stored in the memory
can be called from the memory and can be reviewed
on analyzer display in the form of a diagram together
with the date, time and parameters of the measurement. A fragment of the diagram (peak) can be selected and the number of counts in the selected
fragment is automatically displayed.
To ensure stable operation of measuring channel of the analyzer, automatic gain control circuit
is used. Light emitting diode (LED) is used as reference signal. During gain control process, the
amplitude of LED pulse is measured and the high
voltage of photomultiplier tube is changed until a
correct pulse amplitude is achieved. Automatic
gain control is activated after mains voltage is
switched on, and later before start of analysis of a
new strip.
Fig.2. TLC carried out to check the progress of a
S3(99mTcO)SPh complex formation [S3=S(CH2CH2SH)2]:
A – TLC of pertechnetate obtained from a 99Mo/99mTc
generator-Amersham (heptavalent technetium), B
– TLC of 99mTcO-ethylene glycol complex (pentavalent technetium), C – TLC of intermediate complex 99mTcO-thiophenol, D – TLC of mixed-ligand
complex S3(99mTcO)SPh.
One of the SC-05 analyzers was installed in the
Department of Radiochemistry of the INCT where
it is used for routine investigations. Example chromatograms achieved with the help of the analyzer
are shown in Fig.2.
References
[1]. http://www.raytest.de/radiochromatography/products/
Rita-Star.
[2]. http://www.chem.ucla.edu/~bacher/General/30BL/
tips/TLC1.html.
INVESTIGATION OF DUST POLLUTION IN ASSEMBLING HALL
OF TV SETS
Jan Pieńkos, Piotr Urbański
It is well known that airborne dust pollution has a
harmful influence on human being health. Because
of that, a maximum permissible level of dust pol-
lution was set, and dust concentration in the air is
measured. The smaller is the diameter of the dust
particles, the more deeply the particles can pen-
etrate into the lung. Average daily permissible level
of dust concentration in ambient air with particle
diameter <10 μm is set to 50 μg/m3.
Air dust pollution is important not only from
the point of view of human being protection. It is
also important from the point of view of clean air
161
of measuring results to an external PC computer.
Operation of the dust monitor was controlled by
the stuff of the Institute of Nuclear Chemistry and
Technology (INCT) and the measuring results were
also available by the INCT, although the distance
of assembling hall from Warsaw was more than 200
km. Work in the assembling hall was carried out
Fig.1. Localization of dust monitor in the assembling hall.
that is required in some industries. On request of
a producer of TV set, measurements of dust concentration were measured inside assembling hall
to investigate what is the dust pollution and how it
varies. The AMIZ-2004G monitor for automatic
measurement of airborne dust pollution of ambient air was used to investigate the dust concentration in the air. The dust monitor was located in the
middle of the assembling hall between the transporters moving the TV sets (Fig.1). The principle
of operation of the monitor employs attenuation
of beta radiation from 147Pm by the dust deposited
on an air filter to determine the mass of dust. Volume of the air from which the dust is deposited on
the filter is proportional to the time of deposition
(the flow of air through the filter is kept constant).
Dust concentration is the ratio of the dust mass to
the volume of air. The measurements were carried
out in the period of seven days. Total dust air inlet
was installed in the dust monitor. Thus, all the dust
particles without limitation of their diameter were
deposited on the air filter. The monitor was set to
continuous automatic mode of operation with 1 h
dust deposition on the air filter. The measuring
results were stored in the monitor memory. The dust
monitor was equipped with wireless transmission
Fig.2. Dust concentration inside assembling hall.
in two shifts from 6 to 22 h. Measuring results for
the first 4.5 days, illustrating how high was the dust
concentration in μg/m3, and how the dust concentration varied within these days are shown in Fig.2.
Similar dust concentration and similar variations
of dust concentration were observed in the remaining days of investigations. On analyzing the diagram
of dust concentration, the following observations
can be made:
- Dust concentration during work hours is high,
single readings reaching up to 150 μg/m3, and
the average 80-100 μg/m3. At night, when there
was no work activity the dust concentration was
much lower and fell to less than 50 μg/m3, and
on Sunday even to 30 μg/m3.
- It is up to the producer of TV sets to decide if
the recorded levels of dust concentration can be
accepted as sufficiently low, or appropriate steps
should be undertaken to decrease the dust concentration.
- The dust monitor AMIZ-2004G proved to be
an appropriate instrument for checkup measurements of dust concentration inside of some industrial halls.
COMMERCIAL APPLICATION OF ELECTRON BEAM ACCELERATORS
AT R&D AND SERVICE CENTER
Andrzej G. Chmielewski, Wojciech Migdał, Zbigniew Zimek, Iwona Kałuska,
Sylwester Bułka
Two pilot plant installations have been built at the
(INCT) to carry out R&D studies, to evaluate technical and economical requirements for industrial
facilities and to provide radiation processing service on a semi-industrial scale:
- pilot plant installation for polymer modification,
equipped with an electron accelerator ILU-6
type, 2 MeV and 20 kW beam power (supported
by the International Atomic Energy Agency –
IAEA, 1988);
- demonstration facility for flue gas treatment
with flow rate up to 20 000 Nm3/h, with two electron accelerators ELV 3A type 0.7 MeV and 50
kW beam power each (supported by the IAEA),
located at the power station “Kawęczyn” (1991);
162
and two industrial plants:
- radiation sterilization plant equipped with a
microwave linac ELEKTRONIKA 10/10 with
electron energy of 10 MeV and an average beam
power of 15 kW (1993);
- food irradiation plant with two 10 MeV electron
accelerators: PILOT with 1 kW and ELEKTRONIKA 10/10 with 10 kW of beam power (1992) [1].
The commercial irradiation plant was built to
satisfy growing demands for irradiation service. A
facility equipped with the electron accelerator
ELEKTRONIKA 10/10 was put into operation at
the INCT in 1993. The accelerator was manufactured in NPO “Toriy” (Moscow, Russia). 10 MeV
electron energy and up to 15 kW average beam
power is applied for radiation processing This accelerator is based on the running wave accelerating section and is placed vertically to avoid bending magnet and beam power losses related to its
application and a high average power magnetron
was used as a source of microwave energy.
The microprocessor controlled roller and belt
conveyor system is used to carry boxes with typical
size 580x460x200 mm. The speed of the conveyor
section located at the irradiation chamber, where
a stainless steel belt was applied, can be varied continuously within the range 0.3-7 m/min. Additional
equipment for two-sided irradiation can be used
when necessary. The rubber belts are used for transporting boxes between basement and ground levels.
Continuous monitoring of electron beam parameters
and speed of the conveyor were foreseen to fulfil
routine monitoring requirements. Upgraded accelerator control system for delivering required dose
and data acquisition for sterilization process have
been implemented. Figure 1 shows the block diagram of the accelerator installation with pointed
out devices being under computer control.
In Poland till the end of 50s of the XX century,
the research activities in the field of food irradiation were rather of basic research type. Practical
applications of food irradiation on a commercial
scale started in plant in 1993. The plant was established in the scope of government programme and
was equipped with two linear electron accelerators:
PILOT (10 MeV, 1 kW) and ELEKTRONIKA (10
MeV, 10 kW) [2,3].
Electron Gun
Actually, permission by the Ministry of Health
in Poland was granted for irradiation of the following kind of products: potatoes, onions, garlic,
mushrooms, spices and dried vegetables.
The role of the plant is to promote food irradiation technology in Poland by:
- development of new radiation technologies for
the preservation and hygienization of food products;
- development of radiation technologies for the
hygienization of natural components utilized in
the cosmetic industry;
- development of radiation technologies for the
hygienization of natural product utilized in the
pharmaceutical industry;
- development and standardization of control system for electron beam processing of food and
other products;
- organization of local (national) and/or international workshops and symposia devoted to technical, technological and economical aspects of
food irradiation.
Figure 2 shows the block diagram of the accelerator installation at the plant for food irradiation.
In both irradiation plants a computer system has
been installed which assures delivery of the desired
dose of electrons 9.0-9.5 MeV by controlling accelerator parameters with the use of an analog-digital
steering system and collecting data under technological conditions. Basing on the dose measurements
at the adjusted parameters and actual conveyor
speed, the system calculates the dose on-line that
is stored at computer hard disc.
Fig.2. Block diagram of the accelerator installation at the
plant for food irradiation.
*
Accelerating
Section
Magnetron
HV Pulse Power Supply
RF Power
Generator
Scanning
Coils *
*
Control System
Console
Interfaces
&
Signal Processing
Vacuum
Pump
Scanning
Horn
*
EB Extraction
Window
Motor
Steering
Conveyor
* Most important signal sources
for irradiation process status evaluation
Fig.1. Block diagram of the accelerator installation at the
plant for radiation sterilization.
The system enables simultaneous on-line control of irradiation parameters dedicated to food
products in agreement with the EC Directives
1999/2/EC, 1999/3/EC and Decree of the Ministry
of Health dated 15.01.2003 and to medical devices
in agreement with ISO 13485 and ISO 11137.
Dosimetric systems used in both plants are
traceable by the accreditated Laboratory for Measurements of Technological Doses.
In conclusion, two plants (one for sterilization
and the second for food irradiation) equipped with
linear accelerators 10 MeV, 10 kW have been operated for more than ten years. Technical and
economical feasibility of the electron beam technology for these applications have been demonstrated.
Quality assurance and quality control procedures following all ISO and EN standards are fully
implemented. The accredited laboratory for technological dosimetry, beside routine laboratories
led to the establishment of high level quality control
system.
Well prepared and implemented technical, economical and quality systems are inseparably conditions for the establishment of food irradiation and
sterilization facilities.
163
References
[1]. Zimek Z., Rzewuski H., Migdal W.: Nukleonika, 40,
3, 93-113 (1995).
[2]. Migdal W., Walis L., Chmielewski A.G.: Radiat. Phys.
Chem., 42, 1-3, 567-570 (1993).
[3]. Migdal W., Maciszewski W., Gryzlow A.: Radiat. Phys.
Chem., 46, 4-6, 749-752 (1995).
ELECTRON GUN FOR 10 MeV, 10 kW ELECTRON ACCELERATOR
Zygmunt Dźwigalski, Zbigniew Zimek
Main assembly of new electron accelerator which
is under construction at the Institute of Nuclear
Chemistry and Technology is standing wave accelerating structure operated at a frequency of 2856
MHz. The accelerating structure was provided by
“Lepton JSCo” company (St. Petersburg, Russia)
used as a source of electrons in this particular structure. The triode electron gun was designed and made
by the accelerator manufacturer “Toriy” company
(Moscow, Russia).
Electron gun construction modification is necessary to meet the requirements for standing wave struc-
Table. Electron beam parameters.
under the technical cooperation project supported
by the International Atomic Energy Agency. Electron beam emitted from an electron gun is introduced to the first resonator area of the accelerating structure. The electron beam parameters should
be compatible with electrical specification of the
structure (Table). Table contains the data related
to parameters of the electron beam which is introduced in the first resonator area of “Elektronika
10/10” accelerator. In that case the accelerating
structure is designed for travelling wave operating
mode at a frequency of 1863 MHz. The triode electron gun with a spherical impregnated cathode is
ture applied in a new accelerator. The following
modifications were introduced in vacuum area of
the triode electron gun:
- enlargement of the distance “L” between the
cathode and the grid from 1 to 3.6 mm (Fig.1);
- enlargement of the distance “A” between the
grid and the anode from 20 to 35 mm (Fig.1);
Fig.1. Electron gun – distances between electrodes.
Fig.2. Electron gun – additional element.
164
- additional element whose shape beam dimensions was incorporated (Fig.2).
The modification should allow to obtain desirable shape of the electron beam shown in Fig.3.
Shapes of the equipotential lines are congenial to
real shapes of the lines in the electron beam area,
Fig.4. Electron gun – silicon rubber insulator and additional insulator.
Fig.3. Electron gun – equipotential lines and electron trajectories.
but the lines differ from the real ones and far from
the beam area. It is due to the accepted mathematical model.
The electron gun main insulator, made from
silicon rubber, operating in air, could be not sufficient in the new working environment at the highest electrical strength. Electrical strength of the
insulator is too low, especially in long-term exploitation. Due to that, additional insulating part,
made from acrylic glass or epoxy glass will be incorporated (Fig.4). The glass ring will be connected
constantly with the main insulator. Electrical strength
of such a modified insulator will be much higher
than 50 kV.
165
ARTICLES
1.
Apel P.Yu., Blonskaya I.V., Dmitriev S.N., Orelovitch O.L., Sartowska B.
Structure of polycarbonate track-etch membranes: origin of the “paradoxical” pore shape.
Journal of Membrane Science, 282, 393-400 (2006).
2.
Asmus K.-D., Hug G.L., Bobrowski K., Mulazzani G., Marciniak B.
Transients in the oxidative and H-atom-induced degradation of 1,3,5-trithiane. Time-resolved studies
in aqueous solution.
Journal of Physical Chemistry A, 110, 9292-9300 (2006).
3.
Bartłomiejczyk T., Iwaneńko T., Wojewódzka M., Woliński J., Zabielski R., Kruszewski M.
Differential action of ghrelin and leptin, a human metabolism and energy regulators, on the lymphocyte
susceptibility to oxidative stress.
Journal of Physiology and Pharmacology, 57, Suppl. 2, 118 (2006).
4.
Bartłomiejczyk T., Iwaneńko T., Wojewódzka M., Woliński J., Zabielski R., Kruszewski M.
Ghrelin administration sensitizes blood mononuclear cells to oxidative stress.
Journal of Physiology and Pharmacology, 57, Suppl. 2, 119 (2006).
5.
Bartoś B., Bilewicz A.
Effect of crown ethers on Sr2+, Ba2+, and Ra2+ uptake by tunnel-structure ion exchangers.
Solvent Extraction and Ion Exchange, 24, 261-269 (2006).
6.
Barysz M., Kędziera D., Leszczyński J., Bilewicz A.
Structure and hydrolysis of the heavy alkaline earth cations: relativistic studies.
International Journal of Quantum Chemistry, 106, 2422-2427 (2006).
7.
Bilewicz A., Bartoś B., Misiak R., Petelenz B.
Separation of 82Sr from rubidium target for preparation of 82Sr/82Rb generator.
Journal of Radioanalytical and Nuclear Chemistry, 268, 3, 485-487 (2006).
8.
Bojanowska-Czajka A., Drzewicz P., Kozyra Cz., Nałęcz-Jawecki G., Sawicki J., Szostek B.,
Trojanowicz M.
Radiolytic degradation of herbicide 4-chloro-2-methyl phenoxyacetic acid (MCPA) by γ-radiation for
environmental protection.
Ecotoxicology and Environmental Safety, 65, 265-277 (2006).
9. Bojanowska-Czajka A., Drzewicz P., Nałęcz-Jawecki G., Sawicki J., Trojanowicz M.
Zastosowanie promieniowania jonizującego do degradacji wybranych pestycydów w wodach i ściekach
(Application of ionizing radiation to the decomposition of selected pesticides in waters and sewages).
Postępy Techniki Jądrowej, 49, 1, 26-31 (2006).
10. Bonilla F.A, Skeldon P., Thompson G.E., Piekoszewski J., Chmielewski A.G., Sartowska B.,
Stanisławski J.
Corrosion resistant Ti-Pd surface alloys produced by high intensity pulsed plasma beams. Part 2. Deposition by pulsed implantation doping mode with palladium implantation using a MEVVA source.
Surface and Coatings Technology, 200, 4684-4692 (2006).
11. Bonilla F.A, Skeldon P., Thompson G.E., Piekoszewski J., Chmielewski A.G., Sartowska B.,
Stanisławski J., Bailey P., Noakes T.C.Q.
Corrosion resistant Ti-Pd surface alloys produced by high intensity pulsed plasma beams. Part 1. Deposition by pulsed erosion and vacuum evaporation/pulsed implantation doping modes.
Surface and Coatings Technology, 200, 4674-4683 (2006).
166
12. Brzóska K., Iwaneńko T., Wojewódzka M., Woliński J., Kruszewski M.
Differential action of human metabolism regulators on the lymphocyte susceptibility to oxidative stress.
Acta Biochimica Polonica, 53, Suppl. 1, 172 (2006).
13. Brzóska K., Kruszewski M., Szumiel I.
Nonhomologous end-joining deficiency of L5178Y-S cells is not associated with mutation in the ABCDE
autophosphorylation cluster.
Acta Biochimica Polonica, 53, 1, 233-236 (2006).
14. Brzóska K., Męczyńska S., Kruszewski M.
Iron-sulfur clusters proteins: electron transfer and beyond.
15. Brzóska K., Męczyńska S., Kruszewski M.
Non-haem iron proteins: new functions of old pals.
16. Chmielewska D.K., Łukasiewicz A., Michalik J., Sartowska B.
Silica materials with biocidal activity.
Nukleonika, 51, Suppl. 1, s69-s72 (2006).
17. Chmielewski A.G.
Worldwide developments in the field of radiation processing of materials in the down of 21st century.
18. Chmielewski A.G., Licki J., Pawelec A., Tymiński B., Zimek Z.
Operational experience of the industrial plant for electron beam flue gas treatment.
Ecological Chemistry and Engineering, 13, 10, 1057-1063 (2006).
19. Chmielewski A.G., Palige J., Zakrzewska-Trznadel G.
Izotopy widzą wszystko (Isotopes see everything).
Almanach Ekologii, 122-124 (2006).
20. Chmielewski A.G., Tymiński B., Pawelec A., Palige J., Dobrowolski A.
Modelowanie przepływu gazu w reaktorze do oczyszczania spalin metodą radiacyjną z użyciem metod
CFD (Modelling of gas flow in a reactor for electron beam flue gas treatment using CFD methods).
Prace Naukowe Instytutu Inżynierii Chemicznej PAN, 7, 59-71 (2006).
21. Chwastowska J., Danko B.
Analiza materiałów środowiskowych (Analysis of environmental materials).
Ekologia, 4, 38-39 (2006).
22. Cieśla K., Salmieri S., Lacroix M.
γ-Irradiation influence on the structure and properties of calcium caseinate-whey protein isolate based
films. Part 1. Radiation effect on the structure of proteins gels and films.
Journal of Agricultural and Food Chemistry, 54, 6374-6384 (2006).
γ-Irradiation influence on the structure and properties of calcium caseinate-whey protein isolate based
films. Part 2. Influence of polysaccharide addition and radiation treatment on the structure and functional properties of the films.
Journal of Agricultural and Food Chemistry, 54, 8899-8908 (2006).
Modification of the properties of milk protein films by gamma radiation and polysaccharide addition.
Journal of the Science of Food and Agriculture, 86, 908-914 (2006).
25. Dalivelya O., Savina N., Kuzhir T., Buraczewska I., Wojewódzka M., Szumiel I.
Effects of an antimutagen of 1,4-dihydropyridine series on cell survival and DNA damage in L5178Y
murine sublines.
Nukleonika, 51, 3, 141-146 (2006).
26. Danilczuk M., Lund A., Sadło J., Yamada H., Michalik J.
Conduction electron spin resonance of small silver particles.
Spectrochimica Acta A, 63, 189-191 (2006).
167
27. Danilczuk M., Pogocki D., Lund A., Michalik J.
EPR and DFT study on the stabilization of radiation-generated methyl radicals in dehydrated Na-A
zeolite.
Journal of Physical Chemistry B, 110, 24492-24497 (2006).
28. Danko B., Samczyński Z., Dybczyński R.
Analytical scheme for group separation of the lanthanides from biological materials before their determination by neutron activation analysis.
Chemia Analityczna, 51, 527-539 (2006).
29. Dembiński W., Herdzik I., Skwara W., Bulska E., Wysocka A.I.
Isotope effects of gallium and indium in cation exchange chromatography.
Nukleonika, 51, 4, 217-220 (2006).
30. Deperas-Kamińska M., Szumiel I., Wójcik A.
Elementy radiologii dla pilota Pirxa (Elements of radiobiology for pilot Pirx).
Kosmos, Problemy Nauk Biologicznych, 55, 4, 337-345 (2006).
31. Deptuła A., Chwastowska J., Łada W., Olczak T., Wawszczak D., Sterlińska E., Sartowska B.,
Goretta K.C.
Sol-gel-derived hydroxyapatite and its application to sorption of heavy metals.
Advances in Science and Technology, 45, 2198-2203 (2006).
32. Deptuła A., Dubarry M., Noret A., Gaubicher J., Olczak T., Łada W., Guyomard D.
Atypical Li1.1V3O3 prepared by a novel synthesis route.
Electrochemical and Solid-State Letters, 9, 1, A16-A18 (2006).
33. Deptuła A., Łada W., Olczak T., Chmielewski A.G.
Application of Pt/Al2O3 catalysts produced by sol-gel process to uranyl ion reduction.
34. Filipczak K., Woźniak M., Ulański P., Olah L., Przybytniak G., Olkowski R.M., Lewandowska-Szumieł M., Rosiak J.M.
Poly(ε-caprolactone) biomaterial sterilized by e-beam irradiation.
Macromolecular Bioscience, 6, 261-273 (2006).
35. Filipiuk D., Fuks L., Majdan M.
Biosorpcja jako metoda usuwania i odzysku metali ciężkich z wodnych ścieków przemysłowych
(Biosorption as a new method for sequestering heavy metals in industrial aqueous effluents).
Przemysł Chemiczny, 85, 6, 417-422 (2006).
36. Fuks L., Filipiuk D., Majdan M.
Transition metal complexes with alginate biosorbent.
Journal of Molecular Structure, 792-793, 104-109 (2006).
37. Fuks L., Polkowska-Motrenko H.
Interlaboratory comparison of the determination of 137Cs and 90Sr in water, food and soil: preparation
and characterization of test materials.
38. Głuszewski W.
Nowe zakłady produkcji polietylenu PE i polipropylenu PP (New works for the production of polyethylene (PE) and polypropylene (PP).
39. Głuszewski W.
Rak płuca. Wczesne wykrycie = dłuższe życie (Lung cancer. Early detection=longer life)
40. Głuszewski W., Panta P.P., Kubera H.
Wpływ promieniowania jonizującego na właściwości materiałów opakowaniowych (Effect of ionizing
radiation on the properties of packaging materials).
Opakowanie, 9, 24-26 (2006).
168
41. Głuszewski W., Zagórski Z.P.
Zastosowanie chromatografii gazowej (GC) w badaniach modyfikacji radiacyjnej polipropylenu (Application of gas chromatography to the investigation of radiation chemistry of polypropylene).
Czasopismo Techniczne. Mechanika, 6, 190-192 (2006).
Zdolności przerobowe akceleratorów IChTJ do obróbki radiacyjnej (Production capacity of the INCT
accelerators for radiation processing).
Kauczuki Naturalne i Syntetyczne, 3, 28-30 (2006).
43. Gniazdowska E., Kraus W., Emmerling F., Spies H., Stephan H.
Tetrabutylammonium bis(2-amidobenzenethiolato-κ2S,N)oxorhenate(V).
Acta Crystallographica E 62, m1197-m1199 (2006).
44. Grądzka I.
Mechanizmy i regulacja programowanej śmierci komórek (Mechanisms and regulation of the programmed cell death).
Postępy Biochemii, 52, 2, 157-165 (2006).
45. Grigoriew H., Luboradzki R., Gronkowski J.
USAXS studies of monosaccharide gels. I. Dependence of the glucofuranose-based gel structure on
the gelator concentration.
Journal of Non-Crystalline Solids, 352, 3052-3057 (2006).
46. Gryz M., Starosta W., Leciejewicz J.
Bis(μ-pyridazine-3,6-carboxylato-κ4N,O:N’,O’)-bis[diaquazinc(II)].
Acta Crystallographica E, 62, m3470-m3472 (2006).
trans-Diaquabis(pyridazine-3-carboxylato-κ2N,O)-magnesium(II) dihydrate.
48. Grzesiuk W., Nieminuszczy J., Kruszewski M., Iwaneńko T., Płazińska M., Bogdańska M.,
Bar-Andziak E., Królicki L., Grzesiuk E.
DANN damage and its repair in lymphocytes and thyroid nodule cells during radioiodine therapy in
patients with hyperthyroidism.
Journal of Molecular Endocrinology, 37, 527-532 (2006).
49. Khayet M., Mengual J.I., Zakrzewska-Trznadel G.
Direct contact membrane distillation for nuclear desalination. Part II: experiments with radioactive
solutions.
International Journal of Nuclear Desalination, 2, 1, 56-73 (2006).
50. Konarski P., Ćwil M., Piekoszewski J., Stanisławski J.
SIMS characterisation of superconductive MgB2 layers prepared by ion implantation and pulsed plasma
treatment.
Applied Surface Science, 252, 7078-7081 (2006).
51. Kornacka E., Kozakiewicz J., Legocka I., Przybylski J., Przybytniak G., Sadło J.
Radical processes induced in poly(siloxaneurethaneureas) by ionising radiation.
Polymer Degradation and Stability, 91, 2182-2188 (2006).
52. Kornacka E., Kozakiewicz J., Przybytniak G.
Odporność radiacyjna aromatycznych poliuretanów przeznaczonych do zastosowań medycznych (Radiation resistance of aromatic polyurethanes for medical applications).
Inżynieria Biomateriałów, 58-60, 143-145 (2006).
53. Kornacka E.M., Przybytniak G., Święszkowski W.
Wpływ stopnia krystaliczności na stabilność radiacyjną UHMWPE (The influence of crystallinity on
radiation stability of UHMWPE).
Inżynieria Biomateriałów, 58-60, 146-149 (2006).
169
54. Krejzler J., Narbutt J., Foreman M.R.St J., Hudson M.J., Casensky B., Madic C.
Solvent extraction of Am(III) and Eu(III) from nitrate solution using synergistic mixtures of n-tridentate heterocycles and chlorinated cobalt dicarbollide.
Czechoslovak Journal of Physics, 56, Suppl. D, D459-D467 (2006).
55. Lankoff A., Banasik A., Duma A., Ochniak E., Lisowska H., Kuszewski T., Góźdź S., Wójcik A.
A comet assay study reveals that aluminium induces DNA damage and inhibits the repair of radiation-induced lesions in human peripheral blood lymphocytes.
Toxicology Letters, 161, 27-36 (2006).
56. Lankoff A., Bialczyk J., Dziga D., Carmichael W.W., Grądzka I., Lisowska H., Kuszewski T.,
Góźdź S., Piorun I., Wójcik A.
The repair of gamma-radiation-induced DNA damage is inhibited by microcystin-LR, the PP1 and
PP2A phosphate inhibitor.
Mutagenesis, 21, 1, 83-90 (2006).
57. Lankoff A., Bialczyk J., Dziga D., Carmichael W.W., Lisowska H., Wójcik A.
Inhibition of nucleotide excision repair (NER) by microcystin-LR in CHO-K1 cells.
Toxicon, 48, 957-965 (2006).
58. Lankoff A., Wójcik A., Fessard V., Meriluoto J.
Nodularin-induced genotoxicity following oxidative DANN damage and aneuploidy in HepG2 cells.
Toxicology Letters, 164, 239-248 (2006).
59. Liniecki J., Wójcik A.
20 lat po awarii w Czarnobylu. Co dziś wiemy o następstwach zdrowotnych? (20 years after the Chernobyl
accident. What we know today about the radiological consequences?)
60. Lisowska H., Lankoff A., Wieczorek A., Florek A., Kuszewski T., Góźdź S., Wójcik A.
Enhanced chromosomal radiosensitivity in peripheral blood lymphocytes of larynx cancer patients.
International Journal of Radiation Oncology, Biology, Physics, 66, 4, 1245-1252 (2006).
61. Łyczko K., Narbutt J., Paluchowska B., Maurin J.K., Persson I.
Crystal structure of lead(II) acetylacetonate and the structure of the acetylacetone solvated lead(II)
ion in solution studies by large-angle X-ray scattering.
Dalton Transactions, 3972-3976 (2006).
62. Mádl M., Kunicki-Goldfinger J.J.
Eiland: Georg Gundelach and the glassworks on the Dìèin Estate of count Maximilian Thun-Hohenstein.
Journal of Glass Studies, 48, 225-247 (2006).
63. Majkowska A., Bilewicz A.
Formation kinetics and stability of some TRI and tetraaza derivative complexes of scandium.
The Quarterly Journal of Nuclear Medicine and Molecular Imaging, 50, Suppl. 1 to issue 1, 45 (2006).
64. Markowicz S., Niedzielska J., Kruszewski M., Ołdak T., Gajkowska A., Machaj E.K., Skurzak H.,
Pojda Z.
Nonviral transfection of human umbilical cord dentritic cells is feasile, but the yield of dendritic cells
with transgene expression limits the application of this method in cancer immunotherapy.
65. Męczyńska S., Lewandowska H., Kruszewski M.
The role of lysosomal iron in dinitrosyl iron complexes formation.
66. Orelovitch O.L., Apel P.Yu., Sartowska B.
New methods of track membrane treatment in the preparation of samples for further observation with
scanning electron microscopy.
Journal of Microscopy, 224, 100-223 (2006).
67. Palige J., Dobrowolski A., Owczarczyk A., Chmielewski A.G., Ptaszek S.
Badania znacznikowe i CFD procesu sedymentacji osadu w osadniku prostokątnym (Tracer and CFD
investigations of sedimentation processes in a rectangular settler).
Inżynieria i Aparatura Chemiczna, 6a, 181-182 (2006).
170
68. Palige J., Dobrowolski A., Owczarczyk A., Chmielewski A.G., Ptaszek S.
Badania znacznikowe i CFD struktury przepływu ścieków w osadnikach prostokątnych dla różnych
geometrii napływu i wypływu ścieków (Tracer and CFD investigations of flow structure for two wastewater inputs and outputs configurations in rectangular settler).
Inżynieria i Aparatura Chemiczna, 5a, 104-107 (2006).
69. Pawlukojć A., Natkaniec I., Bator G., Sobczyk L., Grech E., Nowicka-Scheibe J.
Low frequency internal modes of 1,2,4,5-tetramethylbenzene, tetramethylpyrazine and tetramethyl-1,4-benzoquinone INS, Raman, infrared and theoretical DFT studies.
Spectrochimica Acta Part A, 63, 766-773 (2006).
70. Pawlukojć A., Sawka-Dobrowolska W., Bator G., Sobczyk L., Grech E., Nowicka-Scheibe J.
X-ray diffraction, inelastic neutron scattering (INS) and infrared (IR) studies on 2:1 hexamethylbenzene
(HMB)-tetracyanoethylene (TCNE) complex.
Chemical Physics, 327, 311-318 (2006).
71. Peimel-Stuglik Z., Fabisiak S.
Solid state “self-calibrated” EPR-dosimeters – advantageous and shortcomings.
Spectrochimica Acta Part A, 63, 855-860 (2006).
72. Podrez-Radziszewska M., Bąkowski D., Lachowicz M., Głuszewski W., Dudziński W.
Charakterystyka twardości i właściwości wytrzymałościowych UHMWPE po napromieniowaniu wiązką
elektronów (Characterization of hardness and strength properties UHMWPE after irradiation with an
electron beam).
Inżynieria Materiałowa, 2, 75-78 (2006).
73. Polkowska-Motrenko H., Chajduk E., Dybczyński R.
Selective separation of trace amounts of selenium using extraction chromatography and its determination by neutron activation analysis in biological samples.
Chemia Analityczna, 51, 581-591 (2006).
74. Polkowska-Motrenko H., Dybczyński R.
Activities of the INCT, Warsaw, in the domain of quality assurance for inorganic analysis.
75. Prager M., Pietraszko A., Sobczyk L., Pawlukojć A., Grech E., Seydel T., Wischnewski A.,
Zamponi M.
X-ray diffraction and inelastic neutron scattering study of 1:1 tetramethylpyrazine chloranilic acid complex: temperature, isotope, and pressure effects.
The Journal of Chemical Physics, 125, 194525-1-11 (2006).
76. Premkumar T., Govindarajan S., Starosta W., Leciejewicz J.
Diaquatetrakis(pyrazine-2-carboxylato-κ2O,N)-thorium(IV) trihydrate.
77. Pruszyński M., Bilewicz A.
211
At-Rh(16-S4-diol) complex as a precursor for astatine radiopharmaceuticals.
The Quarterly Journal of Nuclear Medicine and Molecular Imaging, 50, Suppl. 1 to issue 1, 44 (2006).
78. Pruszyński M., Bilewicz A., Wąs B., Petelenz B.
Formation and stability of astatide-mercury complexes.
79. Przybytniak G., Kornacka E., Ryszkowska J., Bil M., Rafalski A., Woźniak P., Lewandowska-Szumieł M.
Influence of radiation sterilization on poly(ester urethanes) designed for medical applications.
80. Sadlej-Sosnowska N., Ocios A., Fuks L.
Selectivity of similar compounds’ identification using IR spectrometry: β-Lactam antibiotics.
Journal of Molecular Structure, 792-793, 110-114 (2006).
81. Sadło J., Michalik J., Kevan L.
EPR and ESEEM study of silver clusters in ZK-4 molecular sieves.
171
82. Sadło J., Michalik J., Stachowicz W., Strzelczak G., Dziedzic-Gocławska A., Ostrowski K.
EPR study on biominerals as materials for retrospective dosimetry.
83. Samczyński Z.
Ion exchange behavior of selected elements on Chelex 100 resin.
Solvent Extraction and Ion Exchange, 24, 781-794 (2006).
84. Sartowska B., Piekoszewski J., Waliś L., Stanisławski J., Nowicki L., Ratajczak R.
Characterization of the near-surface layers of carbon steels modified by interaction with intense pulsed
plasma beams: scanning electron microscopy investigations.
Journal of Microscopy, 224, 114-116 (2006).
85. Sastry M.D., Gustafsson H., Danilczuk M., Lund A.
Dynamical effects and ergodicity in the dipolar glass phase: evidence from time-domain EPR and
phase memory time studies of AsO44– in Rb1-x(NH4)xH2PO4 (x = 0, 0.5, 1).
Journal of Physics: Condensed Matter, 18, 4265-4284 (2006).
86. Sawka-Dobrowolska W., Bator G., Czarnik-Matusewicz B., Sobczyk L., Pawlukojć A., Grech E.,
Nowicka-Scheibe J., Rundlöf H.
X-ray and neutron diffraction, IR and INS spectroscopic and DFT theoretical studies on the tetramethylpyrazine-1,2,4,5-tetracyanobenzene complex.
Chemical Physics, 327, 237-246 (2006).
87. Schlick S., Bosnjakovic A., Danilczuk M.
Direct ESR and spin trapping methods for the study of radicals in PEMS and model compounds exposed to oxygen radicals.
Abstracts of Papers of the American Chemical Society, Division of Fuel Chemistry, 51, 2, 688-689 (2006).
88. Sommer S., Deperas-Kamińska M., Wójcik A., Szumiel I.
Indywidualna promieniowrażliwość chromosomów i odcisk palca promieniowania. Otwarte pytania w
dziedzinie dozymetrii biologicznej (Individual radiosensitiveness of chromosomes and fingerprint of
radiation. Open questions in the field of biological dosimetry).
89. Starosta W., Buczkowski M., Sartowska B., Wawszczak D.
Studies on template-synthesized polypyrrole nanostructures.
90. Starosta W., Leciejewicz J.
catena-Poly[[aquacalcium(II)]bis(μ-1H-imidazole-4-carboxylato)-κ4N,O:O,O’; κ3O,O’:O’].
91. Starosta W., Leciejewicz J., Premkumar T., Govindarajan S.
Crystal structures of two Ca(II) complexes with imidazole-4,5-dicarboxylate and water ligands.
Journal of Coordination Chemistry, 59, 5, 557-564 (2006).
92. Stupińska H., Iller E., Zimek Z., Kopania E., Palenik J., Milczarek S.
Otrzymywanie mikrokrystalicznej celulozy z zastosowaniem ekologicznych metod depolimeryzacji
celulozy. Część I. Degradacja radiacyjna (Obtaining of microrystalline cellulose with the ecological
method of cellulose depolymerization. Part I. The radiational degradation).
Przegląd Papierniczy, 8, 475-481 (2006).
93. Sun Y., Chmielewski A.G., Bułka S., Zimek Z.
Influence of base gas mixture on decomposition of 1,4-dichlorobenzene in an electron beam generated
plasma reactor.
Plasma Chemistry and Plasma Processing, 26, 347-359 (2006).
94. Szumiel I.
Epidermal growth factor receptor and DNA double strand break repair: the cell’s self-defence.
Cellular Signalling, 18, 1537-1548 (2006).
95. Trojanowicz M.
Analytical applications of carbon nanotubes: a review.
Trends in Analytical Chemistry, 25, 5, 480-489 (2006).
172
96. Trojanowicz M., Wójcik L., Szostek B., Korczak K., Bojanowska-Czajka A., Drzewicz P., Masar M., Kaniansky D.
Application of capillary electrophoresis in analysis of perfluorinated carboxylic acids.
Organohalogen Compounds, 68, 2531-2534 (2006).
97. Trybuła Z., Kempiński W., Andrzejewski B., Piekara-Sady L., Kaszyński J., Trybuła M., Piekoszewski J., Stanisławski J., Barlak M., Richter E.
Superconducting regions and Kondo effect of MgB2 formed by implantation of magnesium ions into
boron substrate.
Acta Physica Polonica A, 109, 4-5, 657-660 (2006).
98. Tymiński B., Zwoliński K., Jurczyk R.
Badania w skali wielkolaboratoryjnej rozkładu odpadów poliolefin na produkty ciekłe (Research on
waste polyolefine degradation into liquid products).
Prace Naukowe Instytutu Inżynierii Ochrony Środowiska Politechniki Wrocławskiej z. 81, Seria:
Konferencje z. 12, 263-267 (2006).
99. Tymiński B., Zwoliński K., Jurczyk R.
Degradation of polyolefine wastes into liquid fuels.
100. Urbański P., Bartak J., Jakowiuk A., Świstowski E., Machaj B., Kowalska E., Pieńkos J.
Nowe urządzenia do promieniowania jonizującego (New instruments for measurements of ionizing
radiation).
Ekopartner, 11, 24-25 (2006).
101. Urbański P., Bartak J., Jakowiuk A., Świstowski E., Machaj B., Kowalska E., Pieńkos J.
Urządzenia promieniowania jonizującego (Instruments of ionizing radiation).
Ekologia, 6, 42-43 (2006).
102. Wierzchnicki R.
Izotopy stabilne w kontroli pochodzenia żywności (Stable isotopes in the control of food authencity).
103. Wojewódzka M., Buraczewska I., Szumiel I., Grądzka I.
DNA double-strand break rejoining in radioadapted human lymphocytes: evaluation by neutral comet
assay and pulse-field gel electrophoresis.
Nukleonika, 51, 4, 185-191 (2006).
104. Wojewódzka M., Kruszewski M., Ołdak T., Bartłomiejczyk T., Goździk A., Szumiel I.
Inhibition of poly(ADP-ribose)polymerase does not affect the recombination events in CHO xrs6 and
wild type cells.
Radiation and Environmental Biophysics, 45, 277-287 (2006).
105. Wojewódzka M., Szumiel I.
Ogniska histonu γ-H2AX. Marker pęknięć podwójnoniciowych DNA (γ-H2AX histone foci – marker
of DNA double strand breaks).
106. Wójcik A., Bochenek A., Lankoff A., Lisowska H., Padjas A., Szumiel I., von Sonntag C., Obe G.
DNA interstrand crosslinks are induced in cells prelabelled with 5-bromo-2’-deoxyuridine and exposed
to UVC radiation.
Journal of Photochemistry and Photobiology B: Biology, 84, 15-20 (2006).
107. Wójcik A., Szumiel I., Liniecki J.
Hormeza czy to zjawisko powszechne i powszechnie nieznane? (Hormesis, a common phenomenon
and commonly unknown?)
108. Yordanov N.D., Fabisiak S., Lagunov O.
Effect of the shape and size of dosimeters on the response of solid state/EPR dosimetry.
Radiation Measurements, 41, 257-263 (2006).
109. Zagórski Z.P.
Radiation chemistry of radioactive waste to be stored in the salt mine repository.
173
110. Zagórski Z.P.
Radiation induced dehydrogenation of organics: from amino acids, to synthetic polymers, to bacterial
spores.
Indian Journal of Radiation Research, 3, 2-3, 89-93 (2006).
111. Zakrzewska-Trznadel G.
Membrane processes for environmental protection: application in nuclear technology.
Tritium removal from water solutions.
Desalination, 200, 737-738 (2006).
113. Zhydachevskii Ya., Suchocki A., Sugak D., Luchechko A., Berkowski M., Warchoł S., Jakieła R.
Optical observation of the recharging processes of manganese ions in YalO3:Mn crystals under radiation and thermal treatment.
Journal of Physics: Condensed Matter, 18, 5389-5403 (2006).
114. Zimek Z.
Chemia i technika radiacyjna (Radiation chemistry and technology).
115. Zimek Z., Przybytniak G., Kałuska I.
Radiation processing of polymers and semiconductors at the Institute of Nuclear Chemistry and Technology.
116. Zimek Z., Przybytniak G., Nowicki A., Mirkowski K.
Zastosowanie techniki radiacyjnej do otrzymywania napełniaczy bentonitowych i ich mieszanek z polipropylenem (Application of radiation technique to obtain bentonite fillers and their mixtures with polypropylene).
Inżynieria Materiałowa, 6, 1333-1336 (2006).
BOOKS
1. Chmielewski A.G., Kang C.M., Kang C.S., Vujic J.L.
Radiation technology. Introduction to industrial and environmental applications.
Seoul National University Press, Seoul 2006, 274 p.
CHAPTERS IN BOOKS
1. Chiarizia R., Jensen M.P., Borkowski M., Nash K.L.
A new interpretation of third-phase formation in the solvent extraction of actinides by TBP.
In: Separation for the nuclear fuel cycle in the 21st century. G.L. Lumetta, K.L. Nash, S.B. Clark, J.I. Friese
(eds). ACS Symposium Series no. 933. American Chemical Society, Washington, DC 2006, pp. 135-150.
2. Chmielewski A.G., Sun Y.
Air emission and off-gas treatment technologies – overview.
In: Ochrona powietrza w teorii i praktyce. Tom 1. Red. J. Konieczyński. Instytut Podstaw Inżynierii PAN,
Zabrze 2006, pp. 9-16.
3. Deptuła A., Goretta K.C., Olczak T., Łada W., Chmielewski A.G., Jakubaszek U., Sartowska B.,
Alvani C., Casadio S., Contini V.
Preparation of titanium oxide and metal titanates as powders, thin films, and microspheres by novel inorganic sol-gel process.
In: Nanoparticles and nanostructures in sensors and catalysis. Chuan-Jian Zhong, N.A. Kotov, W. Daniell,
F.P. Zamborini (eds). Materials Research Society Symposium Proceedings vol. 900E. MRS, Warrendale
2006, pp. 0900-O09-10.1-10.6.
4. Jakowiuk A., Świstowski E., Urbański P., Pieńkos J., Machaj B., Salwa J.
System monitoringu zapylenia powietrza (Wireless system for air dust concentration monitoring).
174
Zabrze 2006, pp. 119-127.
5. Pruszyński M., Bilewicz A.
Binding of 131I to rhodium(III) complexes: model studies on attaching 211At to metal complexes.
In: Application of radiotracers in chemical, environmental and biological sciences. S. Lahiri, D. Layak, A.
Mukhopadhyay (eds). Saha Institute of Nuclear Physics, Kolkata 2006. Vol. 2, pp. 20-22.
6. Sun Y., Chmielewski A.G., Bułka S., Zimek Z.
Organic pollutants treatment from air using electron beam technology.
Zabrze 2006, pp. 253-257.
7. Zimek Z.
Economic benefits of radiation processing applied in Poland.
In: A study on economical benefits of industrial applications of radiation and radioisotopes. Report of
Consultants Meeting, Vienna 6-9 December 2004. IAEA, Vienna 2006, pp. 56-63.
THE INCT REPORTS
1. INCT Annual Report 2005.
Institute of Nuclear Chemistry and Technology, Warszawa 2006, 235 p.
2. Zakrzewska Trznadel G.
Procesy membranowe w technologiach jądrowych (Membrane processes in nuclear technologies).
Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria A nr 1/2006, 191 p.
3. Zakrzewska Trznadel G.
Procesy membranowe w technologiach jądrowych – wybrane zagadnienia modelowania transportu masy
oraz projektowania systemów rozdzielania (Membrane processes in nuclear technologies – selected issues
of mass tansport modeling and separation systems design).
4. Polkowska-Motrenko H., Dybczyński R., Chajduk E., Danko B., Kulisa K., Samczyński Z., Sypuła M., Szopa Z.
Polish reference material: Corn Flour (INCT-CF-3) for inorganic trace analysis – preparation and certification.
Institute of Nuclear Chemistry and Technology, Warszawa 2006. Raporty IChTJ. Seria A nr 3/2006, 47 p.
Polish reference material: Soya Bean Flour (INCT-CBF-4) for inorganic trace analysis – preparation
and certification.
Institute of Nuclear Chemistry and Technology, Warszawa 2006. Raporty IChTJ. Seria A nr 4/2006, 51 p.
6. Herdzik I.
ICP-MS jako metoda oznaczania stosunków izotopowych galu, indu i talu w badaniach efektów izotopowych w układach chromatograficznych (ICP-MS as the method of the determination of gallium, indium
and tallium isotope ratios in the studies of isotope effects in the chromatography systems).
7. Pawlukojć A.
Badania widm oscylacyjnych, w obszarze niskich częstości, wybranych kompleksów molekularnych z przeniesieniem ładunku oraz ich składników metodą nieelastycznego rozpraszania neutronów termicznych
(The investigations of low frequency oscillation spectra of selected charge transfer molecular complexes
and their compounds by inelastic thermal neutron spectroscopy).
8. Chmielewski A.G.
Packaging for food irradiation.
Institute of Nuclear Chemistry and Technology, Warszawa 2006. Raporty IChTJ. Seria B nr 1/2006, 26 p.
175
9. Polkowska-Motrenko H., Dudek J., Chajduk E., Sypuła M., Sadowska-Bratek M.
Badania biegłości ROŚLINY 6 – oznaczanie zawartości As, Cd, Cu, Hg, Pb, Se i Zn w grzybach suszonych
(maślak sitarz) (Proficiency test PLANT 6 – determination of As, Cd, Cu, Hg, Pb, Se and Zn in dry
mushroom powder (Suillus bovinus)).
Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria B nr 2/2006, 22 p.
10. Zimek Z., Dźwigalski Z., Warchoł S., Roman K., Bułka S.
Modernizacja Stacji Sterylizacji Radiacyjnej wyposażonej w akcelerator elektronów ELEKTRONIKA
10/10. Część I (Upgrading of Radiation Sterilization Facility equipped with electron accelerator
ELEKTRONIKA 10/10. Part I).
11. Malec-Czechowska K., Laubsztejn M., Strzelczak G., Stachowicz W.
Wykrywanie napromieniowania farmaceutyków zawierających składniki pochodzenia roślinnego metodą
pomiaru termoluminescencji oraz metodą spektroskopii elektronowego rezonansu paramagnetycznego
(Detection of irradiation in herbal pharmaceuticals with the use of thermoluminescence and electron
paramagnetic resonance spectroscopy).
12. Mehta K., Bułka S.
Dosimetry for combustion flue gas treatment with electron beam.
Institute of Nuclear Chemistry and Technology, Warszawa 2006. Raporty IChTJ. Seria B nr 5/2006, 26 p.
13. Lewandowska-Siwkiewicz H., Kruszewski M.
Dinitrozylowe kompleksy żelaza w układach biologicznych (Dinitrosyl iron complexes in biological systems).
CONFERENCE PROCEEDINGS
1. Bojanowska-Czajka A., Drzewicz P., Trojanowicz M., Nałęcz-Jawecki G., Sawicki J., Zimek Z.,
Nichipor H.
Analityczne badania radiolitycznej degradacji wybranych pestycydów (Analytical control of radiolytical
decomposition of selected pesticides).
Dla miasta i środowiska – IV konferencja: Problemy unieszkodliwiania odpadów, Warszawa, Poland,
27.11.2006, pp. 23-26.
2. Chmielewski A.G.
Practical applications of radiation chemistry.
Physical chemistry. Proceedings of the 8th international conference on fundamental and applied aspects
of physical chemistry, Belgrade, Serbia, 26-29.09.2006. Vol. 1, pp. 38-46.
3. Chmielewski A.G., Pawelec A., Tymiński B., Zimek Z.
Parametric analysis of the electron beam process for SO2 and NOx removal.
V European meeting on chemical industry and environment, 3-5.05.2006, Vienna, Austria. W. Höflinger
(ed.). Vienna University of Technology, Vienna. Vol. I, pp. 598-606.
4. Chmielewski A.G., Sun Y., Bułka S., Zimek Z.
Chlorinated organic compounds decomposition in air in an electron beam generated plasma reactor.
The First Central European Symposium on Plasma Chemistry, Gdańsk, Poland, 28-31.05.2006. Proceedings, [3] p.
5. Dybczyński R.
The position of NAA among the methods of inorganic trace analysis in the past and now.
Proceedings of the enlargement workshop on neutron measurement, evaluations and applications
NEMEA-2, Bucharest, Romania, 20-23.10.2004. A.J.M. Plompen (ed.). Report EUR 22136 EN. Institute for Reference Materials and Measurements, Luxemburg [2006], pp. 85-88.
6. Harasimowicz M., Orluk P., Zakrzewska-Trznadel G., Chmielewski A.G.
Application of polyimide membranes for biogas purification and enrichment.
176
7. Harasimowicz M., Ziółkowska W., Zakrzewska-Trznadel G., Chmielewski A.G.
Economical comparison of absorption and membrane methods applied for enrichment of methane in biogas.
“Ars Separatoria 2006”: Proceedings of the XXI International Symposium on Physico-Chemical Methods
of Separation, Toruń, Poland, 2-5.07.2006. J. Ceynowa, R. Wódzki (eds.). Nicolaus Copernicus University,
Toruń 2006, pp. 52-54.
8. Łyczko M., Schibli R., Narbutt J.
Substitution of imidazole and bombesin for water in aquatricarbonyl(n-methyl-2-piridenecarbothioamide)
technetium(I) cation. [2+1] approach.
Technetium, rhenium and other metals in chemistry and nuclear medicine. Proceedings of the 7th International symposium on technetium in chemistry and nuclear medicine, Italy, 6-9.09.2006. U. Mazzi (ed.)
SGE Editoriali, Padova 2006, pp. 335-336.
9. Owczarczyk A., Palige J., Dobrowolski A., Chmielewski A.G., Ptaszek S.
CFD and RTD methods for industrial wastewater treatment plants settler investigation.
10. Polkowska-Motrenko H., Dobkowski Z.
Rola porównań międzylaboratoryjnych w procesie doskonalenia systemu zarządzania (Role of ILC in
the advancement of management system).
XII Sympozjum: Doskonalenie systemu zarządzania w laboratorium, Gdańsk-Sobieszowa, Poland,
21-23.05.2006. (I tura). Materiały sympozjum, pp. 73-78.
11. Polkowska-Motrenko H., Dobkowski Z.
Rola porównań międzylaboratoryjnych w procesie doskonalenia systemu zarządzania (Role of ILC in
the advancement of management system).
XII Sympozjum: Doskonalenie systemu zarządzania w laboratorium, Ustroń, Poland, 10-12.09.2006. (II
tura), pp. 85-90.
12. Samczyński Z., Łyczko M., Dybczyński R., Narbutt J.
Ion exchange studies on the organometallic aqua-ion fac-[99mTc(CO)3(H2O)3]+ in acidic aqueous solutions.
Technetium, rhenium and other metals in chemistry and nuclear medicine. Proceedings of the 7th International symposium on technetium in chemistry and nuclear medicine, Italy, 6-9.09.2006. U. Mazzi (ed.).
SGE Editoriali, Padova 2006, pp. 125-126.
13. Zagórski Z.P.
Radiation induced dehydrogenation of organics: from amino acids, to synthetic polymers, to bacterial
spores.
Proceedings of Trombay Symposium on Radiation and Photochemistry, Mumbai, India, 5-9.01.2006.
Vol. I: Invited talks, pp. 97-99.
14. Zakrzewska-Trznadel G., Harasimowicz M., Miśkiewicz A., Chmielewski A.G., Dłuska E., Wroński S., Jaworska A.
Reducing the fouling and boundary layer phenomena in membrane processes for radioactive wastes
treatment.
“Ars Separatoria 2006”: Proceedings of the XXI International Symposium on Physico-Chemical Methods
of Separation, Toruń, Poland, 2-5.07.2006. J. Ceynowa, R. Wódzki (eds.). Nicolaus Copernicus University,
Toruń 2006, pp. 140-141.
15. Zimnicki R., Owczarczyk A., Chmielewski A.G.
Obserwacja zmian parametrów hydrochemicznych wód podziemnych w rejonie powstającej kopalni
odkrywkowej węgla brunatnego (Investigations of groundwater composition and hydrological condition
changes in area of formation of an open-cast lignite mine).
Postęp w inżynierii środowiska. IV Ogólnopolska konferencja naukowo-techniczna, Rzeszów-Bystre k.
Baligrodu, Poland, 21-23.09.2006. Pod red. J.A. Tomaszka, pp. 521-529.
CONFERENCE ABSTRACTS
1.
Bobrowski K., Hug G.L., Hörner G., Marciniak B., Pogocki D., Schöneich C.
Sulfide radical cation chemistry in cyclic dipeptides.
20th International Symposium on Radical Ion Reactivity: ISRIR 2006, Rome, Italy, 2-6.07.2006, IL14,
[1] p.
177
2.
Bobrowski K., Hug G.L., Pogocki D., Hörner G., Marciniak B., Schöneich C.
Stabilization of sulfide cations: mechanisms relevant to oxidation of peptides and proteins containing
methionine.
The 1st Asian-Pacific Symposium on Radiation Chemistry, Shanghai, China, 17-21.09.2006. Conference
abstract book, pp. 58-59.
3.
Bobrowski K., Hug G.L., Pogocki D., Marciniak B., Schöneich C.
Stabilization of sulfide radical cations through complexation with the peptide bond.
RADAM’06: Radiation Damage in Biomolecular Systems, Groningen, The Netherlands, 6-9.06.2006,
[1] p.
Bojanowska-Czajka A., Drzewicz P., Trojanowicz M.
Analityczne badania radiolitycznej degradacji karbendazymu (Analytical control of carbendazim decomposition by gamma irradiation).
ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006.
Streszczenia, p. 21.
4.
5.
Brzóska K., Kruszewski M., Szumiel I.
Defect in double-stranded DNA breaks repair in L5178Y-S cells is not associated with alterations in
the autophosphorylation sites of DNA-dependent protein kinase.
The 10th Anniversary of Gliwice Scientific Meetings, Gliwice, Poland, 17-18.11.2006, p. 37.
6.
Celuch M., Enache M., Pogocki D.
Acid-base catalysis of singlet oxygen-induced oxidation of alkylthiocarboxylic acids.
12th International Conference on Physical Chemistry - Romphyschem-12, Bucharest, Romania, 6-8.09.2006.
Abstract book, p. 60.
7.
Celuch M., Enache M., Pogocki D.
Reakcje jednoelektronowego utleniania kwasów alkilotiokarboksylowych (Reactions of one-electron
oxidation of alkylthiocarboxylic acids).
8.
Chajduk E., Dybczyński R.
Nowa metoda oznaczania śladowych ilości As w materiałach biologicznych za pomocą radiochemicznej
neutronowej analizy aktywacyjnej (Determination of trace amounts of arsenic in biological samples by
RNAA).
XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, S8-P20, p.
200.
9.
Chajduk E., Polkowska-Motrenko H., Dybczyński R.
Konstruowanie metod o najwyższej randze metrologicznej dla oznaczania Se w materiałach biologicznych
za pomocą RNAA (A new, high accuracy RNAA method for selenium determination in biological
materials).
10. Chajduk E., Polkowska-Motrenko H., Dybczyński R.
Metoda definitywna oznaczania selenu w matrycach biologicznych (Definitive method for selenium
determination in biological materials).
VI Sesja przeglądowa analityki żywności, Warszawa, Poland, 17.11.2006. Materiały sesji, p. 17.
Industrial scale processing of flue gases from electric and heat power plants.
Workshop on the Plasma-Assisted Combustion and Plasma-Aftertreatment of Combustion Flue Gases
for Power Industry, Gdańsk, Poland, 28-31.05.2006. Book of abstracts, p. 13.
Industrial applications of electron beam flue gas treatment – from laboratory to the practice.
11th Tihany Symposium on Radiation Chemistry, Eger, Hungary, 26-31.08.2006. Program and abstracts,
p. 50.
Technologiczne aspekty chemii radiacyjnej (Technological aspects of radiation chemistry).
XLIX Zjazd PTChem i SIPChem, Gdańsk, Poland, 18-21.09.2006. Materiały zjazdowe, S12, W-1, p.
283.
178
Water pollutants degradation by electron beam.
The First Central European Symposium on Plasma Chemistry, Gdańsk, Poland, 28-31.05.2006. Book
of abstracts, p. 17.
15. Chmielewski A.G., Chmielewska D.K., Sampa M.H.
Prospects and challenges in application of gamma and electron beam processing of nanomaterials.
IRaP 2006: 7th International Symposium on Ionizing Radiation and Polymers, Antalya, Turkey,
23-28.09.2006. Book of abstracts, p. 44.
16. Chmielewski A.G., Haji-Saeid M., Ramamoorthy N.
Fostering new developments in radiation processing and IAEA’s role.
14th International Meeting on Radiation Processing, Kuala Lumpur, Malaysia, 26.02.-3.03.2006. Conference abstracts book, [1] p.
17. Chmielewski A.G., Migdał W., Świętosławski J., Jakubaszek U., Tarnowski T.
Chemical-radiation degradation of natural oligo-aminopolysaccharides and product agricultural applications.
14th International Meeting on Radiation Processing (IMRP), Kuala Lumpur, Malaysia, 26.02.-3.03.2006.
Conference abstracts book, p. 198.
Chlorinated organic compounds decomposition in air in an electron beam generated plasma reactor.
The First Central European Symposium on Plasma Chemistry, Gdańsk, Poland, 28-31.05.2006. Book
of abstracts, p. 55.
Dosimetric methods for laboratory scale VOC treatment.
The Workshop on dosimetry for radiation applications in technologies for environment pollution control, Warszawa, Poland, 5.04.2006, p. 4.
20. Chwastowska J., Skwara W., Sterlińska E., Dudek J., Pszonicki L.
Oznaczanie kadmu, ołowiu, miedzi i bizmutu w wodach mineralnych metodą GF-AAS po wydzieleniu
za pomocą ekstrakcji do fazy stałej (Determination of cadmium, lead, copper and bismuth in mineral
waters by GF-AAS after preconcentration on dithizone sorbent).
Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XV
Poznańskiego konwersatorium analitycznego, Poznań, Poland, 20-21.04.2006, p. 115.
Sorbent chelatujący z ditizonem, własności analityczne i możliwości zastosowania (Chelating sorbent
with dithizon – analytical property and possibility of use).
Własności analityczne i możliwości zastosowania sorbentu chelatującego z ditizonem (Analytical properties and applications of dithizone sorbent).
XI Konferencja: Zastosowanie metod AAS, ICP-AES, ICP-MS w analizie środowiskowej – Thermo
Electron, Warszawa, Poland, 9-10.11.2006, PO-03, p. 22.
Zastosowanie ekstrakcji do fazy stałej przy oznaczaniu metali ciężkich metodą GF-AAS (Application
of solid-phase extraction for determination of heavy metals by GF-AAS).
XI Konferencja: Zastosowanie metod AAS, ICP-AES, ICP-MS w analizie środowiskowej – Thermo
Electron, Warszawa, Poland, 9-10.11.2006, PO-04, p. 23.
24. Cieśla K., Eliasson A.-C.
DSC studies of retrogradation and amylose-lipid complex transition taking place in gamma irradiated
wheat starch.
25. Cieśla K., Lundqvist H., Eliasson A.-C.
Surface tension and WAXS diffraction studies of binding cetyltrimethyl-ammonium bromide to gamma
irradiated and nonirradiated potato starch.
XIV International Starch Convention Cracow-Moscow, Cracow, Poland, 20-24.06.2006, pp. 66-67.
179
26. Cieśla K., Rahier H.
Gamma irradiation effect on interaction of potato starch with lipids and surfactants studied by DSC.
ESTAC 9: 9th European Symposium on Thermal Analysis and Calorimetry, Kraków, Poland, 27-31.08.2006,
p. 26.
27. Cieśla K., Sartowska B., Królak E.
Gamma irradiation influence on structure of potato starch gels studied by SEM.
XIV International Starch Convention Cracow-Moscow, Cracow, Poland, 20-24.06.2006, pp. 106-107.
28. Cieśla K., Vansant E.F.
Physico-chemical changes taking place in gamma irradiated bovine globulins studied by thermal analysis.
ESTAC 9: 9th European Symposium on Thermal Analysis and Calorimetry, Kraków, Poland, 27-31.08.2006,
p. 37.
29. Danko B., Dybczyński R., Kulisa K., Samczyński Z.
Oznaczanie lantanowców w próbkach biologicznych za pomocą neutronowej analizy aktywacyjne i chromatografii jonów (Determination of the lanthanides in biological samples by NAA and IC).
XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, S8-P23, p.
200.
30. Danko B., Dybczyński R., Kulisa K., Samczyński Z.
Schemat wydzielania frakcji lantanowców z materiałów pochodzenia roślinnego oraz środowiskowego
(A scheme for the separation of lanthanide fraction from materials of biological and environmental
origin).
31. Dybczyński R.
Contribution of NAA to the certification of reference materials for inorganic trace analysis.
NEMEA-3: 3rd Workshop on Neutron Measurements, Evaluations and Applications, Borovets, Bulgaria, 25-28.10.2006. Book of abstracts, p. 19.
32. Dybczyński R.
Neutronowa analiza aktywacyjna i jej znaczenie dla zapewnienia jakości wyników analitycznych w nieorganicznej analizie śladowej (Neutron activation and its significance for the assurance of the quality
of analytical results in inorganic trace analysis).
XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, S12-W2, p.
283.
33. Dybczyński R.
Zarys historii, zastosowania i znaczenie materiałów odniesienia w nieorganicznej analizie śladowej
(Historical outline of the application and significance of reference materials in inorganic trace analysis).
34. Dybczyński R., Danko B., Polkowska-Motrenko H., Samczyński Z.
Metody definitywne oparte na radiochemicznej neutronowej analizie aktywacyjnej i ich miejsce w metrologii chemicznej (Definitive methods based on radiochemical neutron activation and their position in
chemical metrology).
Ogólnopolska konferencja naukowa: Jakość w chemii analitycznej, Warszawa, Poland, 23-24.11.2006,
[1] p.
35. Dybczyński R., Danko B., Polkowska-Motrenko H., Samczyński Z.
The place of highly accurate methods by RNAA in metrology.
15th Radiochemical Conference, Mariánské Lázne, Czech Republic, 23-28.04.2006. Booklet of abstracts, p. 84.
36. Dybczyński R., Kulisa K.
Wpływ temperatury na proces rozdzielania w chromatografii jonowymiennej i chromatografii pasma
chromatograficznego (Influence of temperature on the separation process in ion exchange chromatography and ion chromatography and the mechanism of band spreading).
VII Konferencja chromatograficzna: chromatografia i techniki pokrewne a zdrowie człowieka, Białystok,
Poland, 10-13.10.2006, pp. 19-20.
37. Filipczak K., Ulanski P., Przybytniak G., Olah L., Rosiak J.M.
Some observations on the effect of ionizing radiation on poly(ε-caprolactone).
180
p. 91.
38. Filipczak K., Ulanski P., Przybytniak G., Rosiak J.M.
Studies on the free radical chemistry of poly(ε-caprolactone).
39. Fuente J. De la, Sobarzo-Sánchez E., Bobrowski K.
Spectroscopic characterization of radicals species from 2,3-dihydro-oxoisoaporphines generated by flash
photolysis and pulse radiolysis.
XVIII International Conference on Physical Organic Chemistry, Warsaw, Poland, 20-25.08.2006, p. 57.
40. Fuks L.
Pt(II) chloride complexed by tetrahydrofurylthiourea or tetrahydrotiophenylthiourea: structural and
biological features.
3rd Central European Conference: Chemistry towards biology – CHTB 2006, Kraków, Poland, 8-12.09.2006,
P-8, [1] p.
41. Giglio J., León E., Rey A., Künstler J.-U., Gniazdowska E., Decristoforo C., Pietzsch H.-J.
99m
Tc-labelled RGD-peptides using the „4+1” mixed-ligand approach.
Technetium, rhenium and other metals in chemistry and nuclear medicine. 7th International Symposium, Italy, 6-9.09.2006. U. Mazzi, A. Nadali (eds). Abstracts, 3AP12, p. 46.
Chemia radiacyjna mieszanin polimerowych PP/PS (Radiation chemistry of PP/PS polymer mixtures).
Radiation effects on PP/PS blends as a model of protection effects by aromatics.
Zjawiska ochronne w chemii radiacyjnej polimerów (Protective phenomena in the radiation chemistry
of polymers).
9. Spotkanie Inspektorów Ochrony Radiologicznej, Dymaczewo Nowe, Poland, 20.05.-2.06.2006.
Materiały konferencyjne, pp. 15-16.
45. Grądzka I., Sochanowicz B., Buraczewska I., Szumiel I.
Participation of the EGF receptor in the response to X-irradiation in human glioma M059 K and J cells.
46. Grodkowski J., Kocia R., Mirkowski J.
Radioliza impulsowa przejściowych widm absorpcyjnych p-terfenylu w cieczy jonowej bis[(trifluorometylo)sulfonylo] imidzie metylotributyloamoniowym (R4NNTF2) (Pulse radiolysis of intermediate
absorption spectra of p-terphenyl in ionic liquid methyltributylammonium bis[(trifluoromethyl)sulfonyl]imide).
Crystal structure of zinc(II) pyrazolate trihydrate.
48. Konwersatorium krystalograficzne, Wrocław, Poland, 29-30.06.2006. Streszczenia komunikatów,
A-22, p. 71.
Monomeric molecules in the crystal structures of magnesium(II) and zinc(II) structures with imidazole-4-carboxylate and water ligands.
A-23, pp. 72-73.
49. Herdzik I.
Separacja izotopów galu i indu z wykorzystaniem chromatografii jonowymiennej (Separation of gallium and indium isotopes using ion-exchange chromatography).
181
50. Kałuska I., Lazurnik V.T., Lazurnik V.M., Popov G.F., Rogov Y.V., Zimek Z.
The features of electron dose distribution in circular objects: comparison of Monte Carlo simulation
predictions with dosimetry.
14th International Meeting on Radiation Processing (IMRP), Kuala Lumpur, Malaysia, 26.02.-3.03.2006.
Conference abstracts book, p. 206.
51. Kciuk G., Hug G., Mirkowski J., Bobrowski K.
Intramolecular electron transfer in dipeptides containing tyrosine.
p. 10.
Radiation-induced oxidation of dipeptides containing tyrosine and methionine: influence of amino
acid sequence, pH and conformation.
12th International Conference on Physical Chemistry – Romphyschem-12, Bucharest, Romania, 6-8.09.2006.
Utlenianie dipeptydów zawierających reszty tyrozyny i metioniny: badania metodą radiolizy impulsowej
(Oxidation of dipeptides containing tyrosine and methionine; studies by pulse radiolysis).
54. Kocia R., Grodkowski J., Mirkowski J.
Pulse radiolysis study of the formation the p-terphenyl radical anion in the ionic liquid methyltributylammonium bis[(trifluoromethyl)sulfonyl]imide (R4NNTf2).
12th International Conference on Physical Chemistry - Romphyschem-12, Bucharest, Romania, 6-8.09.2006.
55. Kornacka E.M., Przybytniak G., Rafalski A., Kozakiewicz J.
Radiation induced effects in segmented poly(siloxaneurethane) ureas based on aliphatic and aromatic
diisocyanates.
p. 77.
56. Kornacka E.M., Przybytniak G., Święszkowski W.
Influence of crystallinity on radiation stability of PE.
Workshop on Biotribology, COST 533, Warszawa, Poland, 6.10.2006, pp. 8-9.
57. Krejzler J., Narbutt J., Foreman M.R.St J., Hudson M.J., Casensky B., Madic C.
Solvent extraction of Am(III) and Eu(III) from nitrate solution using synergistic mixtures of n-tridentate heterocycles and chlorinated cobalt dicarbollide.
15th Radiochemical Conference, Mariánské Lázne, Czech Republic, 23-28.04.2006. Booklet of abstracts, p. 212.
58. Kruszewski M., Iwaneńko T., Woliński J., Wojewódzka M.
Differential action of human metabolism and energy regulators on the lymphocyte susceptibility to
ionizing radiation.
III International and VI Cuban Mutagenesis, Teratogenesis and Carcinogenesis Workshop, Havana,
Cuba, 25-27.09.2006, p. 8.
59. Kruszewski M., Iwaneńko T., Woliński J., Wojewódzka M.
Ghrelin, a natural ligand for the GHS receptor, sensitizes blood mononuclear cells to oxidative stress.
Cuba, 25-27.09.2006, p. 30.
60. Kruszewski M., Iwaneńko T., Woliński J., Zabielski R., Wojewódzka M.
Ghrelin, a natural ligand for the growth hormone secretagogue receptor, sensitizes blood mononuclear
cells to oxidative stress.
182
61. Kruszewski M., Lewandowska H., Męczyńska S., Sochanowicz B., Sadło J.
Differential action of permeable and non-permeable iron chelators on formation on dinitrosyl iron
complexes in vivo.
16th International Conference on Chelators (ICOC), Limassol, Cyprus, 25-31.10.2006, p. 32.
62. Kulisa K., Dybczyński R., Danko B., Samczyński Z.
Wstępne wydzielanie grupy lantanowców z materiałów biologicznych i środowiskowych i ich oznaczanie
za pomocą chromatografii jonów (Preliminary separation of the lanthanides as a group from biological
and environmental materials and their determination by ion chromatography).
Poland, 10-13.10.2006, p. 97.
63. Łyczko K., Starosta W.
The structures of lead(II) complexes with tropolone.
64. Łyczko M.
Trikarbonylkowe kompleksy technetu(I) z lipofilowymi ligandami bidentnymi (Tricarbonyl complexes
of technetium(I) with bidentate lyophylic ligands).
65. Łyczko M., Schibli R., Narbutt J.
Substitution of imidazole and bombesin for water in aquatricarbonyl(n-methyl-2-piridenecarbothioamide) technetium(I) cation. 2+1 approach.
66. Maddukuri L., Christiansen M., Dudzińska D., Zaim J., Obutulowicz T., Komisarski M., Wójcik
A., Kusmierek J., Stevnsner T., Bohr A., Tudek B.
Cockayane syndrome group B protein in involved in repairing of DNA adducts induced by trans-4-hydroxy-2-nonenal.
67. Majkowska A., Bilewicz A.
Formation kinetics and stability of some TRI and tetraaza derivative complexes of scandium.
68. Marciniak B., Hug G.L., Hörner G., Bobrowski K.
Reactive intermediates in the photo-oxidation of sulfur-containing organic compounds.
20th International Symposium on Radical Ion Reactivity: ISRIR 2006, Rome, Italy, 2-6.07.2006, IL3,
[1] p.
69. Męczyńska S., Lewandowska H., Kruszewski M.
The role of lysosomal iron in NO signaling.
·
70. Męczyńska S., Lewandowska-Siwkiewicz H., Kruszewski M.
Interaction of dinitrosyl iron complexes with DNA.
71. Narbutt J., Krejzler J.
Heteroleptic complexes of Am(III) and Eu(III) with a triazinylbipyridine derivative. Multiple regression analysis of solvent extraction data.
37th International Conference on Coordination Chemistry (ICCC), Cape Town, South Africa, 13-18.08.2006.
D.J. Robinson, I.M. Robinson (eds.). Oral abstracts, p. 222.
72. Narbutt J., Krejzler J.
Oddzielanie trójwartościowych aktynowców od lantanowców w odpadach promieniotwórczych z przerobu wypalonych paliw jądrowych (Separation of trivalent actinides from lanthanides in radioactive
wastes from reprocessing of spent nuclear fuels).
XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, S12-W4, p.
284.
183
73. Ostapczuk A.
Electron beam application for volatile organic compounds removal.
74. Pawlukojć A., Starosta W., Leciejewicz J., Natkaniec I., Nowak D.
The molecular structure and dynamics of 2-aminopyridine-3-carboxylic acid by X-ray diffraction, inelastic neutron scattering, infrared, Raman spectroscopy and from first principles calculations.
V Workshop on investigations at the IBR-2 pulsed reactor, Dubna, Russia, 14-17.06.2006. Programme
and abstracts, p. 58.
75. Polkowska-Motrenko H.
Badania biegłości laboratoriów oznaczających pierwiastki toksyczne w żywności (Proficiency testing of
laboratories determining toxic elements in food).
XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, p. 221.
76. Polkowska-Motrenko H., Chajduk E., Dybczyński R.
Oznaczanie selenu w materiałach biologicznych za pomocą metody definitywnej opartej na radiochemicznej neutronowej analizie aktywacyjnej (Determination of selenium in biological samples by
definitive method based on RNAA).
Działalność Instytutu Chemii i Techniki Jądrowej w dziedzinie zapewnienia jakości w nieorganicznej
analizie śladowej (Activities of the Institute of Nuclear Chemistry and Technology in the domain of
quality assurance for inorganic trace analysis).
VI Sesja przeglądowa analityki żywności, Warszawa, Poland, 17.11.2006. Materiały sesji, p. 13.
Program badań biegłości ROŚLINY – oznaczanie zawartości As, Cd, Cu, Hg, Se, Pb i Zn w żywności
pochodzenia roślinnego (PT scheme: PLANTS – determination of As, Cd, Cu, Hg, Se, Pb and Zn in
food of plant origin).
[1] p.
Nowe polskie atestowane materiały odniesienia: Mąka Kukurydziana INCT-CF-3 i Mąka Sojowa
INCT-SBF-4 dla potrzeb nieorganicznej analizy śladowej – przygotowanie i atestacja (New Polish CRMs:
Corn Flour INCT-CF-3 and Soya Bean Flour INCT-SBF-4 for the purpose of inorganic trace analysis
– preparation and certification).
[1] p.
Nowe polskie certyfikowane materiały odniesienia dla potrzeb nieorganicznej analizy śladowej: Mąka
Kukurydziana INCT-CF-3 i Mąka Sojowa INCT-SBF-4 (New Polish certified reference materials: Corn
Flour INCT-CF-3 and Soya Beam Flour INCT-SBF-4 for inorganic trace analysis).
XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006, S8-K40, p. 194.
81. Polkowska-Motrenko H., Fuks L., Sypuła M.
Badania biegłości laboratoriów monitorujących skażenia promieniotwórcze kraju (Proficiency testing
of laboratories monitoring country radionuclide contamination).
XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, p. 289.
82. Polkowska-Motrenko H., Sadowska-Bratek M.
Badanie trwałości materiałów odniesienia metodą NAA (Studies of the stability of reference materials
by the NAA method).
83. Przybytniak G., Kornacka E.M., Kozakiewicz J.
Radical processes in segmented poly(siloxaneurethaneureas) induced by ionizing radiation.
184
84. Przybytniak G., Kornacka E., Mirkowski K., Nowicki A., Rafalski A.
Radiation degradation of blends polypropylene/poly(ethylene-co-vinyl acetate).
p. 16.
85. Rafalski A., Przybytniak G., Kornacka E., Mirkowski K., Nowicki A.
Influence of copolymers on radiation resistance of polypropylene blends.
XVII International Conference on Physical Organic Chemistry, Warszawa, Poland, 20-25.08.2006, p.
80.
86. Ramamoorthy N., Haji-Saeid M., Chmielewski A.G., Chupov A.
IAEA’s support to radiation processing technology practices in developing countries.
14th International Meeting on Radiation Processing, Kuala Lumpur, Malaysia, 26.02.-3.03.2006. Conference abstracts book, [1] p.
87. Sadło J., Michalik J., Danilczuk M., Turek J.
Silver clusters in molecular sieves.
E-MRS 2006 Fall Meeting, Warszawa, Poland, 4-8.09.2006. Book of abstracts, p. 71.
Badania trikarbonylkowych kompleksów technetu(I) metodą chromatografii jonowymiennej i elektroforezy bibułowej (Investigations of tricarbonyl complexes of technetium(I) by ion exchange chromatography and paper electrophoresis).
Poland, 10-13.10.2006, pp. 72-74.
Ion exchange studies on the organometallic aqua-ion fac-[99mTc(CO)3(H2O)3]+ in acidic aqueous solutions.
The crystal structure of a calcium(II) complex with pyridazine-3-carboxylate and water ligands.
B-27, p. 161.
Three-dimensional polymeric molecular pattern in the crystal structure of a Ca(II) complex with pyrazine-2,3,5,6-tetracarboxylate and water ligands.
B-28, pp. 162-163.
92. Trojanowicz M., Drzewicz P., Bojanowska-Czajka A., Nałęcz-Jawecki G., Sawicki J.
Radiolytic removal of selected pesticides from industrial wastes.
SETAC Asia/Pacific 2006. Growth with a limit: the integration of ecosystem protection for human
health benefits, Peking, China, 18-20.09.2006. Abstracts, [1] p.
93. Trojanowicz M., Szydłowska D., Campas M., Marty J.-L.
Determination of microcystins in surface waters using amperometric screen-printed biosensor with
immobilized protein phosphatase and high-performance liquid chromatography.
SETAC Asia/Pacific 2006. Growth with a limit: the integration of ecosystem protection for human
health benefits, Peking, China, 18-20.09.2006. Abstracts, [1] p.
94. Turek J., Michalik J.
Rodniki srebroorganiczne (Organosilver radicals).
95. Wierzchnicki R., Derda M.
Stable isotopes composition in milk origin control.
3rd Central European Congress on Food, Sofia, Bulgaria, 22-24.05.2006. Book of abstracts, p. 209.
185
96. Wojewódzka M., Kruszewski M., Buraczewska I., Xu W., Massuda E., Zhang J., Szumiel I.
Sirtuin inhibition increases the rate of DNA-PK-independent double-strand break repair.
Cuba, 25-27.09.2006, p. 31.
97. Wojewódzka M., Kruszewski M., Buraczewska I., Xu W., Massuda E., Zhang J., Szumiel I.
Type III histone deacetylases inhibition increases the rate of DNA-PK-independent DSB repair.
98. Zagórski Z.P.
Prebiotic chemical raw material for life.
4th International School on Complexity: Basic questions about the origin of life, Cerice, Italy, 2-5.10.2006,
p. 26.
99. Zagórski Z.P.
Pulse radiolysis of solids.
Pune University Workshop on Radiation and Photochemistry (PUWORP-2006), Pune, India, 10-11.01.2006,
[1] p.
100. Zagórski Z.P.
Role of ionizing in contribution to homochirality as the signature of life.
4th International School on Complexity: Basic questions about the origin of life, Cerice, Italy, 2-5.10.2006,
p. 51.
101. Zimek Z.
Characteristics and capabilities of X-ray converters applied in radiation processing.
p. 35.
102. Zimek Z.
Dosimetric method for industrial scale flue gas treatment.
103. Zimek Z., Chmielewski A.G.
Implementation of high power electron accelerators for environmental protection.
RuPAC 2006: XXth Russian Conference on Charged Particle Accelerators, Novosibirsk, Russia,
10-14.09.2006. Abstracts brochure, p. 109.
104. Zimek Z., Dźwigalski Z., Warchoł S., Bułka S., Roman K.
Upgrading of accelerator facility for radiation sterilization.
RuPAC 2006: XXth Russian Conference on Charged Particle Accelerators, Novosibirsk, Russia,
10-14.09.2006. Abstracts brochure, p. 108.
105. Zimek Z., Przybytniak G., Nowicki A., Mirkowski K.
Modification of bentonite fillers using ionizing radiation.
E-MRS 2006 Fall Meeting, Warszawa, Poland, 4-8.09.2006. Book of abstracts, p. 113.
SUPPLEMENT LIST OF THE INCT PUBLICATIONS IN 2005
CHAPTERS IN BOOKS
1. Dalivelya O., Savina N., Buraczewska I., Grądzka I., Szumiel I.
Effects of an antimutagen of 1,4-dihydropyridine series on cell survival in X-irradiated murine L5178Y
sublines.
In: Molekularnaya i prikladnaya genetika. Institut Genetiki i Citologii Nacional’noj Akademii Nauk
Belarusi, Minsk 2005. Naucnye trudy, Tom 1, p. 292.
186
NUKLEONIKA
NUKLEONIKA
THE INTERNATIONAL JOURNAL OF NUCLEAR RESEARCH
EDITORIAL BOARD
Andrzej G. Chmielewski (Editor-in-Chief, Poland), Krzysztof Andrzejewski (Poland), Janusz Z. Beer
(USA), Jacqueline Belloni (France), Grażyna Bystrzejewska-Piotrowska (Poland), Gregory R.
Choppin (USA), Władysław Dąbrowski (Poland), Hilmar Förstel (Germany), Andrei Gagarinsky
(Russia), Andrzej Gałkowski (Poland), Evgeni A. Krasavin (Russia), Stanisław Latek (Poland),
Robert L. Long (USA), Sueo Machi (Japan), Dan Meisel (USA), Jacek Michalik (Poland), James
D. Navratil (USA), Robert H. Schuler (USA), Christian Streffer (Germany), Irena Szumiel
(Poland), Piotr Urbański (Poland), Alexander Van Hook (USA)
CONTENTS OF No. 1/2006
Proceedings of the 2nd IAEA Research Co-ordination Meeting of the Co-ordinated Research Project on
Dense Magnetized Plasma, 1-3 June 2005, Kudowa Zdrój, Poland
1. Foreword
A. Malaquias
2. Dense magnetized plasma and its applications: a view of the 3-year activity of the IAEA Co-ordinated
Research Programme
V.A. Gribkov, A. Malaquias
3. Development of diagnostic tools for Plasma Focus derived X-ray source
E. Angeli, C. Bonifazzi, A. Da Re, M. Marziani, A. Tartari, M. Frignani, S. Mannucci, D. Mostacci, F. Rocchi,
M. Sumini
4. Dense Plasma Focus as a powerful source of monochromatic X-ray radiation
A.V. Dubrovsky, V.A. Gribkov, Yu.P. Ivanov, L. Karpiński, M.A. Orlova, V.M. Romanova, M. Scholz,
I.V. Volobuev
5. Production of negative hydrogen ions using a low-pressure reflex discharge source
E.I. Toader
6. Development of a large beam facility
B.H. Oh, S.R. In, K.W. Lee, S.H. Jeong, C.S. Seo, D.H. Chang
7. Experimental study of a small gas-puff Z-pinch device
C.M. Luo, X.X. Wang, X.B. Zou
8. D(3He,p)4He and D(d,p)3H fusion in a small plasma focus operated in a deuterium helium-3 gas mixture
S.V. Springham, T.H. Sim, R.S. Rawat, P. Lee, A. Patran, P.M.E. Shutler, T.L. Tan, S. Lee
9. PF-6 – an effective plasma focus as a source of ionizng radiation and plasma streams for application in
material technology, biology and medicine
V.A. Gribkov, A.V. Dubrovsky, M. Scholz, S. Jednorog, L. Karpiński, K. Tomaszewski, M. Paduch,
R. Miklaszewski, V.N. Pimenov, L.I. Ivanov, E.V. Dyomina, S.A. Maslyaev, M.A. Orlova
10. Colored-noise-induced anomalous transport in periodic structures
T. Laas, A. Sauga, R. Mankin, A. Ainsaar, Ü. Ugaste, A. Rekker
11. Surface and bulk processes in materials induced by pulsed ion and plasma beams at Dense Plasma Focus
devices
V.N. Pimenov, S.A. Maslyaev, L.I. Ivanov, E.V. Dyomina, V.A. Gribkov, A.V. Dubrovsky, M. Scholz,
R. Miklaszewski, Ü.E. Ugaste, B. Kolman
12. Status of a mega-joule scale Plasma-Focus experiments
M. Scholz, B. Bieńkowska, M. Borowiecki, I. Ivanova-Stanik, L. Karpiński, W. Stępniewski, M. Paduch,
K. Tomaszewski, M. Sadowski, A. Szydłowski, P. Kubeš, J. Kravárik
13. High kinetic energy dense plasma jet
A.V. Voronin, V.K. Gusev, Yu.V. Petrov, N.V. Sakharov, K.B. Abramova, K.G. Hellblom
NUKLEONIKA
187
1. The quantum diffusion of carbon in α-iron in low temperature
L. Dąbrowski, A. Andreev, M. Georgiev
2. Investigation of low temperature diffusion of carbon in martensite by Mössbauer spectroscopy and X-ray
diffraction
A. Jabłońska, L. Dąbrowski, J. Suwalski, S. Neov
3. Surface structure changes of InP and GaAs single crystals irradiated with high energy electrons and swift
heavy ions
A.Yu. Didyk, F.F. Komarov, L.A. Vlasukova, V.N. Yuvchenko, A. Hofman
4. Preparation of [61Cu]DTPA complex as a possible PET tracer
A.R. Jalilian, P. Rowshanfarzad, M. Sabet, M. Kamalidehghan
5. Production of [103Pd]Bleomycin complex for targeted therapy
A.R. Jalilian, Y. Yari-Kamrani, M. Sadeghi
6. Gamma-ray beam attenuation to assess the influence of soil texture on structure deformation
L.F. Pires, O.O.S. Bacchi, N.M.P. Dias
7. A radiographic facility at the Sołtan Institute for Nuclear Studies (SINS) at Świerk, Poland
J. Bigolas, W. Drabik, E. Pławski, A. Wysocka-Rabin
8. Air aerosol sampling station AZA-1000 at Polish Polar Station in Hornsund, Spitsbergen
B. Mysłek-Laurikainen, M. Matul, S. Mikołajewski, H. Trzaskowska, Z. Preibisz, I. Garanty, M. Kubicki,
P. Rakowski, T. Krynicki, M. Stefański
1. Effects of an antimutagen of 1,4-dihydropyridine series on cell survival and DNA damage in L5178Y
murine sublines
O. Dalivelya, N. Savina, T. Kuzhir, I. Buraczewska, M. Wojewódzka, I. Szumiel
2. Production and quality control of 66Ga radionuclide
M. Sabet, P. Rowshanfarzad, A.R. Jalilian, M.R. Ensaf, A.A. Rajamand
3. Development of [66Ga]oxine complex; a possible PET tracer
A.R. Jalilian, P. Rowshanfarzad, M. Sabet, A. Rahiminejad-Kisomi, A.A. Rajamand
4. Computation of concentration changes of heavy metals in the fuel assemblies with 1.6% enrichment by
ORIGEN code for VVER-1000
M. Rahgoshay
5. Monte-Carlo simulation of a neutron source generated with electron linear accelerator
A. Wasilewski, S. Wronka
6. Investigation of high-dose irradiation effects on polystyrene calorimeter response
F. Ziaie, A. Noori
7. Influence of temperature on breakdown voltage of 10 MeV electron beam irradiated LDPE and HDPE
M. Borhani, F. Ziaie, M.A. Bolorizadeh, G. Mirjalili
1. Obituary
Professor Barbara Hołyńska (1930-2006)
2. DNA double-strand break rejoining in radioadapted human lymphocytes: evaluation by neutral comet
assay and pulse-field gel electrophoresis
M. Wojewódzka, I. Buraczewska, I. Szumiel, I. Grądzka
3. Influence of 137Cs and 90Sr on vegetative and generative organs of Lepidium sativum L. and Tradescantia
clone 02
D. Mar èiulionienë, B. Lukšienë, D. Kiponas, D. Montvydien ë, G. Maksimov, J. Darginavi èien ë, V.
Gavelienë
4. Preparation and biodistribution of [201Tl](III)vancomycin complex in normal rats
A.R. Jalilian, M.A. Hosseini, A. Karimian, F. Saddadi, M. Sadeghi
5. Production, quality control and initial imaging studies of [82mRb]RbCl for PET studies
P. Rowshanfarzad, A.R. Jalilian, M. Kiyomarsi, M. Sabet, A.R. Karimian, S. Moradkhani, M. Mirzaii
6. Isotope effects of gallium and indium in cation exchange chromatography
W. Dembiński, I. Herdzik, W. Skwara, E. Bulska, A.I. Wysocka
188
NUKLEONIKA
7. Production and separation of manganese-54 from alpha-irradiated V2O5 target
M. Kłos, M. Bartyzel, B. Petelenz
8. Design, construction and performance of a pressure chamber for water retention curve determination
through traditional and nuclear methods
L.F. Pires, O.O.S. Bacchi
SUPPLEMENT No. 1/2006
Proceedings of the 2nd Polish-Japanese Workshop on Materials Science “Materials for Sustainable
Development in the 21st Century”, 12-15 October 2005, Warsaw, Poland
1. Foreword
J. Michalik, K. Halada
2. Worldwide developments in the field of radiation processing of materials in the down of 21st century
A.G. Chmielewski
3. Design of high quality doped CeO2 solid electrolytes with nanohetero structure
T. Mori, J. Drennan, D.R. Ou, F. Ye
4. Structure and properties of nanomaterials produced by severe plastic deformation
Z. Pakieła, H. Garbacz, M. Lewandowska, A. Drużycka-Wiencek, M. Suś-Ryszkowska, W. Zieliński,
K.J. Kurzydłowski
5. Synthesis of nanostructured tetragonal ZrO2 of enhanced thermal stability
A. Adamski, P. Jakubus, Z. Sojka
6. Studies on template-synthesized polypyrrole nanostructures
W. Starosta, M. Buczkowski, B. Sartowska, D. Wawszczak
7. Structural characterization of room-temperature synthesized fullerene nanowhiskers
K. Miyazawa, J. Minato, T. Mashino, S. Nakamura, M. Fujino, T. Suga
8. EPR and ESEEM study of silver clusters in ZK-4 molecular sieves
J. Sadło, J. Michalik, L. Kevan
9. Properties of novel silicon nitride-based materials
K. Itatani
10. Development of environmental purification materials with smart functions
H. Yamada, Y. Watanabe, K. Tamura
11. Silica materials with biocidal activity
D.K. Chmielewska, A. Łukasiewicz, J. Michalik, B. Sartowska
12. High pressures studies on hydrides of selected manganese alloys
H. Sugiura, S.M. Filipek, V. Paul-Boncour, I. Marchuk, R.-S. Liu, S.I. Pyun
13. Application of Pt/Al2O3 catalysts produced by sol-gel process to uranyl ion reduction
A. Deptuła, W. Łada, T. Olczak, A.G. Chmielewski
14. Hybrid atomization method suitable for production of fine spherical lead-free solder powder
K. Minagawa, H. Kakisawa, S. Takamori, Y. Osawa, K. Halada
15. Degradation of polyolefine wastes into liquid fuels
B. Tymiński, K. Zwoliński, R. Jurczyk
16. EPR study on biominerals as materials for retrospective dosimetry
J. Sadło, J. Michalik, W. Stachowicz, G. Strzelczak, A. Dziedzic-Gocławska, K. Ostrowski
17. Membrane processes for environmental protection: applications in nuclear technology
G. Zakrzewska-Trznadel
18. Advanced processing for recycling of iron scrap with impurities
Y. Osawa, S. Takamori, K. Minagawa, H. Kakisawa, K. Halada
19. Influence of radiation sterilization on poly(ester urethanes) designed for medical applications
G. Przybytniak, E. Kornacka, J. Ryszkowska, M. Bil, A. Rafalski, P. Woźniak, M. Lewandowska-Szumieł
20. Radiation processing of polymers and semiconductors at the Institute of Nuclear Chemistry and Technology
Z. Zimek, G. Przybytniak, I. Kałuska
Proceedings of the IV All-Polish Conference on Radiochemistry and Nuclear Chemistry, 9-11 May 2005,
Kraków-Przegorzały, Poland
NUKLEONIKA
189
1. Preface
L. Fuks
2. Thermochromatographic separation of 206,208Po from a bismuth target bombarded with protons
B. Wąs, R. Misiak, M. Bartyzel, B. Petelenz
3. Carbon isotope effects in the studies of the mechanism of action of tyrosine phenol-lyase
W. Augustyniak, R. Kański, M. Kańska
4. Synthesis of ring labeled [1’-14C]-L-tyrosine
R. Kański, W. Augustyniak, M. Kańska
5. Tritium kinetic isotope effects on enzymatic decomposition of L-tryptophan
E. Boroda, R. Kański, M. Kańska
6. Self-absorption correction in gamma-ray spectrometry of environmental samples – an overview of
methods and correction values obtained for the selected geometries
P. Jodłowski
7. Interlaboratory comparison of the determination of 137Cs and 90Sr in water, food and soil: preparation
and characterization of test materials
L. Fuks, H. Polkowska-Motrenko
8. Studies on concentration of some heavy metals and strontium 90Sr and cesium 137Cs isotopes in bottom
sediments of selected lakes of Łęczyńsko-Włodawskie Pojezierze
J. Solecki, M. Reszka, S. Chibowski
9. Determination of the sediment deposition rates in the Kuwait Bay using 137Cs and 210Pb
A.Z. Al-Zamel, F. Bou-Rabee, M.A. Al-Sarawi, M. Olszewski, H. Bem
10. Radionuclides of iron (55Fe), nickel (63Ni), polonium (210Po), uranium (234U,
(238Pu, 239-240Pu, 241Pu) in Poland and Baltic Sea environment
B. Skwarzec, D.I. Strumińska, A. Boryło
235
U,
238
U) and plutonium
11. Investigation of the influence of high humidity and exposure duration on the measurement results of
radon concentration by means of PicoRad system in the CLOR calibration chamber
O. Stawarz, M. Karpińska, K. Mamont-Cieśla
12. Accumulation properties of Norway spruce (Picea abies) for different radionuclides
E. Tomankiewicz, J.W. Mietelski, P. Gaca, S. Błażej
13. Spatial 137Cs distribution in forest soil
A. Dołhańczuk-Śródka, T. Majcherczyk, M. Smuda, Z. Ziembik, M. Wacławek
14. Isotope effects on selected physicochemical properties of nitromethane and 1-pentanol
A. Makowska, J. Szydłowski
15. Radiation chemistry of radioactive waste to be stored in the salt mine repository
Z.P. Zagórski
Proceedings of the 18th International Conference on Nucleus-Nucleus Collisions, 4-9 August 2005, Budapest,
Hungary
1. Preface
J. Pluta
2. Freeze-out and anisotropic flow in microscopic models
L.V. Bravina, K. Tywoniuk, E.E. Zabrodin, G. Burau, J. Bleibel, C. Fuchs, A. Faessler
––
3. Can thermal model explain Λ/p puzzle?
L.V. Bravina, M.S. Nilsson, K. Tywoniuk, E.E. Zabrodin
4. Rapidity distributions of strange particles in Pb-Pb at 158 A GeV
G.E. Bruno on behalf of the NA57 Collaboration
5. Elliptic flow at RHIC with NeXSPheRIO
R.P.G. Andrade, F. Grassi, Y. Hama, T. Kodama, O. Socolowski Jr., B. Tavares
6. Effect of hadronic rescattering on the elliptic flow after the hydrodynamics model
G.L. Ma, Y.G. Ma, B.H. Sa, X.Z. Cai, Z.J. He, H.Z. Huang, J.L. Long, W.Q. Shen, C. Zhong, J.H. Chen,
J.X. Zuo, S. Zhang, X.H. Shi
7. Systematic study of directed flow at RHIC energies
A.C. Mignerey for the PHOBOS Collaboration
190
NUKLEONIKA
8. The azimuthal anisotropy of electrons from heavy flavor decays in
by PHENIX
S. Sakai for the PHENIX Collaboration
sNN = 200 GeV Au-Au collisions
9. Influence of the non-flow effects and fluctuations on the v2 measurements at RHIC
X. Zhu, M. Bleicher
10. Freeze-out process with in-medium nucleon mass
S. Zschocke, L.P. Csernai, E. Molnár, J. Manninen, A. Nyiri
11. Non-identical particle correlations in central Pb+Au collisions at 158 A GeV
D. Antończyk for the CERES Collaboration
12. Charge balance functions and the transverse flow
P. Bożek
13. Preliminary results on direct photon-photon HBT measurements in sNN = 62.4 GeV and 200 GeV
Au+Au collisions at RHIC
D. Das, G. Lin, S. Chattopadhyay, A. Chikanian, E. Finch, T.K. Nayak, S.Y. Panitkin, J. Sandweiss,
A.A. Suaide, H. Zhang for the STAR Collaboration
14. Baryon-baryon correlations in Au+Au collisions at sNN = 62 GeV and sNN = 200 GeV, measured in
the STAR experiment at RHIC
H.P. Gos for the STAR Collaboration
15. Charge transfer fluctuations as a QGP signal
S. Jeon, L. Shi, M. Bleicher
16. Strangeness conservation and pair correlations of neutral kaons with close momenta in inclusive processes
V.L. Lyuboshitz, V.V. Lyuboshitz
17. Obtaining the specific heat of hadronic matter from CERN/RHIC experiments
A. Mekjian
18. The evolution of correlation functions from low to high pT in PHENIX: from HBT to jets
J.T. Mitchell for the PHENIX Collaboration
19. Effect of hard processes on momentum correlations in pp and pp– collisions
G. Paić, P.K. Skowroński
20. A survey of multiplicity fluctuations in PHENIX
J.T. Mitchell for the PHENIX Collaboration
21. How to measure specific heat using event-by-event average pT fluctuations
M.J. Tannenbaum for the PHEHIX Collaboration
22. A statistical model analysis of yields and fluctuations in 200 GeV Au-Au collisions
G. Torrieri, S. Jeon, J. Rafelski
23. Proposition of numerical modelling of BEC
O.V. Utyuzh, G. Wilk, Z. Włodarczyk
24. Transverse momentum distributions and string percolation study in p+p, d+Au and Au+Au collisions
at sNN = 200 GeV
B.K. Srivastava, R.P. Scharenberg, T.J. Tarnowsky for the STAR Collaboration
Information
INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY
NUKLEONIKA
Dorodna 16, 03-195 Warszawa, Poland
phone: (+4822) 504-11-32; fax: (+4822) 811-15-32; e-mail: [email protected]
Abstracts and full texts are available on-line at http://www.ichtj.waw.pl/ichtj/general/nukleon.htm
INTERVIEWS IN 2006
191
INTERVIEWS IN 2006
Niedzicki W.: Sylwetki uczonych (Profiles of scientistis). TVP, Program 1, 20.09.2006.
Truszczak D.: Osiągnięcia nauki (Achievements of science). Polskie Radio, Program 1, 20.09.2006.
Giurla S.: A tecnologia avança e a humanidade agradece (High-tech serving the people). Brasil Nuclear,
11, 29, 20-22 (2006).
Łoś P.: Akceleratory elektronów w ochronie środowiska (Application of electron accelerators in environmental protection). Radio dla Ciebie, 30.10.2006.
192
PATENTS
1. Sposób otrzymywania paliw ciekłych z odpadów tworzyw sztucznych, zwłaszcza odpadów poliolefinowych
i urządzenie do realizacji tego sposobu (Method for obtaining liquid fuels from wastes of plastics, particularly of polyolefines, and a facility to realize the method)
A.G. Chmielewski, J. Jerzy, T. Siekierski, B. Tymiński, K. Zwoliński
Polish Patent No. 191891
2. Sposób usuwania lotnych zanieczyszczeń organicznych gazowych takich jak wielopierścieniowe węglowodory
aromatyczne z przemysłowych gazów odlotowych (Method for elimination of gaseous organic impurities
such as polycyclic aromatic hydrocarbons from industrial flue gases)
A.G. Chmielewski, A. Ostapczuk, K. Kubica, J. Licki
3. Sposób zwiększenia efektywności oczyszczania promieniotwórczych ścieków nisko i średnio aktywnych
zatężanych metodą odwróconej osmozy (Method for enhancement of purification effectiveness of low
and medium level radioactive wastes concentrated by reverse osmosis)
A.G. Chmielewski, M. Harasimowicz, B. Tymiński, G. Zakrzewska-Trznadel
PATENT APPLICATIONS
1. Detektor do pomiaru stężenia produktów rozpadu radonu w powietrzu (Detector for measuring the concentration of radon decay products in air)
B. Machaj, J. Bartak
P 378974
2. Sposób otrzymywania dwuwolframianu itrowo-potasowego oraz nanokompozytu tego dwuwolframianu
dotowanego iterbem (Method for obtaining ittrium-potassium ditungstate and a nanocomposite of this
compound doped with ytterbium)
A. Deptuła, W. Łada, T. Olczak, D. Wawszczak, M. Borowiec, H. Szymczak, W. Diakonow, M. Barański
P 379537 (with the Institute of Physics, Polish Academy of Sciences)
3. Sposób otrzymywania napełniaczy o strukturze montmorylonitu (Method for obtaining fillers of montmorillonite structure)
Z. Zimek, I. Legocka, K. Mirkowski, A. Nowicki, G. Przybytniak
P 379779
4. Sposób otrzymywania terapeutycznych ilości radionuklidu 177Lu (Method for obtaining therapeutic quantities of the 177Lu radionuclide)
A. Bilewicz, E. Iller
P 379829
5. Sposób wytwarzania mikrokrystalicznej celulozy (Method for obtaining microcrystalline cellulose)
H. Stupińska, J. Palenik, E. Kopania, D. Wawro, D . Ciechańska, G. Krzyżanowska, E. Iller, Z. Zimek
P 380328 (with the Institute of Biopolymers and Chemical Fibres, and the Pulp and Paper Research
Institute)
193
CONFERENCES ORGANIZED AND CO-ORGANIZED
BY THE INCT IN 2006
1. REGIONAL TRAINING COURSE “APPLICATION OF MONTE CARLO MODELING
METHODS FOR DOSIMETRY CALCULATION IN RADIATION PROCESSING” IN THE
FRAME OF THE TECHNICAL COOPERATION PROJECT RER/8/010 “QUALITY
CONTROL METHODS AND PROCEDURES FOR RADIATION TECHNOLOGY”, 3-7
APRIL 2006, WARSZAWA, POLAND
Organized by the Institute of Nuclear Chemistry and Technology, International Atomic Energy Agency
Organizing Committee: I. Kałuska, M.Sc., Z. Zimek, Ph.D., Prof. A.G. Chmielewski, Ph.D., D.Sc.
OPENING
J. Michalik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
A. Chupov (International Atomic Energy Agency, Vienna, Austria)
H. Sampa (International Atomic Energy Agency, Vienna, Austria)
LECTURES
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
New development in constuction and operation of radiation processing plants
A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Warsaw University of Technology, Poland)
The use of dosimetry in process validation and facility qualification
A. Kovacs (Institute of Isotopes and Surface Chemistry, Budapest, Hungary)
The role of Monte Carlo methods in industrial radiation application
J. Mittendorfer (MEDISCAN, Austria)
Physical and mathematical methods for simulation of radiation processing
V. Lazurik (Kharkov State University, Ukraine)
Models of an irradiation process for EB technologies (numerical code RT-Office)
G. Popov (Kharkov State University, Ukraine)
Software for EB processing: ModeRTL, ModeDF, ModeCEB
Architecture of RT-Office software
V. Lazurik (Kharkov State University, Ukraine)
The use of dosimetry and interpretation of dosimetry data
K. Mehta (International Atomic Energy Agency, Vienna, Austria)
Calorimeters and alanine, CTA, PVC foil dosimeters
Z. Stuglik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Dosimetry system for EB irradiation
A. Kovacs (Institute of Isotopes and Surface Chemistry, Budapest, Hungary)
Introduction to intercomparison experiments
Z. Stuglik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Uncertainty in dose measurements
Uncertainty evaluation of computer programs based on Monte Carlo method for dose calculations
J. Mittendorfer (MEDISCAN, Austria)
Validation of radiation sterilization process
I. Kałuska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
X-ray application for radiation processing
Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Radiation processing of polymers
A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Warsaw University of Technology, Poland)
194
•
•
•
•
•
Simulation of irradiation process on radiation-technological lines (RTL) with scanned beam; software
ModeRTL
V. Lazurik, G. Popov (Kharkov State University, Ukraine)
Evaluation of intercomparison experiments
K. Mehta (International Atomic Energy Agency, Vienna, Austria), A. Kovacs (Institute of Isotopes and
Surface Chemistry, Budapest, Hungary)
Comparison of the experimental results with simulation predictions
V. Lazurik (Kharkov State University, Ukraine), G. Popov (Kharkov State University, Ukraine), Z. Zimek
(Institute of Nuclear Chemistry and Technology, Warszawa, Poland), I. Kałuska (Institute of Nuclear
Chemistry and Technology, Warszawa, Poland)
Simulation of irradiation process of multi-layer circular objects such as wire, cables, tubing, pipes with
scanned beam
Examples of some actual problems solutions in radiation processing
V. Lazurik (Kharkov State University, Ukraine), G. Popov (Kharkov State University, Ukraine)
SPECIAL LECTURES – technical visit to the Institute of Nuclear Chemistry and Technology
•
•
•
•
Film Dose Reader CD-02
B. Machaj (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Radiation facilities at the Institute of Nuclear Chemistry and Technology]
Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Sadło (Institute of
Nuclear Chemistry and Technology, Warszawa, Poland), I. Kałuska (Institute of Nuclear Chemistry and
Technology, Warszawa, Poland), S. Bułka (Institute of Nuclear Chemistry and Technology, Warszawa,
Poland)
The experimental validation of simulation predictions for dose mapping in heterogeneous targets irradiation with scanned EB
I. Kałuska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), S. Bułka (Institute of
Nuclear Chemistry and Technology, Warszawa, Poland), Z. Stuglik (Institute of Nuclear Chemistry and
Technology, Warszawa, Poland), G. Popov (Kharkov State University, Ukraine)
Biological dosimetry in human biomonitoring
M. Kruszewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), K. Brzozowska
(Institute of Nuclear Chemistry and Technology, Warszawa, Poland), T. Bartłomiejczyk (Institute of
Nuclear Chemistry and Technology, Warszawa, Poland), A. Wójcik (Institute of Nuclear Chemistry and
Technology, Warszawa, Poland)
2. THE WORKSHOP “DOSIMETRY FOR RADIATION APPLICATION IN TECHNOLOGIES
FOR ENVIRONMENT POLLUTION CONTROL” IN THE FRAME OF THE MARIE
CURIE HOST FELLOWSHIPS FOR THE TRANSFER OF KNOWLEDGE: ADVANCED
METHODS FOR ENVIRONMENT RESEARCH AND CONTROL (AMERAC), 5 APRIL
2006, WARSZAWA, POLAND
Organized by the Institute of Nuclear Chemistry and Technology
LECTURES
•
•
•
•
•
Overview of dosimetry methods for radiation technologies for environment preservation
Application of dosimetry for wastewater treatment – Brazilian experience
M.H.O Sampa (International Atomic Energy Agency, Vienna, Austria), P.R. Rela (Instituto de Pesquisas
Energéticas e Nucleares (IPEN), São Paulo, Brazil), C.L. Duarte (Instituto de Pesquisas Energéticas e
Nucleares (IPEN), São Paulo, Brazil), C.S. Rela (Instituto de Pesquisas Energéticas e Nucleares (IPEN),
São Paulo, Brazil), F.E. Costa (Instituto de Pesquisas Energéticas e Nucleares (IPEN), São Paulo, Brazil)
Dosimetry for wastewater treatment tests – Italian experience
M. Lavalle (Institute for Organic Synthesis and Photoreactivity (ISOF), National Research Council
(CNR), Bologna, Italy)
Dosimetric methods for industrial scale flue gas treatment
Dosimetric methods for laboratory scale VOC treatment
A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Warsaw University of Technology, Poland), Y. Sun (Institute of Nuclear Chemistry and Technology, Warszawa,
•
195
Poland), S. Bułka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Electron beam application for volatile organic compounds removal
A. Ostapczuk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
3. THE WORKSHOP “METHODS OF ENVIRONMENTAL RESEARCH” IN THE FRAME
OF THE MARIE CURIE HOST FELLOWSHIPS FOR THE TRANSFER OF KNOWLEDGE:
ADVANCED METHODS FOR ENVIRONMENT RESEARCH AND CONTROL (AMERAC),
10 AUGUST 2006, WARSZAWA, POLAND
LECTURES
•
•
•
The use of stable isotopes of carbon to study the sources and sinks of some greenhouse gases (CO2, CH4)
in air
S.M. Cuna (National Institute for Research and Development of Isotopic and Molecular Technologies,
Cluj-Napoca, Romania)
Design of novel membranes and their application for desalination by membrane distillation
M. Khayet Souhaimi (University Complutense of Madrid, Spain)
Modelling and optimization of experimental processes in environmental engineering using Response
Surface Methodology (RSM)
C. Cojocaru (”Gh.Asachi” Technical University of Iaºi, Romania)
DISCUSSION: conclusions, recommendations
Moderator: A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Warsaw
University of Technology, Poland)
4. SYMPOZJUM „CHEMIA I TECHNIKA RADIACYJNA: WYZWANIA I MOŻLIWOŚCI –
JUBILEUSZ 80-LECIA PROF. DR HAB. ZBIGNIEWA P. ZAGÓRSKIEGO” (SYMPOSIUM
ON CHEMISTRY AND RADIATION TECHNIQUES: CHALLENGE AND POSSIBILITIES
– JUBILEE OF THE 80th ANNIVERSARY OF Prof. ZBIGNIEW P. ZAGÓRSKI, Ph.D.,
D.Sc. (17 OCTOBER 2006, WARSZAWA, POLAND)
LECTURES
•
•
•
•
•
•
•
•
Laudation
L. Waliś (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Mayer (Institute of
Applied Radiation Chemistry, Łódź, Poland), Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Przyszłość chemii radiacyjnej, jak ją widziano w roku 1946 (Future of radiation chemistry as was seen in
1946)
Z.P. Zagórski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Znane i nieznane aspekty pierwszych etapów działania promieniowania jonizującego w biopolimerach
i polimerach syntetycznych (Known and unknown aspects of primary stages of ionizing radiation treatment of biopolymers and synthetic polymers)
G. Przybytniak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Pomiary odległości metodą EPR (Distance measurements by the EPR method)
J. Michalik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Wolne rodniki w związkach o znaczeniu biologicznym (Free radicals in biological important compounds)
K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Ciecze jonowe – rozpuszczalniki przyszłości? (Ionic liquids – solvents of future?)
J. Grodkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Relaksacja elektronów pułapkowanych w etanolu oraz mieszaninach etanol-woda i etanol-metanol w temperaturze 10-77 (100) K (Relaxation of trapped electrons in ethanol and ethanol-methanol mixtures at a
temperature of 10-77 (100) K)
J.P. Suwalski (Institute of Applied Radiation Chemistry, Łódź, Poland)
Obecne i przyszłe zastosowania technik radiacyjnych w przetwórstwie polimerów (Present and future
applications of radiation processing in polymer modification)
A. Rafalski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
196
•
•
•
Antologia dozymetrii radiacyjnej dużych dawek (Antology of high dose radiation dosimetry)
P. Panta (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Radiacyjna modyfikacja elastomerów (Radiation modification of elastomers)
W. Głuszewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Chemia i technika radiacyjna - i co dalej? (Radiation chemistry and radiation processing – what the next
thing?)
5. IV KONFERENCJA „PROBLEMY UNIESZKODLIWIANIA ODPADÓW” (IV CONFERENCE
ON PROBLEMS OF WASTE DISPOSAL), 27 NOVEMBER 2006, WARSZAWA, POLAND
Organized by the Warsaw University of Technology, Plant for Utilization of Solid Municipal Wastes
(Warszawa), Institute of Nuclear Chemistry and Technology, Gdańsk University of Technology
Organizing Committee: M. Obrębska, Ph.D., A. Polak, M.Sc.
OPENING
Jerzy Bałdyga (Warsaw University of Technology, Poland)
Session IA. NAUKOWO-TECHNICZNA (SCIENCE AND TECHNOLOGY)
Chairman: A. Biń (Warsaw University of Technology, Poland)
•
•
•
Przemysłowe testy współspalania komunalnych osadów ściekowych z węglem w kotle pyłowym (Combustion of municipal sludge with coal in a dust boiler – industrial tests)
R. Wasilewski (Institute for Chemical Processing of Coal, Zabrze, Poland), S. Stelmach (Institute for
Chemical Processing of Coal, Zabrze, Poland), J. Zuwała (Institute for Chemical Processing of Coal,
Zabrze, Poland)
Współspalanie odpadów, biomasy i paliw kopalnych w kotłach energetycznych (Combustion of wastes,
biomass and fossil fuels in energetic boilers)
H. Karcz (Wrocław University of Technology, Poland), M. Krzysztof (ZBUS Combustion, Głowno,
Poland), K. Folga (ZBUS Combustion, Głowno, Poland)
Wykorzystanie odpadowej biomasy do oczyszczania roztworów wodnych (Application of waste biomass
for purification of water solutions)
K. Bratek (Wrocław University of Technology, Poland), W. Bratek (Wrocław University of Technology,
Poland)
Session IB. SAMORZĄDOWO-EKONOMICZNO-PRAWNA (MUNICIPAL-ECONOMIC-LAWFUL)
Chairman: P. Grzybowski (Warsaw University of Technology, Poland)
•
•
EUROVIX – biotechnologie dla życia (EUROVIX – Biotechnologies for life)
K. Łuczak (EUROVIX S.r.l., Italy)
Dlaczego powinniśmy spalać odpady? (Why we should incinerate the wastes?)
G. Wielgosiński (Technical University of Łódź, Poland)
Session IIA. NAUKOWO-TECHNICZNA (SCIENCE AND TECHNOLOGY)
Chairman: R. Zarzycki (Technical University of Łódź, Poland)
•
•
•
Analityczne badania radiolitycznej degradacji wybranych pestycydów (Radiolytical degradation of selected pesticides – analytical investigations)
A. Bojanowska-Czajka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), P. Drzewicz
(Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Trojanowicz (Institute of Nuclear
Chemistry and Technology, Warszawa; Warsaw University of Technology, Poland), G. Nałęcz-Jawecki
(Medical University of Warsaw, Poland), J. Sawicki (Medical University of Warsaw, Poland), Z. Zimek
(Institute of Nuclear Chemistry and Technology, Warszawa, Poland), H. Nichipor (Institute of Radiation Physical-Chemical Problems, National Academy of Sciences of Belarus, Minsk, Belarus)
Unieszkodliwianie odpadów drobiarskich poprzez fermentacje metanową (Disposal of poultry wastes
by methane fermentation)
A. Zawadzka (Technical University of Łódź, Poland), K. Sikora-Łępicka (Technical University of Łódź,
Poland)
Opracowanie sposobu zmniejszenia zrzutu azotu amonowego w ścieku technologicznym (A method for
the reduction of ammonia in technological wastewater)
J. Zieliński (Institute of Industrial Organic Chemistry, Warszawa, Poland), K. Zwierzyński (Institute of
Industrial Organic Chemistry, Warszawa, Poland), M. Lewandowska (Institute of Industrial Organic
Chemistry, Warszawa, Poland)
197
Session IIB. SAMORZĄDOWO-EKONOMICZNO-PRAWNA (MUNICIPAL-ECONOMIC-LAWFUL)
Chairman: G. Wielgosiński (Technical University of Łódź, Poland)
•
•
Spalać czy składować? (To incinerate or to storage on landfill sites)
J. Kaznowski (SPEC S.A., Warszawa, Poland)
Eliminacja przykrych zapachów w oczyszczalniach ścieków (Elimination of stench in wastewater treatment)
M. Szatkowski (Westrand Polska, Warszawa, Poland)
Session IIIA. NAUKOWO-TECHNICZNA (SCIENCE AND TECHNOLOGY)
Chairman: M. Obrębska (Warsaw University of Technology, Poland)
•
•
•
Przetwarzanie poużytkowych opakowań z poli(tereftalanu etylenu) na węgiel aktywny (Processing of
used PET packaging into active carbon)
A. Świątkowski (WAT Military University of Technology, Warszawa, Poland), A. Padée (Warsaw Agricultural University, Poland)
Analiza własności ciekłych produktów termicznej depolimeryzacji polipropylenu (Properties of liquid
products of polypropylene degradation)
P. Grzybowski (Warsaw University of Technology, Poland)
Problemy związane z upłynnianiem odpadów poliolefin (Problems of liquefaction of polyolefine wastes)
B. Tymiński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), R. Jurczyk (Institute
of Nuclear Chemistry and Technology, Warszawa, Poland)
198
Ph.D. THESES
1. Hanna Lewandowska-Siwkiewicz, M.Sc.
Powstanie, struktura i przemiany dinitrozylowych kompleksów żelaza w modelowych układach biologicznych (Formation, structure and interactions of dinitrosyl iron complexes in model biological systems)
supervisor: Assoc. Prof. Marcin Kruszewski, Ph.D., D.Sc.
Institute of Nuclear Chemistry and Technology, 23.02.2006
D.Sc. THESES
1. Grażyna Zakrzewska-Trznadel, Ph.D.
Procesy membranowe w technologiach jądrowych (Membrane processes in nuclear technologies)
Technical University of Łódź
EDUCATION
199
EDUCATION
Ph.D. PROGRAMME IN CHEMISTRY
The Institute of Nuclear Chemistry and Technology holds a four-year Ph.D. degree programme for graduates of chemical, physical and biological departments of universities, for graduates of medical universities and to engineers in chemical technology and material science.
The main areas of the programme are:
• radiation chemistry and biochemistry,
• chemistry of radioelements,
• isotopic effects,
• radiopharmaceutical chemistry,
• analytical methods,
• chemistry of radicals,
• application of nuclear methods in chemical and environmental research, material science and protection of historical heritage.
The candidates accepted for the mentioned programme can be employed in the Institute. The candidates can apply for a doctorial scholarship. The INCT offers accommodation in 10 rooms in the
guesthouse for Ph.D. students not living in Warsaw.
During the four-year Ph.D. programme the students participate in lectures given by senior staff from
the INCT, Warsaw University and the Polish Academy of Sciences. In the second year, the Ph.D. students
have teaching practice in the Chemistry Department of Warsaw University. Each year the Ph.D. students
are obliged to deliver a lecture on topic of his/her dissertation at a seminar. The final requirements for the
Ph.D. programme graduates, consistent with the regulation of the Ministry of Education and Science,
are:
• submission of a formal dissertation, summarizing original research contributions suitable for publication;
• final examination and public defense of the dissertation thesis.
In 2006, the following lecture series were organized:
• “Fundalmentals of coordination chemistry” – Prof. Jerzy Narbutt, Ph.D., D.Sc. (Institute of Nuclear
Chemistry and Technology, Warszawa, Poland);
• “Spectrometry mass techniques (ICP MS, electrospray MS, MALDI MS) in analytical chemistry” –
Prof. Ryszard Łobiński, Ph.D. (Centre National de la Recherche Scientifique – CNRS, Pau, France);
• “Radiation technologies and nuclear techniques in environmental protection” – Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa; Warsaw University
of Technology, Poland).
The qualification interview for the Ph.D. programme takes place in the mid of October. Detailed
information can be obtained from:
• Head: Assoc. Prof. Aleksander Bilewicz, Ph.D., D.Sc.
(phone: (+4822) 504 13 57, e-mail: [email protected]);
• Secretary: Dr. Ewa Gniazdowska
(phone: (+4822) 504 10 74 or 504 11 78, e-mail: [email protected]).
TRAINING OF STUDENTS
Country
N umber of
participants
Period
A GH U niversity of Science and Technology
Poland
3
2 weeks
Chalmers U niversity of Technology
Sweden
21
one-day
practice
European U nion
France
1
2 months
I nstitution
200
EDUCATION
Country
N umber of
participants
Period
European U nion
R omania
1
3 months
Forschungszentrum D resden-R ossendorf
I nstitute of R adiopharmacy
Germany
3
2 weeks
I nternational A tomic Energy A gency
Egypt
1
3 months
Jordan
1
1 month
V ietnam
1
3 months
Technical School of Chemistry
Poland
(W arszawa)
2
1 month
U niversity of Z urich
I nstitute of Chemistry
Switzerland
1
1 week
W arsaw U niversity
Poland
1
2 months
W arsaw U niversity of Technology
Faculty of Chemical and Process Engineering
Poland
6
one-day
practice
Faculty of Chemistry
Poland
2
1 month
Faculty of Electronics and I nformation Technology
Poland
1
1 month
Faculty of M aterials Science and Engineering
Poland
5
1 month
Faculty of Physics
Poland
27
one-day
practice
I nstitution
201
RESEARCH PROJECTS GRANTED
BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION
IN 2006 AND IN CONTINUATION
1. Neutron activation analysis and ion chromatography as a tool for reliable lanthanides determination in biological and environmental samples.
supervisor: Bożena Danko, Ph.D.
2. The chemical isotope effects of gallium, indium and thallium in ligand exchange and red-ox reactions.
supervisor: Wojciech Dembiński, Ph.D.
3. Comparative analysis of telomere length, chromosomal aberration frequency and DNA repair kinetics
in peripheral blood lymphocytes of healthy donors and cancer patients.
supervisor: Prof. Andrzej Wójcik, Ph.D., D.Sc.
4. Oxidation of thioether by organic complexes of copper. Processes of potential importance for pathogenesis of some neurodegenerative diseases.
supervisor: Assoc. Prof. Dariusz Pogocki, Ph.D., D.Sc.
5. New methods of the study and reduction of fouling in processes of micro- and ultrafiltration of liquid
radioactive waste.
supervisor: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc.
6. Modelling of the dispersion of pollutants and studying their transport in natural water receivers
using stable isotopes as tracers.
supervisor: Andrzej Owczarczyk, Ph.D./Jacek Palige, Ph.D.
7. Influence of gamma irradiation on starch properties: starch interaction with water and lipids,
starch-lipid films.
supervisor: Krystyna Cieśla, Ph.D.
8. Changes of sulphur isotope ratio in the products of coal combustion and flue gas desulphurization
processes.
supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.
9. Process of nanostructure formation of small-molecule organic gels using synchrotron methods.
supervisor: Assoc. Prof. Helena Grigoriew, Ph.D., D.Sc.
10. Analytical studies of products of degradation of selected chlorophenols and pesticides caused by
ionizing radiation.
supervisor: Prof. Marek Trojanowicz, Ph.D., D.Sc.
11. Studies of coordination of magnesium and zinc ions in their complexes with the azine dicarboxylate
ligands.
supervisor: Prof. Janusz Leciejewicz, Ph.D., D.Sc.
12. Stable isotope applications to quality and origin control of milk and milk products.
supervisor: Ryszard Wierzchnicki, Ph.D.
13. Protection phenomena in radiation chemistry of polypropylene.
supervisor: Prof. Zbigniew P. Zagórski, Ph.D., D.Sc.
14. Modification of the near surface layer of carbon steels with intense argon and nitrogen plasma pulses.
supervisor: Prof. Jerzy Piekoszewski, Ph.D., D.Sc.
15. Pilot plant for thermocatalytic degradation of polyolefine and polystyrene wastes into liquid fuels.
supervisor: Bogdan Tymiński, Ph.D.
202
16. Cheap and non-toxic dosimeter for measurement of absorbed dose in radiation processing of fluidized
beds and fluid streams.
supervisor: Zofia Stuglik, Ph.D.
17. Analytical studies of decomposition of selected pesticides using ionizing radiation.
supervisor: Prof. Marek Trojanowicz, Ph.D., D.Sc.
18. Complexes of astatine-211 with metals as potential precursors of radiopharmaceuticals.
supervisor: Assoc. Prof. Aleksander Bilewicz, Ph.D., D.Sc.
κB signalling in response to oxidative stress.
19. The role of pirin in regulation of NF-κ
20. Examination of the antimutagenic effects of 1,4-dihydropyridine on mammalian cells after exposure
to X-rays.
supervisor: Prof. Irena Szumiel, Ph.D., D.Sc.
RESEARCH PROJECTS ORDERED
BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION
IN 2006
1. Radiation processing application to form nanofillers with different structure including hybrid and
functionalized.
PBZ-KBN-095/T08/2003
supervisor: Zbigniew Zimek, Ph.D.
2. Mutual interactions between nutritional components in steering of development of the intestinal immunological system.
PBZ-KBN-093/P06/2003
IAEA RESEARCH CONTRACTS IN 2006
1. Application of ionizing radiation for removal of pesticides from ground waters and wastes.
12016/RO
principal investigator: Prof. Marek Trojanowicz, Ph.D., D.Sc.
2. Radiation resistant polypropylene for medical applications and as a component of structural engineering materials.
12703/RO
principal investigator: Zbigniew Zimek, Ph.D.
3. Electron beam for VOCs treatment emitted from oil combustion process.
13136/RO
principal investigator: Anna Ostapczuk, M.Sc.
IAEA TECHNICAL CONTRACTS IN 2006
1. Methyl bromide generator type ABC with accesories for transportation and labeling with radioactive
gaseous methyl bromide.
RAF4016-92242C
EUROPEAN COMMISSION RESEARCH PROJECTS IN 2006
1. FP6 Integrated Project European research program for the partitioning of actinides from high active
wastes issuing the reprocessing of spent nuclear fuels (EUROPART).
FP6-508854
203
2. FP5 Research Training Network: Sulfur radical chemistry of biological significance: the protective and
damaging roles of thiol and thioether radicals (SULFRAD).
principal investigator: Prof. Krzysztof Bobrowski, Ph.D., D.Sc.
RTN-2001-00096 under FP5
3. FP6 Marie Curie Host Fellowships for the Transfer of Knowledge: Advanced methods for environment
research and control (AMERAC).
principal investigator: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc.
MTKD-CT-2004-509226
4. FP6 Marie Curie Host Fellowships for the Transfer of Knowledge: Chemical studies for design and production of new radiopharmaceuticals (POL-RAD-PHARM).
principal investigator: Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.
MTKD-CT-2004-509224
5. European cooperation in the field of scientific and technical research. COST D27 – Prebiotic chemistry and
early evolution. Role of radiation chemistry in the origin of life on Earth.
supervisor: Prof. Zbigniew Zagórski, Ph.D., D.Sc.
6. European cooperation in the field of scientific and technical research. COST P9 – Radiation damage in
biomolecular systems (RADAM). Mechanisms of radiation damage transfer in polypeptide molecules.
supervisor: Prof. Krzysztof Bobrowski, Ph.D., D.Sc.
OTHER FOREIGN CONTRACTS IN 2006
1. Laboratory scale experimental analysis of electron beam treatment of flue gases from combustion of
liquid petroleum oils.
Contract with King Abdulaziz City for Science and Technology, Atomic Energy Research Institute, Saudi
Arabia
2. Feasibility study for electron beam flue gas treatment at oil fired boiler.
Contract with King Abdulaziz City for Science and Technology, Atomic Energy Research Institute, Saudi
Arabia
3. The realization and delivery of nickel electrodes coated with magnesium doped lithium cobaltite.
Research contract with ENEA, the Italian Agency for New Technologies, Energy and Environment
204
1. Agorastos Nikos, University of Zurich, Switzerland, 21-26.05.
2. Ajji Zaki, Atomic Energy Commission of Syria, Damascus, Syria, 07-12.05.
3. Araya Ramiro, Universidad de Chile, Chile, 19-27.08.
4. Bekmuratov Timur, Institute of Nuclear Physics, National Nuclear Centre of the Republic of Kazakhstan,
Almaty, Kazakhstan, 05.04.
5. Belchior Ana, Instituto Nacional de Engenharia e Technologia Industrial (INETI), Sacavém, Portugal, 05.04.
6. Belgaya Tamas, Institute of Isotope and Surface Chemistry, Budapest, Hungary, 16-20.10.
7. Botelho Maria Luisa, Nuclear and Technological Institute (ITN), Sacavém, Portugal, 05.04.
8. Bznuni Surik, Nuclear and Radiation Safety Center of Armenian Nuclear Regulatory Authority,
Yerevan, Armenia, 05.04.
9. Cabalka Martin, Nuclear Research Institute, Øež, Czech Republik, 05.04.
10. Chorniy Anton, Kharkov State University, Ukraine, 05.04.
11. Chukalov Sergey, Institute of Nuclear Physics, National Nuclear Center of the Republic of Kazakhstan,
Almaty, Kazakhstan, 28-29.06.
12. Cojocaru Corneliu, “Gh. Asachi” Technical University of Iaºi, Romania, 04.07.-04.10.
13. Cuna Stela, National Institute for Research and Development of Isotopic and Molecular Technologies,
Cluj-Napoca, Romania, 18.07.-18.09.
14. Dalivelya Olga, Institute of Genetics and Cytology, National Academy of Sciences of Belarus, Minsk,
Belarus, 03-21.07.
15. Demski Mikhail, The D.V. Efremov Scientific Research Institute of Electrophysical Apparatus
(NIIEFA), St. Petersburg, Russia, 01-06.10.
16. Drapkin Valery, St. Petersburg Instruments Ltd., Russia, 22-29.04.
17. Duc Ho Minh, Institute for Nuclear Science and Techniques, Vietnam Atomic Energy Commission
(VAEC), Hanoi, Vietnam, 02-14.10.
18. Enache Mirela, Institute of Physical Chemistry “I.G. Murgulescu”, Romanian Academy, Bucharest,
Romania, 01.01.-31.03.
19. Fuente Julio de la, Universidad de Chile, Chile, 08-27.08.
20. Fulop Marko, Institute of Preventive and Clinical Medicine, Bratislava, Slovakia, 05.04, 26-27.10.
21. Georgescu Rodica-Maria, Horia Hulubei National Institute of Physics and Nuclear Engineering,
Bucharest, Romania, 05.04.
22. Gryzlov Anatolij, NPO “Toriy”, Moscow, Russia, 20.06.-05.07, 18-24.09.
23. Gürtler Sylvia, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany, 17-29.09.
24. Houeé-Levin Chantal, Université Paris-Sud, France, 17-18.02.
25. Hug Gordon L., University of Notre Dame Radiation Laboratory, USA, 03-06.01, 17-18.02, 28.09.-01.10.
26. Hustuc Aleksandru, National Scientific Center of Applied Preventive Medicine, Chisinau, Moldavia, 05.04.
27. Ivanov A., The D.V. Efremov Scientific Research Institute of Electrophysical Apparatus (NIIEFA), St.
Petersburg, Russia, 22-28.10.
28. Jafarov Yadigar, Institute of Radiation Problems, Azerbaijan National Academy of Sciences, Baku,
Azerbaijan, 05.04.
29. Kasztovszky Zsolt, Institute of Isotope and Surface Chemistry, Budapest, Hungary, 16-20.10.
30. Khalil Luai Ahmad, Jordan Atomic Energy Commission, Amman, Jordan, 08.10.-09.11.
31. Khayet Souhaimi Mohamad, University Complutense of Madrid, Spain, 03.07.-29.08.
32. Kim Jinkyu, EB-Tech Co., Ltd., Daejeon, Korea, 19-24.08.
33. Kovacs Andras, Institute of Isotope Research, Hungarian Academy of Sciences, Budapest, Hungary, 05.04.
205
34. Knyazev Mikhail, St. Petersburg Instruments Ltd., Russia, 22-29.04, 07-12.08, 07-12.11.
35. Krpan Katarina, Rudjer Boskovic Institute, Zagreb, Croatia, 05.04.
36. Kuenstler Jens-Uwe, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany,
26.06.-26.07.
37. Lazurik Valentina, Kharkiv National University, Ukraine, 02-07.04.
38. Lavalle Marco, Institute for the Organic Synthesis and Photoreactivity, National Research Council of
Italy (ISOF-CNR), Bologna, Italy, 02-09.04.
39. Le Minh Tuan, Research and Development Center for Radiation Technology, Vietnam Atomic Energy
Commission (VINA GAMMA), Ho Chi Minh City, Vietnam, 07.05.-08.08.
40. Lebeda Ondrei, Nuclear Physics Institute, Academy of Sciences of the Czech Republic, Øež, Czech
Republic, 18.03-18.05.
41. Lebedev Vjacheslav, Joint Institute for Nuclear Research, Dubna, Russia, 13-20.08.
42. Letournel Eric, VIVIRAD SA, France, 12-13.12.
43. Lyssukin Sergey, Institute of Nuclear Physics, Almaty, Kazakhstan, 28-29.06.
44. Łobiński Ryszard, Centre National de la Recherche Scientifique – CNRS, France, 05.04.-05.06.
45. März Peter, EPR Division, Bruker Biospin GmbH, Silberstreifen, Germany, 20-25.11.
46. Mehta Kishor, International Atomic Energy Agency, United Nations, 28.02.-28.04.
47. Mozziconazzi Olivier, France, 01.01.-28.02.
48. Neves Maria, Instituto Tecnologico e Nuclear, Sacavém, Portugal, 04.09.-04.11.
49. Nichipor Henrietta, Institute of Radiation Physical-Chemical Problems, National Academy of Sciences
of Belarus, Minsk, Belarus, 17-28.07, 01-04.10.
50. Novikova Galina, National Research Restoration Centre of Ukraine, Kiev, Ukraine, 01-07.08.
51. Pawlukojć Andrzej, Joint Institute for Nuclear Research, Dubna, Russia, 17-19.09.
52. Pietzsch Juergen Hans, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany,
05-10.04.
53. Politkovskij Fiodor, NPO “Toriy”, Moscow, Russia, 20.06-05.07.
54. Popov Genadiv, Kharkiv State University, Ukraine, 05.04, 06-08.11.
55. Ramirez Trajano, National Technological University, Quito, Ecuador, 11-12.09.
56. Romanova Irina, Institute of Genetics, Academy of Sciences of Moldavia, Chisinau, Moldavia, 05.04.
57. Redaelli Renato, Universita degli Studi di Milano, Italy, 31.10.-02.11.
58. Rieck Stefanie, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany, 17-29.09.
59. Ritter Alina, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany, 17-29.09.
60. Said Amr El-Hag Ali, National Center for Radiation Research and Technology, Cairo, Egypt, 04.04.-29.06.
61. Saidi Mouldi, National Center for Nuclear Sciences and Technologies, Tunis, Tunisia, 16.05.-16.07.
62. Sampa Maria Helena, International Atomic Energy Agency, United Nations, 05.04.
63. Savina Natalya, Institute of Genetics and Cytology, National Academy of Sciences of Belarus, Minsk,
Belarus, 03-21.07.
64. Sheyno Igor, Institute of Biophysics, State Scientific Center, Moscow, Russia, 05.04.
65. Skarnemark Gunnar, Chalmers University of Technology, Göteborg, Sweden, 06.08.-05.09.
66. Smolko Edvardo, Irradiation Processing Laboratory, Centro Atomico Buenos Aires, Argentina, 07-11.09.
67. Spies Hartmut, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany,
18.03.-18.04.
68. Svinin Mikhail, The D.V. Efremov Scientific Research Institute of Electrophysical Apparatus (NIIEFA),
St. Petersburg, Russia, 22-28.10.
69. Taroyan Sargis, Yerevan Physics Institute, Yerevan Armenia, 05.04.
70. Tereshatov Evgeny, Joint Institute for Nuclear Research, Dubna, Russia, 13-20.08.
71. Tsrunchev Tsvetelin, National Centre of Radiobiology and Radiation Protection (NCRRP), Sofia,
Bulgaria, 05.04.
72. Weissabel Robert, Slovak Office of Standards, Metrology and Testing, Bratislava, Slovakia, 26-27.10.
206
1. Ewelina Chajduk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Prace nad konstruowaniem metod o najwyższej randze metrologicznej do oznaczania Se i As w materiałach
biologicznych za pomocą RNAA (High-accuracy RNAA methods for the determination of Se i As in
biological samples)
2. Prof. Zbigniew Florjańczyk (Warsaw University of Technology, Poland)
Polimery hybrydowe (Hybrid polymers)
3. Michał Gryz, M.Sc. (Office for Registration of Medicinal Products, Medical Devices and Biocides, Warszawa, Poland)
Cynk i magnez w procesach biologicznych (Zinc and magnesium in biological processes)
4. Gabriel Kciuk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Wpływ grup funkcyjnych aminokwasów na mechanizmy reakcji rodnikowych w peptydach zawierających
tyrozynę (The influence of the amino acid functional groups on the mechanism of radical reactions in
peptides containing tyrosine)
5. Monika Łyczko, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Trikarbonylkowe kompleksy technetu(I) z amidowymi pochodnymi kwasu pikolinowego i tiopikolinowego
jako prekursory radiofarmaceutyków (Tricarbonyl technetium(I) complexes with amide derivatives of
picolinic and thiopicolinic acid as potential radiopharmaceuticals)
6. Prof. Józef Mayer (Technical University of Łódź, Poland)
Reakcje jonowe w poli(chlorku winylu) (Ionic reactions in polyvinyl chloride)
7. Sylwia Męczyńska, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Wpływ OH i ONOO– na konformację i aktywność białek zawierających żelazo (The influence of nitric
oxide and peroxynitrite on conformation and activity of the iron proteins)
·
8. Dr. Maria Neves (Instituto Tecnologico e Nuclear, Sacavém, Portugal)
Radiation in medicine and biology
9. Sławomir Ostrowski, M.Sc. (Industrial Chemistry Research Institute, Warszawa, Poland)
Mechanizm reakcji wydłużania łańcucha i właściwości fizykochemiczne związków alkiloaromatycznych.
Badania metodami chemii obliczniowej (Mechanism of chain elongation reactions and physicochemical
properties of alkylaromatic compounds. Studies using calculation chemistry methods)
10. Wojciech Ozimiński, M.Sc. (National Institute of Public Health, Warszawa, Poland)
Tautometria pięcioczłonowych pierścieni heterocyklicznych zawierających trzy heteroatomy. Badania
obliczeniowe (Tautomerism of five-membered heterocyclic rings containing three heteroatoms. Calculation studies)
11. Sylwia Ptaszek, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Zastosowanie znaczników i CFD do badania dynamiki przepływu w oczyszczalni ścieków (Application
of tracers and CFD for the study of flow dynamics in wastewater treatment plant)
12. Dr. Tomasz Szreder (Institute of Dyes and Organic Products, Zgierz, Poland)
Indywidua przejściowe generowane radiacyjnie w cieczach jonowych: badania wykorzystujące pikosekundowy akcelerator elektronów w Narodowym Laboratorium w Brookhaven (USA) (Radiationally
generated transients in ionic liquids: investigations using picosecond electron accelerator in the Brookhaven National Laboratory (USA))
13. Dr. Daniel Tedder (Georgia Institute of Technology, USA)
Efficient strategies for partitioning actinides from alkaline wastes
14. Jerzy Turek, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Budowa i oddziaływania rodników srebroorganicznych. Badania EPR i DFT (Structure and interaction
of organosilver radicals. EPR and DFT study)
15. Dr. Grażyna Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Procesy membranowe w technologiach jądrowych (Membrane processes in nuclear technologies)
207
LECTURES AND SEMINARS DELIVERED OUT OF THE INCT
IN 2006
LECTURES
1. Bilewicz A.
Influence of relativistic effect on hydrolysis of heavy cations.
First International Symposium on Hydration and Hydroxo Complexation of Cations, Minsk, Belarus,
05-06.10.2006.
2. Bobrowski K.
Protection of tyrosine in Met-enkephalin against oxidation by blocking the amine function.
CNR Conference “Free Radicals in Chemical Biology”, Bologna, Italy, 30.06.2006.
3. Bojanowska-Czajka A., Drzewicz P., Trojanowicz M.
Analityczne badania radiolitycznej degradacji karbendazymu (Analytical control of carbendazim decomposition by gamma irradiation).
III Warszawskie Seminarium Doktorantów Chemików ChemSession’06, Warszawa, Poland, 19.05.2006.
4. Brzozowska K.
Wypadek radiacyjny w Białostockim Ośrodku Onkologicznym (The radiological accident in the Białystok
Oncological Center).
II Krakowsko-Poznańskie Studenckie Seminarium Fizyki Biomolekularnej i Medycznej, Poznań, Poland,
22-25.02.2006.
5. Brzozowska K., Wójcik A.
Wpływ temperatury na poziom mikrojąder indukowanych promieniowaniem jonizującym w ludzkich limfocytach krwi obwodowej (Influence of temperature on radiation-induced micronuclei in human peripheral
blood lymphocytes).
II Krakowsko-Poznańskie Studenckie Seminarium Fizyki Biomolekularnej i Medycznej, Poznań, Poland,
22-25.02.2006.
6. Brzóska K.
Piryna: nowy element regulacji sygnalizacji szlaku NFκB (Piryn: a new regulatory element of the NFκB
signaling pathway).
Sympozjum “Rola żelaza w organizmie”, Warszawa, Poland, 25.11.2006.
7. Chmielewski A.G.
Techniki i technologie jądrowe w zastosowaniach przemysłowych (Application of radiation and nuclear
technologies in industry).
Seminarium Naukowe “Technika jądrowa w służbie społeczeństwa”, Warszawa, Poland, 30.11.2006.
8. Chmielewski A.G., Kałuska I., Zimek Z., Migdał W., Bułka S.
Radiolytic decomposition of pesticide MCPA in various conditions – comparison of experimental data
and calculated kinetic model.
14th International Meeting on Radiation Processing, Kuala Lumpur, Malaysia, 26.02.-03.03.2006.
9. Chmielewski A.G., Migdał W., Zimek Z., Kałuska I., Bułka S.
Commercial application of an electrom beam accelerator at the R&D and service center.
14th International Meeting on Radiation Processing, Kuala Lumpur, Malaysia, 26.02.-03.03.2006.
10. Dembiński W.
Chemia materiałów paliwowych dla reaktorów jądrowych w “Nukleonice” (Chemistry of fuel materials
for nuclear reactors in “Nukleonika”).
Seminarium z okazji 50-lecia “Nukleoniki”, Warszawa, Poland, 30.06.2006.
11. Kałuska I.
Legislation and standardization concerning radiation sterilization process.
208
IAEA Course “Economical and Social Benefits of Radiation Processing; Standardization and Legislation
Issues Regarding Radiation Processing Implementation in Europe”, Eger, Hungary, 26.08.-02.09.2006.
12. Kałuska I.
Dose setting procedures for radiation deactivation and sterilization.
IAEA Course “Radiation Deactivation and Sterilization of Biohazards”, Vadodara, India, 28.10.-04.11.2006.
13. Kałuska I.
Physical, chemical and biological dose modifying factors.
14. Kałuska I.
Dosimetry systems for radiation processing.
15. Kałuska I.
Quality assurance in radiation processing.
16. Kruszewski M.
Białka żelazowo-siarkowe, nowe funkcje starych klastrów (Iron-sulphur cluster proteins, old pals with
new functions).
17. Męczyńska S.
Dinitrozylowe kompleksy żelaza: powstawanie i rola w organizmie (Dinitrosyl iron complexes: formation and the role in organisms).
18. Narbutt J.
Thermodynamics of solvent extraction of metal ions: fundamentals.
Fifth Half-yearly Meeting of EUROPART, Roma, Italy, 26-29.06.2006.
19. Narbutt J.
50 lat radiochemii w “Nukleonice” (50 years of radiochemistry in “Nukleonika”).
Seminarium z okazji 50-lecia “Nukleoniki”, Warszawa, Poland, 30.06.2006.
20. Sauerwein W., Malago M., Moss R., Wójcik A., Altieri S., Hampel G., Wittig A., Nievaart V.,
Collette L., Mauri P., Huiskamp R., Michel J., Daquino G., Gerken G., Bornfeld N., Broelsch C.E.
Boron neutron capture therapy (BNCT) for treating disseminated, non-resectable liver metastases.
International Workshop on Fast Neutron Therapy, Essen, Germany, 14-16.09.2006.
21. Wójcik A.
Aberacje chomosomowe i mikrojądra (Chromosomal aberrations and micronuclei).
Kurs Radiobiologii, Kielce, Poland, 20-23.03.2006.
22. Wójcik A.
Odczyny popromienne (Post-radiation early and late tissue injuries).
23. Wójcik A.
Hipoksja i jej rola w promieniowrażliwości guzów (Hypoxia and its role in tumor radiosensitivity).
24. Wójcik A.
Percepcja ryzyka dla zdrowia promieniowania jonizującego (Perception of ionizing radiation).
Letnia Szkoła Energetyki Jądrowej „Dunaj’06”, Warszawa, Poland, 06.04.2006.
25. Wójcik A., Bochenek A., Lankoff A., Lisowska A., Padjas A., von Sonntag C., Szumiel I., Obe G.
DNA interstrand crosslinks are induced in cells prelabelled with BrdU and exposed to UVC radiation.
35th Annual Meeting of European Radiation Research Society – European Radiation Research 2006,
Kiev, Ukraine, 22-25.08.2006.
26. Wójcik A., Sommer S., Deperas-Kaminska M., Moss R., Sauerwein W.
Effects of high LET (C-12) and low LET (Co-60) irradiation on chromosomal aberrations in peripheral
blood lymphocytes.
International Workshop on Fast Neutron Therapy, Essen, Germany, 14-16.09.2006.
209
27. Wójcik A., Wittig A., Sauerwein W.
What is the tolerance dose of the liver?
International Conference “Innovative Treatment Concepts for Liver Metastases”, Essen, Germany,
07-09.12.2006.
28. Zagórski Z.P.
Panspermia revisited?
Gordon Research Conference “Origin of Life”, Lewiston, Maine, USA, 23-28.07.2006.
Conditioning of biogas from biomass fermentation by membrane method.
7th Framework Programme in Poland, Warszawa, Poland, 16-17.11.2006.
30. Zimnicki R.
Sulphur isotopes ratio as a marker of pollutant migration in the ecosystem – opencast mine landfil.
2nd International Workshop “Pathways of pollutants from landfills to air and water-soil systems and
mitigation strategies of their impact on the ecosystems”, Kazimierz Dolny, Poland, 17-20.09.2006.
SEMINARS
1. Bilewicz A.
Radiofarmaceutyki (Radiopharmaceuticals).
Warsaw University, Poland, 16.05.2006.
2. Krzysztof Bobrowski
Stabilization of sulfide radical cations in linear and cyclic peptides containing methionine.
National Research Council (CNR), Institute for Organic Synthesis and Photoreactivity (ISOF), Bologna,
Italy, 24.02.2006.
Stabilization of sulfide radical cations: mechanisms relevant to oxidation of peptides and proteins containing methionine.
Swiss Federal Institute of Technology – ETH, Zurich, Switzerland, 23.03.2006.
Stabilization of sulfide radical cations: mechanisms relevant to oxidation of peptides and proteins containing methionine.
University Paris XI, Orsay, France, 12.05.2006.
Free radicals in chemistry, biology and medicine: contribution of radiation chemistry.
Universidad de Chile, Santiago de Chile, Chile, 13.11.2006.
Oxidation of methionine containing peptides: mechanism relevant to biological conditions of oxidative stress.
Universidad de Valparaiso, Chile, 20.11.2006.
Oxidation of methionine containing peptides: mechanism relevant to biological conditions of oxidative stress.
Universidad de Chile, Santiago de Chile, Chile, 22.11.2006.
8. Andrzej G. Chmielewski
Electron beam flue gas treatment – the basics.
University of Pavia, Italy, 08.05.2006.
Electron beam flue gas treatment – VOC and industrial applications.
Environmental protection - worldwide developments.
210
11. Adrian Jakowiuk
Bezprzewodowe sieci monitoringu z radioizotopowymi czujnikami zapylenia powietrza AMIZ-2004 (Wireless dust concentration monitoring network based on the radioisotope gauge AMIZ-2004).
International Ecological Fair POLEKO, Poznań, Poland, 23.11.2006.
12. Iwona Kałuska
Dozymetria procesów radiacyjnych (Dosimetry of radiation processes)
Poznań University of Medical Sciences, Poland, 15.03.2006.
13. Andrzej Wójcik
Popromienne aberracje chromosomowe: mechanizmy powstawania i biofizyczne modele, czyli badania
na pograniczu biologii i fizyki (Radiation induced chromosomal aberrations, on studies on the border of
biology and physics).
Warsaw University, Poland, 24.02.2006.
14. Andrzej Wójcik
Awaria reaktora w Czarnobylu: przyczyny i skutki (Accident of the Chernobyl reactor: causes and results).
Polskie Sieci Energetyczne, Warszawa, Poland, 24.04.2006.
15. Andrzej Wójcik
Czarnobyl 20 lat po: co wiemy o skutkach dla zdrowia? (Chernobyl 20 years after: what do we know about
the health effects?)
Świętokrzyska Academy, Kielce, Poland, 26.04.2006.
16. Andrzej Wójcik
20 lat po awarii w Czarnobylu: co dziś wiemy o skutkach zdrowotnych? (20 years after the Czernobyl
accident: what do we know today on the health effects?)
Świętokrzyska Academy, Kielce, Poland, 26.06.2006.
17. Andrzej Wójcik
Cytogenetic markers of individual radiation sensitivity.
Gesellschaft für Schwerionenforschung (GSI), Darmstadt, Germany, 25.10.2006.
18. Zbigniew Zimek
Electron beam flue gas treatment process.
Saudi Aramco, Dhahran, Saudi Arabia, 19.02.2006.
19. Zbigniew Zimek
High power electron accelerators for flue gas treatment.
Institute of Atomic Energy Research, King Abdulaziz City of Science and Technology, Riyadh, Saudi
Arabia, 20.02.2006.
20. Zbigniew Zimek
Akceleratory dla techniki jądrowej (Accelerators for nuclear power generation).
Polish Nuclear Society, Warszawa, Poland, 30.11.2006.
21. Zbigniew Zimek
Electron accelerators for radiation processing.
Office of Normalization and Metrology, Bratislava, Slovakia, 13.12.2006.
AWARDS IN 2006
211
AWARDS IN 2006
1.
Down-regulation of iron regulatory protein 1 activities and expression in superoxide dismutase 1 knock-out
mice is not associated with alterations in iron metabolism
Second degree group award of the Polish Genetic Society for the best work carried out in Polish
laboratories and published in 2005
R.R. Starzyński, P. Lipiński, J.-C. Drapier, A. Diet, E. Smuda, T. Bartłomiejczyk, M.A. Gralak,
M. Kruszewski
2.
Method for obtaining the Ni/NiO cathodes
Bronze medal at the 34th International Exhibition of Inventions, New Techniques and Products of Geneva,
Switzerland, 05-09.04.2006
W. Łada, A. Deptuła, T. Olczak, A.G. Chmielewski, A. Moreno
3.
Method for obtaining the Ni/NiO cathodes
Gold medal at the 55th World Exhibition of Innovation, Research and New Technology “Brussels Eureka
2006”, Belgium, 23-27.11.2006
W. Łada, A. Deptuła, T. Olczak, A.G. Chmielewski, A. Moreno
4.
Diploma of the Ministry of Education and Science for the project “Method for obtaining hollow spherical
particles from ceramic and metallic materials reduced by hydrogen”
A. Deptuła, A.G. Chmielewski, W. Łada, T. Olczak
5.
Congratulatory letter of the Ministry of Education and Science for the project “Method for obtaining
calcium phosphate layers, especially hydroxyapatite”
A. Deptuła, W. Łada, T. Olczak, R.Z. LeGeros, J.P. LeGeros
6.
Method for removal of nitrogen oxides from industrial gases. A facility for mixing gases reacting chemically. Method for removal volatile organic impurities such as polycyclic aromatic hydrocarbons from
industrial flue gases
Gold medal at the 55th World Exhibition of Innovation, Research and New Technology “Brussels Eureka
2006”, Belgium, 23-27.11.2006
A.G. Chmielewski
7.
Method for removal of nitrogen oxides from industrial gases. A facility for mixing gases reacting chemically. Method for removal volatile organic impurities such as polycyclic aromatic hydrocarbons from
industrial flue gases
Special award from the Russian Federal Agency for Science and Invention
A.G. Chmielewski
8.
First place for the meritorious poster “Application of extraction to the solid phase in the determination
of heavy metals by GF-AAS” presented at the XI Conference “Application of AAS, ICP-AES, ICP-MS
methods in the environmental analysis”, Warszawa, Poland, 09-10.11.2006
J. Chwastowska, W. Skwara, E. Sterlińska, J. Dudek, L. Pszonicki
9.
First degree group award of Director of the Institute of Nuclear Chemistry and Technology for two publications in “Talanta” presenting methods for the determination of platinum, palladium and chromium in
trace quantities in environmental samples and speciation analysis of Cr(VI) in the presence of Cr(III)
L. Pszonicki, J. Chwastowska, W. Skwara, E. Sterlińska
10. Second degree group award of Director of the Institute of Nuclear Chemistry and Technology for publications in the journals “Biochemical and Biophysical Research Communications”, “Journal of Biological
Chemistry” and “Acta Biochimica Polonica” devoted to studies of relations between the metabolism of
iron on a cell level and DNA oxidative damage
M. Kruszewski, H. Lewandowska, T. Bartłomiejczyk, T. Iwaneńko, B. Sochanowicz
11. Third degree group award of Director of the Institute of Nuclear Chemistry and Technology for the
essential contribution to the work on basic studies of secondary periodicity of elements of the block p
(group 13) published in “European Journal of Inorganic Chemistry”
S. Siekierski, K. Frąckiewicz
212
INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS
INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL
PILOT PLANTS
I.
DEPARTMENT OF NUCLEAR METHODS OF MATERIALS ENGINEERING
1. Laboratory of Materials Research
Activity profile: Studies of the structure and properties of materials and historical art objects. Modification of surface properties of materials by means of intense plasma pulses and ions beams. Synthesis and studies of new type of materials with predetermined properties (biocidal, fungicidal,
sorptional). Characterization of structural properties of materials using SEM (scanning electron
microscopy), X-ray fiffraction (powder and single crystal). Determination of elemental content of
environmental and geological samples, industrial waste materials, historic glass objects and other
materials by energy dispersive X-ray fluorescence spectrometry using a radioisotope excitation source
as well as a low power X-ray tube and using a 2 kW X-ray tube in total reflection geometry. Determination of radioactive isotope content in environmental samples and historical glass objects by
gamma spectrometry.
• Scanning electron microscope
DSM 942, LEO-Zeiss (Germany)
Technical data: spatial resolution – 4 nm at 30 kV, and 25 nm at 1 kV; acceleration voltage – up to 30 kV;
chamber capacity – 250x150 mm.
Application: SEM observation of various materials such as metals, polymers, ceramics and glasses.
Determination of characteristic parameters such as molecule and grain size.
• Scanning electron microscope equipped with the attachment for fluorescent microanalysis
BS-340 and NL-2001, TESLA (Czech Republic)
Application: Observation of surface morphology and elemental analysis of various materials.
• Vacuum evaporator
JEE-4X, JEOL (Japan)
Application: Preparation of thin film coatings of metals or carbon.
• Gamma radiation spectrometer
HP-Ge, model GS 6020; Canberra-Packard (USA)
Technical data: detection efficiency for gamma radiation – 60.2%, polarization voltage – 4000 V,
energy resolution (for Co-60) – 1.9 keV, analytical program “GENIE 2000”.
Application: Neutron activation analysis, measurements of natural radiation of materials.
•
Gamma spectrometer in low-background laboratory
EGG ORTEC
Technical data: HPGe detector with passive shield; FWHM – 1.9 keV at 1333 keV, relative efficiency – 92%.
•
Total reflection X-ray spectrometer
Pico TAX, Institute for Environmental Technologies (Berlin, Germany)
Technical data: Mo X-ray tube, 2000 W; Si(Li) detector with FHWM 180 eV for 5.9 keV line;
analysed elements – from sulphur to uranium; detection limits – 10 ppb for optimal range of analysed
elements, 100 ppb for the others.
Application: XRF analysis in total reflection geometry. Analysis of minor elements in water (tap, river,
waste and rain water); analysis of soil, metals, raw materials, fly ash, pigments, biological samples.
•
X-ray spectrometer
SLP-10180-S, ORTEC (USA)
Technical data: FWHM – 175 eV for 5.9 keV line, diameter of active part – 10 mm, thickness of active
part of detector – 5.67 mm.
Application: X-ray fluorescence analysis.
•
Coulter Porometer II
Coulter Electronics Ltd (Great Britain)
Application: Pore size analysis in porous media.
•
Vacuum chamber for plasma research
POLVAC Technika Próżniowa
213
Technical data: dimensions – 300x300 mm; high voltage and current connectors, diagnostic windows.
Application: Studies on plasma discharge influence on physicochemical surface properties of polymer
films, particularly TEM (track-etched membranes).
2. Laboratory of Diffractional Structural Research
Activity profile: X-ray diffraction structural studies on metal-organic compounds originating as degradation products of substances naturally occurring in the environment. Röntgenostructural phase
analysis of materials. Studies on interactions in a penetrant-polymer membrane system using small
angle scattering of X-rays, synchrotron and neutron radiation. Studies of structural changes occurring in natural and synthetic polymers under influence of ionising radiation applying X-ray diffraction and differential scanning calorimetry.
• KM-4 X-ray diffractometer
KUMA DIFFRACTION (Poland)
Application: 4-cycle diffractometer for monocrystal studies.
•
CRYOJET - Liquid Nitrogen Cooling System
Oxford Instruments
Application: Liquid nitrogen cooling system for KM-4 single crystal diffractometer.
•
HZG4 X-ray diffractometer
Freiberger Präzisionsmechanik (Germany)
Application: Powder diffractometers for studies of polycrystalline, semicrystalline and amorphous
materials.
•
URD 6 X-ray diffractometer
Freiberger Präzisionsmechanik (Germany)
Application: Powder diffractometers for studies of polycrystalline, semicrystalline and amorphous
materials.
3. Sol-Gel Laboratory of Modern Materials
Activity profile: The research and production of advanced ceramic materials in the shape of powders,
monoliths, fibres and coatings by classic sol-gel methods with modifications – IChTJ Process or by
CSGP (Complex Sol-Gel Method) are conducted. Materials obtained by this method are the following powders: alumina and its homogeneous mixtures with Cr2O3, TiO3, Fe2O3, MgO+Y2O3, MoO3,
Fe, Mo, Ni and CaO, CeO2, Y2O3 stabilized zirconia, β and β’’ aluminas, ferrites, SrZrO3, ceramic
superconductors, type YBCO (phases 123, 124), BSCCO (phases 2212, 2223), NdBa2Cu3Ox, their
nanocomposites, Li-Ni-Co-O spinels as cathodic materials for Li rechargeable batteries and fuel
cells MCFC, BaTiO3, LiPO4, Li titanates: spherical for fusion technology, irregularly shaped as
superconductors and cathodic materials, Pt/WO3 catalyst. Many of the mentioned above systems, as
well as sensors, type SnO2, were prepared as coatings on metallic substrates. Bioceramic materials
based on calcium phosphates (e.g. hydroxyapatite) were synthesized in the form of powders, monoliths and fibres.
• DTA and TGA thermal analyser
OD-102 Paulik-Paulik-Erdey, MOM (Hungary)
Technical data: balance fundamental sensitivity – 20-0.2 mg/100 scale divisions, weight range – 0-9.990 g,
galvanometer sensitivity – 1x10–10 A/mm/m, maximum temperature – 1050oC.
Application: Thermogravimetric studies of materials up to 1050oC.
•
DTA and TGA thermal analyser 1500
MOM (Hungary)
Technical data: temperature range – 20-1500oC; power requirements – 220 V, 50 Hz.
Application: Thermal analysis of solids in the temperature range 20-1500oC.
•
Research general-purpose microscope
Carl Zeiss Jena (Germany)
Technical data: General purpose microscope, magnification from 25 to 2500 times, illumination of
sample from top or bottom side.
•
Metallographic microscope
EPITYP-2, Carl-Zeiss Jena (Germany)
Technical data: magnification from 40 to 1250 times.
Application: Metallographic microscope for studies in polarized light illumination and hardness
measurements.
•
Laboratory furnace
CSF 12/13, CARBOLITE (Great Britain)
Application: Temperature treatment of samples in controlled atmosphere up to 1500oC with automatic adjustment of final temperature, heating and cooling rate.
214
II.
DEPARTMENT OF RADIOISOTOPE INSTRUMENTS AND METHODS
Laboratory of Industrial Radiometry
Activity profile: Research and development of non-destructive methods and measuring instruments
utilizing physical phenomena connected with the interaction of radiation with matter: development
of new methods and industrial instruments for measurement of physical quantities and analysis of
chemical composition; development of measuring instruments for environmental protection (dust
monitors, radon meters); implementation of new methods of calibration and signal processing (multivariate models, artificial neural networks); designing, construction and manufacturing of measuring instruments and systems; testing of industrial and laboratory instruments.
• Multichannel analyser board with software for X and γ-ray spectrometry
Canberra
•
Function generator
FG-513, American Reliace INC
III.
DEPARTMENT OF RADIOCHEMISTRY
1. Laboratory of Coordination and Radiopharmaceutical Chemistry
Activity profile: Preparation of novel technetium(I, III, V) complexes with chelating ligands (monoand bifunctional), labelled with 99mTc, as potential diagnostic radiopharmaceuticals or their precursors. Studying of their hydrophilic-lipophilic properties, structure and their interactions with
peptides. Also analogous rhenium(I) complexes are synthesised and studied. Novel platinum and
palladium complexes with organic ligands, analogs of cisplatin, are synthesised and studied as potential antitumor agents. Solvent extraction separation of trivalent actinides from lanthanides is
studied, directed towards nuclear waste treatment. Studies on chemical isotope effects of metal ions –
search of correlations between isotope separation factor and structure of species exchanging the
isotopes in two-phase chemical systems. (For the research equipment, common for both Laboratories,
see below.)
2. Laboratory of Heavy Elements
Activity profile: Synthesis of novel macrocyclic complexes of 47Sc, 103m,105Rh and 212Bi radionuclides –
potential precursors for therapeutic radiopharmaceuticals. Elaboration of new methods for
astatination (211At) of biomolecules via metal complexes. Design of new medically important radionuclide generators, e.g. 82Sr/82Rb, 103Ru/103mRh, 44Ti/44Sc. Structural studies on the complexes and
solvates of heavy p-block elements in the solid state and in solution.
• Spectrometric set
ORTEC
Multichannel analyser, type 7150, semiconductor detector
Application: Measurements and identification of γ- and α-radioactive nuclides.
•
Gas chromatograph
610, UNICAM (England)
Application: Analysis of the composition of mixtures of organic substances in the gas and liquid state.
•
High Performance Liquid Chromatography system
Gradient HPLC pump L-7100, Merck (Germany) with γ-radiation detector, INCT (Poland)
Application: Analytical and preparative separations of radionuclides and/or various chemical forms
of radionuclides.
•
High Performance Liquid Chromatography system
Gradient HPLC pump LC-10ADvp, with a UV-VIS detector SPD-10Avp/10AVvp, Shimadzu (Japan)
Application: Analytical and preparative separations of radionuclides and/or various chemical forms
of radionuclides.
•
Capillary electrophoresis system
PrinCE Technologies with a UV-VIS detector (Bischoff Lambda 1010) and a radiometric detector
Activity Gauge type Tc-99m (INCT, Poland)
Application: Analytical separation of various radiochemical and chemical species, in particular charged.
•
Gamma isotope TLC analyzer
SC-05 (INCT, Poland)
Application: Measurements of gamma radioactivity distribution along thin-layer-chromatography
plates and electrophoretic strips.
•
UV-VIS spectrophotometer
DU 68, Beckman (Austria), modernized and computerized
Application: Recording of electronic spectra of metal complexes and organic compounds in solution. Analytical determination of the concentration of these compounds.
215
•
FT-IR spectrophotometer
EQUINOX 55, Bruker (Germany)
Application: Measurements of IR spectra of metal complexes and other species in the solid state
and in solution.
IV.
DEPARTMENT OF NUCLEAR METHODS OF PROCESS ENGINEERING
1. Laboratory for Flue Gases Analysis
Activity profile: Experimental research connected with elaboration of removal technology for SO2
and NOx and other hazardous pollutants from flue gases.
• Ultrasonic generator of aerosols
TYTAN XLG
•
Gas chromatograph
Perkin-Elmer (USA)
•
Gas analyser LAND
Application: Determination of SO2, NOx, O2, hydrocarbons, and CO2 concentrations.
•
Impactor MARK III
Andersen (USA)
Application: Measurement of aerosol particle diameter and particle diameter distribution.
2. Laboratory of Stable Isotope Ratio Mass Spectrometry
Activity profile: Study of isotope ratios of stable isotopes in hydrogeological, environmental, medical and food samples.
• Mass spectrometer DELTAplus
Finnigan MAT (Bremen, Germany)
Technical data: DELTAplus can perform gas isotope ratio measurements of H/D, 13C/12C, 15N/14N,
18
O/16O, 34S/32S.
Application: For measurements of hydrogen (H/D) and oxygen (18O/16O) in water samples with two
automatic systems: H/Device and GasBench II. The system is fully computerized and controlled by
the software ISODAT operating in multiscan mode (realtime). The H/Device is a preparation system for hydrogen from water and volatile organic compounds determination. Precision of hydrogen
isotope ratio determination is about 0.5‰ for water. The GasBench II is a unit for on-line oxygen
isotope ratio measurements in water samples by “continuous flow” techniques. With GasBench II,
water samples (0.5 ml) can be routinely analyzed with a precision and accuracy of 0.05‰. The total
volume of water sample for oxygen and hydrogen determination is about 2 ml.
•
Elemental Analyzer Flash 1112 NCS
Thermo Finnigan (Italy)
Application: For measurement of carbon, nitrogen and sulfur contents and their isotope composition in organic matter (foodstuff and environmental samples).
•
Gas chromatograph mass spectrometer
GC MS-QP 5050A, GC-17A, Shimadzu (Japan)
Technical data: capillary column – SPB 5, HP-5MS, SUPELCOWAX™-10.
3. Radiotracers Laboratory
Activity profile: Radiotracer research in the field of: environmental protection, hydrology, underground water flow, sewage transport and dispersion in rivers and sea, dynamic characteristics of
industrial installations and waste water treatment stations.
• Heavy lead chamber (10 cm Pb wall thickness) for up to 3.7x1010 Bq (1 Ci) radiotracer activity
preparations in liquid or solid forms
• Field radiometers for radioactivity measurements
• Apparatus for liquid sampling
• Turner fluorimeters for dye tracer concentration measurements
• Automatic devices for liquid tracers injection
•
Liquid-scintillation counter
Model 1414-003 ”Guardian”, Wallac-Oy (Finland)
Application: Extra low-level measurements of α and β radionuclide concentrations, especially for H-3,
Ra-226, Rn-222 in environmental materials, e.g. underground waters, surface natural waters; in
other liquid samples as waste waters, biological materials, mine waters, etc.
216
4. Membrane Laboratory
Activity profile: Research in the field of application of membranes for radioactive waste processing,
separation of isotopes and gas separation.
• Membrane distillation plant for concentration of solutions
Technical data: output ~0.05 m3/h, equipped with spiral-wound PTFE module G-4.0-6-7 (SEP
GmbH) with heat recovery in two heat-exchangers.
•
•
Ultrafiltration plant equipped with replaceable ceramic multichannel modules
•
•
Laboratory stand with different ceramic replaceable tubular UF modules
US 150 laboratory stand (Alamo Water) for reverse osmosis tests
Technical data: working pressure – up to 15 bar, flow rate – 200 dm3/h, equipped with two RO modules.
Laboratory set-up for small capillary and frame-and-plate microfiltration and membrane distillation module examination (capillary EuroSep, pore diameter 0.2 μm and frame-and-plate the
INCT modules)
• The system for industrial waste water pretreatment
Technical data: pressure – up to 0.3 MPa; equipped with ceramic filters, bed Alamo Water filters
with replaceable cartridge (ceramic carbon, polypropylene, porous or fibrous) and frame-and-plate
microfiltration module.
• Gas separation system equipped with UBE capillary module
• Laboratory stand for pervaporation and vacuum membrane distillation tests
• Automatic refractometer
J357, Rudolph Technologies Inc. (USA)
Technical data: nD=1.29-1.70 , 0-95 BRIX.
• Spectrophotometer
HACH 2000 (Germany)
V.
DEPARTMENT OF RADIATION CHEMISTRY AND TECHNOLOGY
1. Laboratory of Radiation Modified Polymers
Activity profile: Modification of polymers by ionising radiation. Radiation-induced radicals in polymers. Optimization of mechanical and chemical properties of biocompatible materials following
electron beam and gamma irradiation, biological application of polymers. Nanocomposites and
nanofillers modified by ionising radiation.
• Extruder
PLV-151, BRABENDER-DUISBURG (Germany)
Technical data: Plasti-Corder consists of: driving motor, temperature adjustment panel, thermostat, crusher, mixer, extruder with set of extrusion heads (for foils, rods, sleevs, tubes), cooling tank,
pelleting machine, collecting device.
Application: Preparation of polymer samples.
•
Equipment for mechanical testing of polymer samples
INSTRON 5565, Instron Co. (England)
Technical data: high performance load frame with computer control device, equipped with Digital
Signal Processing and MERLIN testing software; max. load of frame is 5000 N with accuracy below
0.4% in full range; max. speed of testing 1000 mm/min in full range of load; total crosshead travel –
1135 mm; space between column – 420 mm; the environmental chamber 319-409 (internal dimensions 660x230x240 mm; temperature range – from -70 to 250oC).
Application: The unit is designed for testing of polymer materials (extension testing, tension,
flexure, peel strength, cyclic test and other with capability to test samples at low and high temperatures).
•
Viscosimeter
CAP 2000+H, Brookfield (USA)
Technical data: range of measurements – 0.8-1500 Pa*s, temperature range – 50-235oC, cone rotation speed – 5-1000 rpm, sample volume – 30 μl. Computer controlled via Brookfield CALPCALC®
software.
Application: Viscosity measurements of liquids and polymer melts.
•
Differential scanning calorimeter
MDSC 2920 CE, TA Instruments
Technical data: equipped with liquid nitrogen cooling adapter (LNCA) for 60 l of liquid nitrogen
and sample encapsulating press for open or hermetically sealed pans. Module for Modulated DSC™
is included. Working temperature – from -150oC with the LNCA to 725oC.
217
Application: Determines the temperature and heat flow associated with material phase transitions
as a function of time and temperature. It also provides quantitative and qualitative data on endothermic (heat absorption) and exothermic (heat evolution) processes of materials during physical transitions that are caused by phase changes, melting, oxidation, and other heat-related changes.
•
Processor tensiometer K100C
Technical data: supplied with the thermostatable sample vessel. Working temperature is from -10
to +100oC. The height of the sampler carrier is adjusted with the help of a high-precision motor.
The balance system is automatically calibrated by a built-in reference weight with a high precision.
Resolutions of measurement is 0.01 mN/m.
Application: Surface and interfacial tension measurement of liquids – Du Noüy Ring method and
Dynamic Wilhelmy method with range 1-1000 mN/m; dynamic contact angle measurements; surface energy calculations on solids, powders, pigments, fibers, etc.; sorption measurements with the
Washburn method for determining the surface energy of a powder-form solid. Controlled by
LabDesk™ software.
•
Spectrophotometer UV-VIS
UNICAM SP 1800 with linear recorder UNICAM AR 25
Technical data: Wavelength – 190-850 nm.
•
Equipment for gel electrophoresis
System consists of: horizontal electrophoresis apparatus SUBMINI Electrophoresis Mini-System,
transilluminator UV STS-20M JENCONS (United Kingdom), centrifuge EBA 12 Hettich/Zentrifugen, microwave oven KOR 8167 Daewoo.
•
Melt flow tester
ZWICK 4105, Zwick GmbH (Germany)
Technical data: temperature of measurements – 150, 190 and 230oC; press load – 2.16 and 5.00 kg;
manual operating.
Application: Determination of standard values of melt-mass flow rate (MFR) of the thermoplastic
materials (polymers) under specified conditions of temperature and load (according to standards:
PN-EN ISO 1133:2005, ASTM 1328); comparison of rheological properties of polymers, including
filled materials; comparison of degree of degradation; testing of catalogue data.
2. Radiation Sterilization Pilot Plant of Medical Devices and Tissue Grafts
Activity profile: Research and development studies concerning new materials for manufacturing
single use medical devices (resistant to radiation up to sterilization doses). Elaboration of monitoring systems and dosimetric systems concerning radiation sterilization processing. Introducing specific procedures based on international recommendations of ISO 13485:2003 and ISO 11137:2006
standards. Sterilization of medical utensils, approx. 70 million pieces per year.
• Electron beam accelerator
UELW-10-10, NPO TORIJ (Moscow, Russia)
Technical data: beam energy – 10 MeV, beam power – 10 kW, supply power – 130 kVA.
Application: Radiation sterilization of medical devices and tissue grafts.
•
Model U-1100, Hitachi
Technical data: wavelength range – 200-1100 nm; radiation source – deuterium discharge (D2) lamp,
and tungsten-iodine lamp.
•
Model SEMCO S/EC
Technical data: wavelength range – 340-1000 nm, radiation source – halogen lamp.
Application: Only for measurements of dosimetric foils.
•
Bacteriological and culture oven with temperature and time control and digital reading
Incudigit 80L
Technical data: maximum temperature – 80oC, homogeneity – ±2%, stability – ±0.25%, thermometer
error – ±2%, resolution – 0.1oC.
3. Laboratory of Radiation Microwave Cryotechnique
Activity profile: Radiation processes in solids of catalytic and biological importance: stabilization of
cationic metal clusters in zeolites, radical reactions in polycrystalline polypeptides, magnetic properties of transition metals in unusual oxidation states; radical intermediates in heterogeneous
catalysis.
• Electron spin resonance (ESR) Q-band spectrometer
Bruker E-500, equipped with continuous flow helium cryostat Oxford Instruments CF935 O and
DICE cw ENDOR/TRIPLE unit Bruker E-560 with rf amplifier 10 kHz-220 MHz.
218
•
Electron spin resonance (ESR) X-band spectrometer
Bruker ESP-300, equipped with: frequency counter Hewlett-Packard 5342A, continuous flow helium
cryostat Oxford Instruments ESR 900, continuous flow nitrogen cryostat Bruker ER 4111VT,
ENDOR-TRIPLE unit Bruker ESP-351.
Application: Studies of free radicals, paramagnetic cations, atoms and metal nanoclusters as well as
stable paramagnetic centers.
•
LAMBDA-9, Perkin-Elmer
Technical data: wavelength range – 185-3200 nm, equipped with 60 nm integrating sphere.
4. Pulse Radiolysis Laboratory
Activity profile: Studies of charge and radical centres transfer processes in thioether model compounds of biological relevance in liquid phase by means of time-resolved techniques (pulse radiolysis
and laser flash photolysis) and steady-state γ-radiolysis.
• Accelerator LAE 10 (nanosecond electron linear accelerator)
INCT (Warszawa, Poland)
Technical data: beam power – 0.2 kW, electron energy – 10 MeV, pulse duration – 7-10 ns and about 100
ns, repetition rate – 1, 12.5, 25 Hz and single pulse, pulse current – 0.5-1 A, year of installation 1999.
Application: Research in the field of pulse radiolysis.
•
Gas chromatograph
GC-14B, Shimadzu (Japan)
Specifications: two detectors: thermal conductivity detectors (TCD) and flame ionization detector
(FID). Column oven enables installation of stainless steel columns, glass columns and capillary
columns. Range of temperature settings for column oven: room temperature to 399oC (in 1oC steps),
rate of temperature rise varies from 0 to 40oC/min (in 0.1oC steps). Dual injection port unit with two
lines for simultaneous installation of two columns.
Application: Multifunctional instrument for analysis of final products formed during radiolysis of
sulphur and porphyrin compounds and for analysis of gaseous products of catalytic reactions in
zeolites.
•
Dionex DX500 chromatograph system
Dionex Corporation
Specifications: The ED40 electrochemical detector provides three major forms of electrochemical detection: conductivity, DC amperometry and integrated and pulsed amperometry. The AD20
absorbance detector is a dual-beam, variable wavelength photometer, full spectral capability is
provided by two light sources: a deuterium lamp for UV detection (from 190 nm) and a tungsten
lamp for VIS wavelength operation (up to 800 nm). The GP40 gradient pump with a delivery
system designed to blend and pump mixtures of up to four different mobile phases at precisely
controlled flow rates. The system can be adapted to a wide range of analytical needs by choice of
the chromatography columns: AS11 (anion exchange), CS14 (cation exchange) and AS1 (ion exclusion).
Application: The state-of-the-art analytical system for ion chromatography (IC) and high-performance liquid chromatography (HPLC) applications. Analysis of final ionic and light-absorbed products formed during radiolysis of sulphur compounds. The system and data acquisition are controlled
by a Pentium 100 PC computer.
•
Digital storage oscilloscope
6051A Wave Runner, LeCroy
Specifications: Bandwidth – 500 MHz; rise time – 750 ps; sample rate - up to 5 Gs/s (by combining
2 channels); acquisition memory – 16 Mpt with 8 Mpt per channel; sensitivity – 2 mV/div to 10 V/div;
fully variable, fully programmable; standard ports – 10/100Base-T Ethernet, Parallel, GPiB –IEEE
488.2, USB 2.0 (5), RS-232, SVGA Video Out, Audio in/out; Windows XP Professional operating
system.
Application: Digital storage oscilloscope (DSO) with high speed and long memory controls pulse
radiolysis system dedicated to the nanosecond electron linear accelerator (LAE 10). The multiple
time scales can be generated by a computer from a single kinetic trace originating from DSO since
the oscilloscope produces a sufficient number of time points (up to 16 M points record length).
•
9354AL, LeCroy
Specifications: Bandwidth DC to 500 MHz; sample rate – 500 Ms/s up to 2 Gs/s (by combining
4 channels); acquisition memory – up to 8 Mpt with 2 Mpt per channel; time/div range – 1 ns/div to
1000 s/div; sensitivity – 2 mV/div to 5 V/div; fully variable, fully programmable via GPIB and
RS-232C.
Application: Digital storage oscilloscope (DSO) with high speed and long memory controls pulse
radiolysis system dedicated to the nanosecond laser flash photolysis. The multiple time scales can
219
be generated by a computer from a single kinetic trace originating from DSO since the oscilloscope
produces a sufficient number of time points (up to 8 M points record length).
•
9304C, LeCroy
Specifications: Bandwidth DC to 200 MHz; sample rate – 100 Ms/s up to 2 Gs/s (by combining 4
channels); acquisition memory – up to 200 kpt per channel; time/div range – 1 ns/div to 1000 s/div;
sensitivity – 2 mV/div to 5 V/div; fully variable.
Application: Digital oscilloscope (DO) is used in pulse radiolysis system dedicated to the nanosecond electron linear accelerator (LAE 10).
•
Nd:YAG laser
Surelite II-10, Continuum (USA)
Specifications: energy (mJ) at 1064 nm (650), 532 nm (300), 355 nm (160) and 266 nm (80); pulse
width – 5-7 ns (at 1064 nm) and 4-6 ns (at 532, 355 and 266 nm); energy stability – 2.5-7%; can be
operated either locally or remotely through the RS-232 or TTL interface.
Application: A source of excitation in the nanosecond laser flash photolysis system being currently
under construction in the Department.
•
Potentiostat/Galvanostat VersaStat II
Princeton Applied Research (USA)
Specifications: Power amplifier compliance voltage single channel – ±20 V, maximum current –
±200 mA, rise time – 100 μs, slew rate – 1 V/μs; system performance: minimum timebase – 100 μs,
minimum potential step – 250 μV, noise and ripple <50 μV rms typically, minimum current range –
1 μA (hardware), minimum current range – 100 nA (software), minimum current resolution – 200
pA, drift – vs. time <50 μV/°C vs. time: <200 μV/week. iR compensation: current interrupt 12-bit
potential error correction total int. time <50-2000 μs. Accuracy: applied potential – 0.2% of reading ±2 mV, applied current – 0.2% of full-scale current. Computer interface: GPIB IEEE-488,
RS-232. Differential electrometer: input bias current <50 pA at 25°C, typically <20 pA at 25°C.
Max. voltage range – ±2 V, max. input voltage differential – ±10 V. Bandwidth – -3 dB at>4 MHz.
Offset voltage <100 μV. Offset temperature stability <5 μV/°C. Common mode rejection >70 dB
at 100 Hz and >60 dB at 100 kHz. Input impedance >1010 Ω, typically 1011 Ω in parallel with
<50 pF.
5. Research Accelerator Laboratory
Activity profile: Laboratory is equipped with accelerators providing electron beams which make
capable to perform the irradiation of investigated objects within wide range of electron energy from
100 keV to 13 MeV and average beam power from 0.1 W do 20 kW, as well as with Co-60 gamma
sources with activity 1.9x1010 to 1.3x1014 Bq and dose rate from 0.03 to 1.8 kGy/h. The described above
irradiators are completed in a unique in world scale set of equipment which can be applied in a wide
range of electron beam and gamma-ray research and radiation processing.
• Accelerator ILU-6
INP (Novosibirsk, Russia)
Technical data: beam power – 20 kW, electron energy – 0.7-2 MeV.
Application: Radiation processing.
•
Linear electron accelerator
LAE 13/9, Institute of Electro-Physical Equipment (Russia)
Technical data: electron energy – 10-13 MeV; electron beam power – 9 kW.
Application: Radiation processing.
•
Cobalt source I
Issledovatel (Russia)
Technical data: 32 sources with an actual activity of 9.2x1013 Bq.
Application: Radiation research.
•
Cobalt source II
Mineyola 1000, INR (Świerk, Poland)
Technical data: 8 rods with an initial activity of 2.66x1013 Bq; the actual activity is 1.07x1013 Bq.
Application: Radiation research.
•
Electron accelerator
AS-2000 (the Netherlands)
Technical data: energy – 0.1-2 MeV, max. beam current – 100 μA.
Application: Irradiation of materials.
•
Spectrometer
DLS-82E, SEMITRAP (Hungary)
Application: Research in radiation physics of semiconductors.
220
•
Argon laser
ILA-120, Carl Zeiss (Jena, Germany)
Application: Measurements of optical properties.
•
Spectrometer
DLS-81 (Hungary)
Application: Measurements of semiconductor properties.
•
Argon laser
LGN-503 (Russia)
Application: Measurements of optical properties.
VI.
DEPARTMENT OF ANALYTICAL CHEMISTRY
1. Laboratory of Spectral Atomic Analysis
Activity profile: atomic absorption and emission spectroscopy, studies on interference mechanisms,
interpretation of analytical signals, service analysis.
• Atomic absorption spectrometer
SH-4000, Thermo Jarrell Ash (USA); equipped with a 188 Controlled Furnace Atomizer (CTF 188),
Smith-Heftie background correction system and atomic vapor (AVA-440) accessory.
Application: For analyses of samples by flame and furnace AAS.
•
Atomic absorption spectrometer
SP9-800, Pye Unicam (England); equipped with SP-9 Furnace Power Supply, PU-9095 data graphics
system, PU-9095 video furnace programmer and SP-9 furnace autosampler.
•
Atomic absorption spectrometer
SOLAR M6 MK II (Thermo Electron Corporation), equipped with: graphite furnace GF 95 with
D2 and Zeeman background correction system, autosampler FS 95 and hydride and cold vapour
generator.
2. Laboratory of Neutron Activation Analysis
Activity profile: The sole laboratory in Poland engaged for 40 years in theory and practice of neutron activation analysis in which the following methods are being developed: reactor neutron activation analysis (the unique analytical method of special importance in inorganic trace analysis),
radiochemical separation methods, ion chromatography. The laboratory is also the main Polish
producer of CRMs and the provider for Proficiency Testing exercises.
• Laminar box
HV mini 3, Holten (Denmark)
Technical data: air flow rate 300 m3/h.
Application: Protection of analytical samples against contamination.
•
Ion chromatograph
2000i/SP, Dionex (USA)
Technical data: data evaluating program AI-450, ion exchange columns of type Dionex Ion Pac,
conductivity detector, UV/VIS detector.
Application: Analyses of water solutions, determination of SO2, SO3 and NOx in flue gases and in
air, determination of metals in biological and environmental samples.
•
HPGe detector, well-type
CGW-3223, Canberra, coupled with analog line (ORTEC) and multichannel gamma-ray analyzer
TUKAN
Application: Instrumental and radiochemical activation analysis.
•
Coaxial HPGe detector
POP-TOP, ORTEC (USA), coupled with analog line (ORTEC) and multichannel gamma-ray analyzer TUKAN
•
HPGe detector, well-type
CGW-5524, Canberra, coupled with multichannel gamma-ray analyzer (hardware and software)
Canberra
Application: Instrumental and radiochemical activation analysis.
• Analytical balance
Sartorius BP2 215
Application: For weighing sample of mass >10 mg to 220 g.
221
• Analytical micro-balance
Sartorius MC5
Application: Preparation of mono- and multi-elemental standards as well as for weighing small
mass samples, less than 10 mg.
• Balance
WPX 650, RADWAG (Poland)
Application: For weighing sample of mass >10 mg to 650 g.
•
Liquid Scintillation Analyzer
TRI-CARB 2900TR, Packard BioScience Company
Application: α- and β-ray measurements.
•
Planetary Ball Mill
PM 100, Retsch
Application: Grinding and mixing: soft, medium hard to extremly hard, brittle or fibrous materials.
•
Balance-drier
ADS50, AXIS (Poland)
Application: Determination of mass and humidity of samples.
•
Microwave digestion system
UnicleverTMII, PLAZMATRONIKA (Poland)
Application: Microwave digestion of samples.
•
Microwave digestion system
BM-1S/II, PLAZMATRONIKA (Poland)
Application: Microwave digestion of samples.
•
Homogenizer
INCT (Poland)
Application: Homogenization of the material used for preparation of CRMs.
•
Peristaltic pump
REGLO ANALOG MS-4/6-100, ISMATEC (Switzerland)
Application: Regulation of flow of eluents during elution process.
3. Laboratory of Chromatography
Activity profile: Development of HPLC methods for determination of environmental pollutants,
application of HPLC and ion-chromatography monitoring of degradation organic pollutants in waters
and wastes using ionizing radiation, development of chromatographic methods, preconcentration
of organic environmental pollutants, development of chromatographic methods of identification of
natural dyes used for ancient textiles.
• Apparatus for biological oxygen demand determination by respirometric method and dissolved
oxygen measurement method
WTW-Wissenschaftlich-Technische Wersttätten (Germany)
Application: Analyses of water and waste water samples.
•
Apparatus for chemical oxygen demand determination by titrimetric method
Behr Labor-Technik (Germany)
•
Set-up for solid phase-extraction (vacuum chamber for 12 columns and vacuum pump)
•
Shimadzu HPLC system consisting of: gradient pump LC-10AT, phase mixer FCV-10AL, diode-array detector SPD-M10A, column thermostat CTO-10AS
Application: Analyses of natural dyes, radiopharmaceuticals, water and waste water samples.
•
Laboratory ozone generator
301.19, Erwin Sander Elektroapparatebau GmbH (Uetze-Eltze, Germany)
Application: Ozone production for degradation of pollutants in waste water samples.
4. Laboratory of General Analysis
Activity profile: Preparation and application of new chelating sorbents to the separation of metal
traces from environmental materials for their determination by atomic absorption spectrometry,
speciation analysis, service analysis.
• Spectrophotometer
PU8625 Series UV/Visible, Philips
Technical data: wavelength range – 200-1100 nm.
Application: Measurements of absorbance in spectrophotometric analysis.
222
•
Spectrophotometer
UV-160, Shimadzu (Japan)
Technical data: wavelength range – 200-1100 nm, with automatic baseline correction and graphic printer.
Application: Routine spectrophotometric analysis and research works.
VII. DEPARTMENT OF RADIOBIOLOGY AND HEALTH PROTECTION
•
Equipment for electrophoretic analysis of DNA
CHEF III, BIO-RAD (Austria)
Application: Analysis of DNA fragmentation as a result of damage by various physical and chemical agents.
•
Microplate reader
ELISA, ORGANON TEKNICA (Belgium)
Application: For measurement of optical density of solutions in microplates.
•
Hybridisation oven
OS-91, BIOMETRA (Germany)
Technical data: work temperatures from 0 to 80oC; exchangeable test tubes for hybridisation.
Application: For polymerase chain reaction (PCR).
•
Spectrofluorimeter
RF-5000, Shimadzu (Japan)
Application: For fluorimetric determinations.
•
Transilluminator for electrophoretic gels
Biodoc, BIOMETRA (Great Britain)
Application: For analysis of electrophoretic gels.
•
Laminar flow cabinet
NU-437-400E, Nu Aire (USA)
Application: For work under sterile conditions.
•
Liquid scintillation counter
LS 6000LL, BECKMAN (USA)
Application: For determinations of radioactivity in solutions.
•
Research microscope universal
NU, Carl Zeiss Jena (Germany)
Application: For examination of cytological preparations.
Comments: Universal microscope for transmission and reflected light/polarised light. Magnification from 25x to 2500x. Possibility to apply phase contrast.
•
Incubator
T-303 GF, ASSAB (Sweden)
Technical data: 220 V, temperature range – 25-75oC.
Application: For cell cultures under 5% carbon dioxide.
•
Incubator
NU 5500E/Nu Aire (USA)
Technical data: 220 V, temperature range from 18 to 55oC.
Application: For cell cultures under 0-20% carbon dioxide.
•
Laminar flow cabinet
V-4, ASSAB (Sweden)
Application: For work under sterile conditions.
•
Image analysis system
Komet 3.1, Kinetic Imaging (Great Britain)
Application: For comet (single cell gel electrophoresis) analysis.
•
ISIS 3
Metasystem (Germany)
Application: Microscopic image analysis system for chromosomal aberrations (bright field and fluorescence microscopy).
VIII. LABORATORY FOR DETECTION OF IRRADIATED FOOD
Activity profile: Detection of irradiated foods. European standards (CEN) adapted as analytical
methods to be routinely used in the Laboratory, are based on electron paramagnetic resonance
(EPR/ESR) spectroscopy, pulsed photostimulated luminescence (PPSL) and thermoluminescence
measurements (TL). The research work is focused mainly on the development of the above three
223
methods and the enlargement of their ability of the detection of irradiation in the variety of foodstuffs. Laboratory is capable to examine food samples by the DNA comet assay (decomposition of
single cell) and statistical germination study. The quality assurance system was adapted in the Laboratory in 1999 and in 2006 was actualised and documented in agreement with the PN-EN 1SO/IEC
17025:2005 standard. Actually Laboratory possesses Accreditation Certificate of Testing Laboratory nr AB 262 issued by the Polish Centre for Accreditation and valid until 24.10.2010.
• Thermoluminescence reader
TL-DA-15 Automated, Risoe National Laboratory (Denmark)
Technical data: turntable for 24 samples, heating range – 50÷500oC, heating speed – 0.5÷10.0oC/s,
optical stimulated luminescence (OSL) system.
Application: Detection of irradiated foods containing silicate minerals, e.g. spices, vegetables shrimps
tc, research work on irradiated foods.
•
Fluorescence microscope
OPTIPHOT Model X-2, NIKON (Japan)
Technical data: halogen lamp 12 V-100 W LL; mercury lamp 100 W/102 DH; lenses (objectives)
CF E Plan Achromat 4x, CF E Plan Achromat 40x, CF FLUOR 20x.
Application: Detection of irradiated foods by the DNA comet assay method, research work on
apoptosis in mammalian cells, biological dosimetry, analysis of DNA damage in mammalian cells.
•
Compact EPR spectrometer
EPR 10-MINI, St. Petersburg Instruments Ltd. (Russia)
Technical data: sensitivity – 3x1010, operating frequency (X band) – 9.0-9.6 GHz, max. microwave
power – 80 mW, magnetic field range – 30-500 mT, frequency modulation – 100 kHz.
Application: Detection of irradiated foods, bone and alanine dosimetry, research work on irradiated foods and bone tissues.
•
Pulsed photostimulated luminescence system
SURRC (United Kingdom)
Technical data: pulsed light source – diodes IR LED; detector – photomultiplier ETL; pulse on and
off periods – 15 μs; sample holder – 50 mm diameter disposable Petri dishes; set up – sample chamber
and detector head assembly, contol unit, on line computer, optional.
Application: Irradiated food screening system.
IX.
EXPERIMENTAL PLANT FOR FOOD IRRADIATION
1. Microbiological Laboratory
Activity profile: optimization of food irradiation process by microbiological analysis.
• Sterilizer
ASUE, SMS (Warszawa, Poland)
Application: Autoclaving of laboratory glass, equipment, and microbiological cultures.
•
Fluorescence microscope
BX, Olimpus (Germany)
Application: Quantitative and qualitative microbiological analysis.
2. Experimental Plant for Food Irradiation
Activity profile: Development of new radiation technologies for the preservation and hygienization
of food products. Development and standarization of the control system for electron beam processing of food. Development of analytical methods for the detection of irradiated food. Organization of
consumer tests with radiation treated food products.
• Accelerator ELEKTRONIKA (10 MeV, 10 kW)
UELW-10-10, NPO TORIJ (Moscow, Russia)
Application: Food irradiation.
224
A
Aleshkevych Pavlo 151
Antunes Ines 67
Anuszewska Elżbieta 77
B
Barański Marek 151
Barcz Adam 141
Barlak Marek 141
Bartak Jakub 156
Bartłomiejczyk Teresa 101
Bartoś Barbara 67
Basfar Ahmed A. 117
Bilewicz Aleksander 67, 69, 70
Bobrowski Krzysztof 19, 21, 22
Bojanowska-Czajka Anna 52
Borowiec Mieczysław T. 151
Brykała Marcin 147, 151
Brzozowska Kinga 104
Brzóska Kamil 99
Buczkowski Marek 145
Bulska Ewa 81
Bułka Sylwester 114, 118, 161
Buraczewska Iwona 109
C
Celuch Monika 25, 27
Chajduk Ewelina 82, 85
Chatgilialoglu Chryssostomos 21
Chmielewska Dagmara K. 141, 153
Chmielewski Andrzej G. 42, 114, 115, 117, 120,
125, 126, 161
Chwastowska Jadwiga 89, 147
Cieśla Krystyna 44, 47, 49
Cojocaru Cornel 121
Cuna Stela Maria 113
D
Danko Bożena 85
Dąbrowski Ludwik 141
Dembiński Wojciech 81
Deperas Joanna 103
Deperas-Kaminska Marta 103, 105
Deptuła Andrzej 147, 151
Derda Małgorzata 113, 123, 126
Dłuska Ewa 121
Dobrowolski Andrzej 125
Domuchowski Wiktor 151
Drzewicz Przemysław 52
Dudek Jakub 82, 89
Dyakonov Vladimir P. 151
Dybczyński Rajmund 73, 85
Dziedzic-Gocławska Anna 30
Dzierżanowski Piotr 134, 136
Dźwigalski Zygmunt 163
E
Edwards Alan 103
Eliasson Ann-Charlotte 47
Enache Mirela 25, 27
F
Ferreri Carla 21
Filipiuk Dorota 79
Fuente Julio R. De la 22
Fuks Leon 77, 79
G
Głuszewski Wojciech 39, 41, 49
Gniazdowska Ewa 159
Goretta Kenneth C. 147
Govindarajan Subbian 93
Grądzka Iwona 106
Grigoriew Helena 153
Grodkowski Jan 23
Gruber Bożena 77
Gryczka Urszula 42
Gryz Michał 91, 92, 96
Guzik Grzegorz P. 56, 63
H
Harasimowicz Marian 120, 121
Herdzik Irena 81
Houée-Levin Chantal 19
I
Iwaneńko Teresa 100, 101, 102
J
Jaworska Agnieszka 121
Jurczyk Renata 119
K
Kalinowska Justyna 141
Kałuska Iwona 161
Kamiński Artur 30
Kciuk Gabriel 22
Kempers Alexander J. 126
Kierzek Joachim 134
Kocia Rafał 23
Kopcewicz Michał 141, 142
Kornacka Ewa M. 36
Kosior Grzegorz 126
Kowalska Ewa 67, 159
Kozakiewicz Janusz 36
Krasavin Eugene A. 105
Krejzler Jadwiga 75
Królak Edward 49
Kruszewska Hanna 77
Kruszewski Marcin 99, 100, 101, 102, 107
Kulisa Krzysztof 85
Kunicki-Goldfinger Jerzy 134, 136
L
Laubsztejn Magdalena 60, 63
Leciejewicz Janusz 91, 92, 93, 94, 96
Lehner Katarzyna 58, 63
Lewandowska Hanna 99
Licki Janusz 115, 117
Lindholm Carita 103
Lloyd David 103
Lundqvist Henrik 47
225
P
Palige Jacek 124, 125
Pańczyk Ewa 128, 130
Pawelec Andrzej 117
Pawlukojć Andrzej 94
Piekoszewski Jerzy 141, 142
Pieńkos Jan 158, 159, 160
Pogocki Dariusz 25, 27
Polkowska-Motrenko Halina 82, 85
Premkumar Thatan 93
Pruszyński Marek 69
Przybylski Jarosław 36
Przybytniak Grażyna 33, 36
Pszonicki Leon 89
Ptaszek Sylwia 125
R
Rahier Hubert 44
Ratajczak Renata 142
Romm Horst 103
Roy Laurence 103
Ł
S
Łada Wiesława 147, 151
Łukasiewicz Andrzej 141
Łyczko Monika 71, 73
Sadlej-Sosnowska Nina 77
Sadło Jarosław 27, 28, 30, 99
Sadowska-Bratek Monika 82
Samczyński Zbigniew 73, 85
Samecka-Cymerman Aleksandra 126
Sartowska Bożena 49, 130, 141, 142, 144, 145, 147
Serdiuk Katarzyna 27
Skarnemark Gunnar 67
Skwara Witold 81, 89
Sobarzo-Sanchez Eduardo 22
Sochanowicz Barbara 99, 106, 108
Sołtyk Wojciech 124
Sommer Sylwester 109
Stachowicz Wacław 56, 58, 60, 63
Stanisławski Jacek 141, 142
Starosta Wojciech 42, 91, 92, 93, 94, 96, 145
Sterlińska Elżbieta 89, 147
Strzelczak Grażyna 30, 60
Sun Yongxia 114
Sypuła Michał 82, 85
Szłuińska Marta 103
Szopa Zygmunt 85
Szostek Bogdan 52
Szumiel Irena 106, 107, 108
Szymczak Henryk 151
M
Machaj Bronisław 156, 159
Mádl Martin 136
Majdan Marek 79
Majkowska Agnieszka 67, 70
Malec-Czechowska Kazimiera 60, 63
Mehta Kishor 118
Męczyńska Sylwia 99
Michalik Jacek 28, 30
Migdał Wojciech 42, 161
Mirkowski Jacek 19, 23
Mirkowski Krzysztof 33
Mirowicz Jan 158
Miśkiewicz Agnieszka 121
Morand Josselin 103
Moss Raymond 103
Mozziconacci Olivier 19, 21
N
Narbutt Jerzy 71, 73, 75
Natkaniec Ireneusz 94
Neves Maria 67
Nichipor Henrietta 52, 114
Nowak Dorota 94
Nowicki Andrzej 33, 144
Nowicki Lech 142
O
Olczak Tadeusz 147, 151
Olszewska-Świetlik Justyna 128
Orelovitch Oleg 144
Ostapczuk Anna 115
Ś
Świstowski Edward 158, 159
T
Timoshenko Gennady N. 105
Trojanowicz Marek 52
Turek Janusz 28
Tymiński Bogdan 117, 119
U
Urbański Piotr 156, 158, 160
226
W
Z
Walendziak Jolanta 124
Waliś Lech 128, 130, 141, 142
Wawszczak Danuta 145, 147, 151
Werner Zbigniew 141
Wierzchnicki Ryszard 113, 123, 126
Wojewódzka Maria 100, 101, 102, 107
Woliński Jarosław 100, 101, 102
Wójcik Andrzej 103, 104, 105, 109
Wroński Stanisław 121
Wysocka Agnieszka 81
Zabielski Roman 101, 102
Zagórski Zbigniew P. 31, 39, 41
Zakrzewska-Trznadel Grażyna 120, 121
Zalutsky Michael R. 69
Zayarnyuk Tetyana 151
Zimek Zbigniew 33, 52, 114, 117, 161, 163
Zimnicki Robert 124
Ziółkowska Weronika 120
Zwoliński Krzysztof 119

- Instytut Chemii i Techniki Jądrowej

Transcription

Similar documents

Report on Scientific Meets on “Radiation and Cancer”

World Youth Day

Radiation Therapy

RadPro International GmbH i

How to Tie a Woggle

lnstallation - ConservationMart.com

radiactividad natural

Your guide to the ACS national meeting in Philly

Dockside Radiation Monitoring System

The Benign Hamburger - National Center for Case Study Teaching