Bimetallic catalysts are widely used in catalysis in the

Transcription

7th JFIC -GIFC, Turin, Italy, May 5th-6th, 2014
VII Giornate Italo-Francesi di Chimica
7èmes Journées Franco-Italiennes de Chimie
Torino
5-6 maggio/mai 2014
Università di Torino
Le sezioni del Piemonte-Valle d'Aosta e della Liguria della Societá Chimica Italiana e
la sezione PACA (Provenza, Alpi e Costa Azzurra) della Societá Chimica Francese, organizzano a Torino nei giorni 5 e 6 maggio 2014 la settima edizione delle Giornate ItaloFrancesi di Chimica.
La manifestazione, che ha cadenza biennale ed è organizzata alternativamente dai due
Paesi, si è precedentemente svolta a Juan-les-Pins (2002), Genova (2004), Torino (2006),
Nizza (2008), Genova (2010) e Marsiglia (2012).
Le GIFC hanno un carattere interdisciplinare e hanno favorito un rapporto di confronto
durevole tra ricercatori delle regioni italiane Liguria, Piemonte e Valle d'Aosta e quelli della regione francese Provenza, Alpi e Costa Azzurra, con l’obiettivo di instaurare una sempre più stretta integrazione scientifica e culturale.
Gli argomenti dei Convegno riguardano tutti i settori della chimica, in particolare la
chimica organica, inorganica, bio-organica, fisica, analitica, farmaceutica, dell'ambiente, dei
materiali e industriale. Inoltre, data la ricorrenza dell’Anno Internazionale della Cristallografia, verrà dato particolare rilievo all’aspetto strutturistico dei materiali studiati nelle
varie discipline.
Ringraziamo tutti gli enti patrocinatori e gli sponsors per avere contribuito al successo
delle VII Giornate Italo-Francesi di Chimica.
Il comitato organizzatore
Les sections Ligurie et Piémont-Val d'Aoste de la Società Chimica Italiana en collaboration avec la section PACA de la Société Chimique de France, organisent à Turin les 5 et 6
mai 2014, la septième édition des Journées Franco-Italiennes de Chimie.Ces journées ont
un caractère interdisciplinaire et ont établi un contact durable entre les chercheurs de la
région Provence-Alpes-Côte d'Azur et ceux des régions de la Ligurie et du Piémont-Vallée
d'Aoste, dans le but d'une intégration toujours plus étroite, au niveau européen tant au
niveau scientifique que culturel.
Cet événement , qui a lieu tous le deux ans et qui est organisé par le deux pays en alternance, a eu lieu en 2002 à Juan-les-Pins, en 2004 à Gêne, en 2006 à Turin, en 2008 à Nice,
en 2010 à Gêne et en 2012 à Marseille.
Ces journées ont un caractère interdisciplinaire et ont soutenu une relation d’échange
durable entre les chercheurs de la Ligurie, du Piémont e de la Val d’Aoste et ceux de la
région Provence-Alpes-Côte d’Azur, dans l’objective d’instaurer une intégration scientifique et culturelle toujours plus étroite.
Les contenus concernent tous les secteurs de la chimie, notamment la chimie organique
et bio-organique, la chimie physique et inorganique, la chimie analitique et pharmaceutique, la chimie de l’environnement, la chimie industrielle et des matériaux. En outre, à
l’occasion de l’Année internationale de la Cristallographie, on mettra en particulier relief
l’aspect structurale des matériaux étudiés dans les différentes disciplines.
Nous remercions tous les organismes et les sponsors qui ont contribué au succès des
VIIme Journées Franco-Italiennes de Chimie.
Le comité d'organisation
Comitato Scientifico /Comité Scientifique
Vito Boido, Università degli Studi di Genova
Giorgio Cevasco, Università degli Studi di Genova
Thierry Constantieux, Aix-Marseille Université – CNRS
Elisabet Dunach, Université de Nice Sophia Antipolis
Philippe Knauth, Aix-Marseille Université – CNRS
Valter Maurino, Università degli Studi di Torino
Lorenza Operti, Università degli Studi di Torino
Mauro Ravera, Università degli Studi del Piemonte Orientale
Comitato Organizzatore/ Comité d’Organisation
Eliano Diana, Università degli Studi di Torino
Enrico Boccaleri, Università degli Studi del Piemonte Orientale
Edoardo Garrone, Politecnico di Torino
Marta Giorgis, Università degli Studi di Torino
Maela Manzoli, Università degli Studi di Torino
Marco Minella, Università degli Studi di Torino
Alessandro Trosa, Ordine dei Chimici del Piemonte-Valle d'Aosta
Marco Pazzi, Universita' degli Studi di Torino
Lunedì 5 maggio
8.30-8.15
Accoglienza
9.15-9.30
Apertura e saluti
9.30-10.15
T. S. Balaban
Supramolecular chirality with porphyrins
10.15-10.30
C. Iacobucci
A quantitative approach of the interaction be- COM1
tween metal triflates and organic ligands using
electrospray mass spectrometry
10.30-10.45
V. Marotta
Experimental and thermodynamic study of the COM2
conversion of mixtures with methane up to 1700°C
10.45-11.00
M. Cocco
Use of the Morita-Baylis-Hillman reaction in the COM3
design of compounds inhibiting NLRP3 inflammasome signaling pathways
11.00-11.30
Pausa caffè e affissione poster (P1-P60)
11.30-12.00
M. Milanesio
The 2nd century of moderm crystallography: from INV1
nano and disordered crystal structures to solidstate reactivity
12.00-12.15
A.Taoufyq
Elaboration and microstructural studies of lumi- COM4
nescent materials based on Ca0.5Cd 0.5WO4 tungstate phases
12.15-12.30
M. I. Martinez Polymerization studies of a novel ammonium- COM5
Espinoza
functionalizated diacetylene self-assembled on
metal nanoparticles.
12.30-12.45
E. Gabano
New Pt(IV) antitumour prodrugs for drug target- COM6
ing and delivery strategies
12.45-13.00
M. Cong
The first mixed ligand Pd-catalyzed C-S coupling: COM7
a highly effective strategy for synthesizing Sarylthioheteroaryl derivatives
13.00-14.30
Pranzo e sessione poster
14.30-15.15
G. Martra
PLE1
Molecular resolution studies of the surface struc- PLE2
ture of nanomaterials by combining experimental
and theoretical investigations
15.15-15.30
G. Fenoglio
Improving portable-XRF analyses on medieval COM8
Limoges enames: opacifiers control in leadbearing glasses.
15.30-15.45
E. Fedeli
Synthesis of cellulose acetate grafted polystyrene COM9
copolymers via nitroxidemediated polymerization
15.45-16.00
E. Tassano
Polyphenols recovery from olive mill waste waters COM10
(OMWW) and synthesis of unusual hydroxytyrosol
derivatives.
16.00-16.15
P. Boulet
Design of open carbon framework structures: a COM11
search for hydrogen adsorbents
16.15-16.30
C. Magistris
Conjugation of bioactive glasses with organic COM12
molecules: a model for the development of new
stimuli-responsive biomaterials for bone tumour
treatment
16.30-17.00
Pausa caffè e sessione poster
17.00-17.30
S. Antonczak
Modelling of a metabolon involved in flavonoid INV2
biosynthesis: theoretical strategies
17.30-17.45
I.Notar
Francesco
Reactivity studies of nanocatalysts under mild COM13
conditions: tandem 1,6-enynes thioacylation / cyclisation with gold and gold-palladium alloy nanoparticles
17.45-18.00
M. Massa
3-Cyclopentyloxy-4-methoxyphenyl-isoxazoline
derivatives as new PDE4 inhibitors
18.00-18.15
A. Masala
CO2 capture and activation in functionalized mi- COM15
croporous materials
18.15-18.30
S. Andjouh
Synthesis and antibiofilm activity of bromotyra- COM16
mines analogues
20.30
Cena sociale
TOP club (www.topclub.playdance.tv)
Adresse: Corso Moncalieri 145, Turin
Martedì 6 maggio
8.30-9.00
Affissione poster (P61-P127)
COM14
9.00-9.50
Grand prix :
H. Tachoire
Scientific teaching and research in Provence: from PLE3
the century of enlightenment to the University of
Aix Marseille
9.55-10.10
R. Di Legami
Novel size- and shape-controlled silica nanofillers COM17
for tires reinforcement
10.10-10.25
J. Botton
AFM Catalysis: focus on spatially resolved surface COM18
functionalization
10.25-10.40
E. Alladio
Chemometric and experimental design approach- COM19
es to open validation protocols. Prediction of validation parameters in multi-residue UHPLCMS/MS methods
10.40-11.10
11.10-11.40
L. Feray
Organometallic-promoted radical-polar cascades INV3
in aerobic medium
11.40-12.00
Prix doctorand:
Energy storage and conversion at the nanoscale
12.00-12.15
L. Assaud
L. Tei
12.15-12.30
D. Fernand
Towards new mesoporous nanomaterials targeted COM22
for biological applications: Sensing of low dose
molecules by SERS effect
12.30-12.45
E. Meta
Development of imidazo-pyrazole derivatives as COM23
potential antimetastatic agents in neuroblastoma
12.45-13.00
A. Felouat
Synthesis and photophysical studies of new boron COM24
difluoride complexes of β-diketonates ligands with
extended conjugation
13.00-14.30
Pranzo e sessione poster
14.30-15.00
C. Artini
Diamond cutting tools: technological issues and INV4
interfacial reactivity
15.00-15.15
P. Ivanchenko
“What the cells see”: factors affecting the orienta- COM25
tion of proteins adsorbed on hydroxyapatite nanoparticles
15.15-15.30
C. A. de March
The human OR1G1 olfactory receptor is involved COM26
in the combinatorial code of β-santalol
COM20
Synthetic approaches to the design of efficient MRI COM21
probes
15.30-15.45
M. Spallarossa
Enantio- and diastereoselective synthesis of highly COM27
substituted benzazepines by a multicomponent
strategy coupled with organocatalytic and enzymatic procedures
15.45-16.00
I. Diaf
Metal triflate-catalysed synthesis of polycyclic ter- COM28
tiary alcohols by cyclisation of γ-Allenic ketones
16.00-16.30
16.30-17.00
A. Spallarossa
(Acyl)thiocarbamates, disulfides and enamines as INV5
novel non-nucleoside HIV-1 reverse transcriptase
inhibitors
17.00-17.15
P. Boggio
Synthetic strategies for the preparation of lipo- COM29
philic MRI/GdBNCT agents
17.15-17.30
A. Toumi
Solid phase photochemistry of acrylonitrile for COM30
titan-like conditions simulated in laboratory
17.30-17.45
C. Sauvée
DNP enhanced NMR spectroscopy: design and syn- COM31
thesis of water-soluble stable free radicals as polarizing agents
17.45-18.00
Chiusura del convegno
Conferenze Plenarie
Conférences Plénières
PLE1
Supramolecular Chirality with Porphyrins
Teodor Silviu Balaban
Aix Marseille Université, CNRS UMR 7313, Institut des Sciences Moléculaires de Marseille, Chirosciences,
Avenue Escadrille Normandie Niemen, Service 442, F-13397 Marseille CEDEX 20, France.
E-mail : [email protected]
Keywords: chirosciences, self-assembly, molecular recognition, symmetry
Chirality is a fascinating property of matter spanning scales from molecules to galaxies brought about by
the non-superimposition of an object with its mirror image. In Marseille, within the Team Chirosciences we have
studied various porphyrins equipped with recognition groups capable of inducing spontaneous self-assembly triggered by certain stimuli and change in the external conditions, such as solvent polarity, temperature and/or pH.
We,[1] as well as other groups,[2-5] are interested at how occurs the transfer of molecular chirality to the
supramolecular level, that is from the nano- to the microscale, especially if this involves a nucleation event followed by chiral amplification, which is still a poorly understood phenomenon.
We will present recent examples of porphyrins equipped either (i) with an atropisomeric recognition
group,[6] (ii) with the phenylalanine-phenylalanine dipeptide (FF) encountered also in the amyloid peptide, notorious for inducing its aggregation into fibrils, tangles and plaques associated with Alzheimer’s disease,[7] as well as
(iii) with sulphonate groups conferring solubility in water. At low pH we observed the formation of helicoidal tubular assemblies from meso-tetrakis-4-sulphonatophenylporphyrin (TPPS4).[8] In this latter case, an apparent achiral
porphyrin, upon self-assembly, generates by symmetry breaking homochiral supramolecular species, a fact which
we are currently trying to rationalize and to control experimentally.
Figure 1. The Milky Way imagined by Sterngucker
References
1
T. S. Balaban “Self-assembling Porphyrins and Chlorins as Synthetic Mimics of the Chlorosomal Bacteriochlorophylls” in
Handbook of Porphyrin Science with Applications to Chemistry, Physics, Materials Science, Engineering, Biology and
Medicine, K. M. Kadish, K. M. Smith and R. Guilard, Eds., World Scientific: Singapore, 2010, Vol. 1, pp. 221-306.
[2] C. Fouquey, J.-M. Lehn, A.-M. Levelut, Adv. Mater. 1990, 2, 254-257.
[3]. P. Iavicoli, H. Xu, L. N. Feldborg, M. Linares, M. Paradinas, S. Stafström, C. Ocal, Nieto-Ortega, J. Casado, J. T. López
Navarrete, R. Lazzaroni, S. De Feyter, D. B. Amabilino, J. Am. Chem. Soc. 2010, 132, 9350-9362.
[4] S. Cantekin, H. M. M. ten Eikelder, A. J. Markvoort, M. A. J. Veld, P. A. Korevaar, M. M. Green, A. R. A. Palmans, E.
W. Meijer, Angew. Chem. Int. Ed. 2012, 51, 6426-6431.
[5] N. Micali, H. Engelcamp, P. G. van Rhee, P. C. M. Christianen, L. Monsù Scolaro, J. C. Maan, Nature Chem. 2012, 4,
201-207.
[6]. C. Chappaz-Gillot, G. Canard, F. Andreoli, N. Vanthuyne, M. Giorgi, J.-V. Naubron, V. Monnier, R. Rosas, C. Roussel, T.
S. Balaban, Eur. J. Org. Chem. 2012, 6526-6536.
[7] G. Charalambidis, E. Georgilis, M. K. Panda, C. E. Anson, A. K. Powell, S. Doyle, D. Moss, T. Jochum, P. N. Horton, S.
Cole, M. Linares, D. Beljonne, J.-V. Naubron, J. Conradt, H. Kalt, A. Mitraki, A. G. Coutsolelos, T. S. Balaban, manuscript in preparation.
[8] J. M. Short, J. A. Berriman, C. Kübel, Z. El-Hachemi, J.-V. Naubron, T. S. Balaban, ChemPhysChem 2013, 14, 32093214.
PLE2
Molecular resolution studies of the surface structure of
nanomaterials by combining experimental and theoretical
investigations
G. Martra
University of Torino, Department of Chemistry and Interdepartmental Centre “Nanostructured interfaces and surfaces – NIS”
Via P. Giuria 7, 10125 Torino (Italy)
[email protected]
Keywords: nanomaterials, surface structure, molecular resolution, vibrational probes
Imaging techniques as high resolution transmission electon microscopy (HRTEM) or atomic force microscopy
(AFM)can provide highly informative insights on shape and size of nano-objects, but besides several advantages
they suffer also of limitations: producing high detailed 2D images of 3D objects (HRTEM), attaining an atomic
resolution only when specific conditions are satisfied. Furthermore, the possibility to extract chemical information
form the data obtained by these technique is quite low. Then, how to simultaneously investigate nature, structure
and chemical features of the atoms exposed at the surface terminations of nanomaterials? A possibility is offered by
the substitution of oscillating tips scanning a surface, as typically occurs in AFM measuremens in the non-contact
mode, by adsorbed molecules the vibrational features of which, modified by the interaction with the surface, can be
monitored by vibrational spectroscopy. In this lecture, the exploitation of IR spectroscopy of adsorbed probe molecules for the elucidation of surface features of nanomaterials of interest for sustainable process and advances in the
energy production and health fields will be reviewed.
PLE3
Scientific Teaching and Research in Provence:
from the Century of Enlightenment to the University of Aix Marseille
Henri Tachoire
University of Aix Marseille, Marseille, France
E-mail: [email protected]
Keywords: history of sciences, Academy of Marseille, Faculty of Sciences
At the beginning of the 15th Century, Louis II of Anjou, count of Provence, founded in Aix a Studium Generale,
recognized by a papal bull. This new university came after those in Bologna, in Paris, in Montpellier. It dispensed
teachings in theology and canonic and civil law. In the middle of the 16 th Century, a faculty of medicine joined
those of theology and law. In 1603, an edict of King Henry IV created the Bourbon Royal College with teachings in
humanities, philosophy, mathematics and physics.
During the 17th Century, teachings of anatomy, botanic and chemistry were created inside the Faculty of Medecine. The County University became Royal. In 1764, part of the Bourbon College was integrated into the university
under the name of Faculty of the Arts. But, until the end of the century, little place was made for high level scientific teaching or for research.
In the 18th Century, science was constructed outside of the universities. A large part of works were made inside
the Academy of Sciences and the about thirty provincial academies founded in the 17 th and 18th centuries. These
academies proposed each year scientific competitions on mostly applied research topics. We will talk about those of
the Academy of Marseille, founded in 1726.
Having suppressed the universities and academies after the revolution in September 1793, the Convention
founded the Ecoles Centrales “for the teaching of sciences, letters and arts”, one school for 300000 inhabitants. The
school of the “Bouches du Rhone” opened in Aix in February 1798. An important place was made to the teaching
of sciences, but the school had little success and was suppressed on December 22, 1803.
A real Ministry of public instruction, the Imperial University was founded in 1806 and organized two years later
with Faculties of Theology, Law, Medecine, Letters and, big innovation at that time, of mathematical and physical
sciences. Aix became the head-city of one of the academies of the Imperial University (for the Departments of
Basses-Alpes, Alpes-Maritimes, Bouches-du-Rhone and Var). A Faculty of Sciences was created in Marseille in
1854, but research subsidies were attributed to certain laboratories only after the foundation of the Ecole Pratique
des Hautes Etudes in 1868.
After the fall of the Second Empire, the University of France replaced the Imperial University. It was only after
the law of July 10, 1896 that universities were again founded in France; faculties of a similar academic resort took
then the name of universities. The Academy of Aix became then the University of Aix Marseille. One was far away
from the “German-type” Universities, then much admired in France.
We will talk about the development of the Faculty of Sciences of Marseille during the 20th Century with the
construction of numerous buildings, the creation of research laboratories (some of which joined the Centre National
de la Recherche Scientifique) and the creation of several engineering schools.
In 1970, the University of Aix Marseille was divided into two universities, Aix Marseille I and Aix Marseille
II…followed by Aix Marseille III in 1973. And finally, since 1st January 2012, the reunification of the three universities is effective…under the name of University of Aix Marseille.
Conferenze Invitate
Conférences Invitées
INV1
The 2nd Century of Moderm Crystallography: from Nano and Disordered Crystal
Structures to Solid-State Reactivity
Marco Milanesio
Dipartimento di Scienze e Innovazione Tecnologica Università del Piemonte Orientale “A. Avogadro”
Viale T. Michel 11, I-15121 Alessandria, Italy
[email protected]
Keywords: Crystallography, X-ray and Electron Diffraction, Layered and Microporous Materials, Solid-State Reactivity.
X-ray diffraction (XRD), after almost 100 years of development, has become a very successful technique for the
structural characterization of condensed matter. XRD was applied successfully also to complex problems in materials science, for instance concerning extra-framework species location in microporous materials1,2,3,4. There are,
however, few fundamental limitations of this technique. One of these is represented by its limited chemical selectivity. In fact, XRD does not allow separating contributions from different atomic subsets. It is possible to obtain a
limited element selectivity by exploiting resonant scattering, but applications are limited to heavy atoms: Z > 15 in
principle but practically Z > 25, in most cases in sufficiently high concentration. Another limitation is the necessity
of growing suitable single crystals for an accurate structural determination. Finally XRD is hystorically a slow and
often static technique, able to taking a structural picture, thus losing all the dynamic effects in the studied system.
In recent years, thanks to the development of synchrotron radiation sousrces, new fast detectors such as the Pilatus
series5, novel massive data anaylsis techniques, and of automated electron tomografphy, all these limitations are
much less stringent, open new avebues to the 2nd century of modern crystallography. In the presentation recent developments about these novel approaches will be described. At first exploitation of new detectors to study solidstate transformations in microporius materials will be described. Then the use of automated electron diffraction
(ADT) to study nanocrystal of layered double hydroxides (LDH) as single crystals will be treated.
XRD first limitation is in general its limited chemical selectivity. Structural information on a subset of atoms can be
obtained by a modulation enhanced diffraction (MED) experiment, using a periodic stimulus supplied in situ on a
crystal, while diffraction data are collected several times within a stimulus period. The data are then treated by statistical methods such as phase sensitive detection (PSD) and Principal component analysis (PCA) techniques. The
application of PSD to diffraction has been proposed as a tool to selectively extract crystallographic information on a
subset of atoms6. Simulated and experimental MED powder data were produced by using a TS-1 zeolite as spectator, in which Xe, acting as active species, is adsorbed and desorbed in a periodically modulated mode. MED allowed obtaining, by demodulating first simulated and then experimental data, the powder diffraction pattern of the
active subset, i.e. obtaining selectively the crystallographic information on Xe, by solving the crystal structure of
the active species out of the zeolite framework. PCA, already widely used in spectroscopic analyses, was applied to
XRD and exploited to understand the data quality and to speed up the data analysis by reducing or eliminating data
pre-treatment, required by PSD approach. It resulted that the first two components obtained by PCA are related to
the 1- and 2- from PSD. The two approached (PCA and PSD) are then compared from the viewpoint of the capacity of gathering information on Xe substructure into the zeolite channels and used in a synergic way to obtain the
optimal data analysis efficiency.
LDH represents a versatile materials used for intercalating bioactive and photoactive molecules, both in pharmaceutical and cosmetic fields, with the purpose of protecting them from degradation, enhancing their water solubility to
increase bioavailability, and/or obtaining modified release properties. The crystal chemistry of hydrotalcite-like
compounds is investigated by XRPD and ADT to shed light on the structure of nitrate-containing hydrotalcite. ADT
allowed shedding light on the conformation nitrate into LDH and on the loss of crystallinity due to the layered morphology. XRPD demonstrated that the presence of carbonate is able to drive the intercalation of organic into LDH,
since CO3 contaminated samples tend to assume d-spacing roughly multiple of LDH-CO3 d-spacing.
References
1 G. Agostini, C. Lamberti, L. Palin, M. Milanesio, et al., ,J. Am. Chem. Soc., 132 (2), 2010 , 667–678
2 L. Palin, G. Croce, D. Viterbo, M. Milanesio, Chem. Mater., 2011, 23 (22), pp 4900–4909
3 M. Milanesio, G. Croce, D. Viterbo, et al., A, J. Phys. Chem. A, 2008, 112 (36), 8403–8410.
4 Palin L., Lamberti C.,Milanesio et al, J. Phys. Chem. B., 107(17), 2003, 4034-4042.
5 Kraft, P.; et al.. J. Synchrotron Radiat. 2009, 16, 368−375.
6 Caliandro, R., H., Chernyshov, D., Emerich, H., Milanesio, M.,, Palin, et al., D., 2012, J. Appl. Cryst., 45,
458-470.
INV2
Modelling of a Metabolon
Theoretical Strategies
Involved
in
Flavonoid
Biosynthesis
:
J. Diharce, J. Golebiowski, S. Fiorucci, S. Antonczak*
ICN-UMR CNRS 7272 Faculté des Sciences, Université de Nice-Sophia Antipolis
28 av. Valrose 06108 Nice Cedex 2
(*) [email protected]
Keywords: metabolon, flavonoid biosynthesis, molecular modelling
Flavonoids are natural compounds known for their organoleptic properties, for the role they play in the
coloration of flowers and fruits and for various anti-radical and anti-oxidant biological activities So far, about several thousands different flavonoids have been characterized. Thus, the biosynthetic pathways leading to their production are complex and involve many steps, each of them associated to the action of a specific enzyme.
In each living system, the concentration of functional biological entities (e.g. proteins, enzymes, peptides…) is incredibly high. Some transient complex-structures may appear and, depending on the affinity the protagonists exhibit for each other, may subsist during sufficiently long timescales that may lead to new functional
systems called metabolons.(1-3) Experiments have demonstrated that some metabolons, see Figure 1, lie at the
vicinity of the membrane.
Recent investigations highlight the existence of such a metabolon in the course of flavonoids production in
which the successive enzymes remain in interaction. The product of an enzymatic reaction becoming the substrate
for the neighbour enzyme, it only has to “jump” from an active site to the next one, diminishing unnecessary diffusion processes and loss of energy during solvation and desolvation processes, yielding an enhanced catalytic efficiency.
Fig. 1. A metabolon is a transient functional complex of several sequential enzymes
held together by noncovalent interactions in a given metabolic pathway. The product
of the first enzyme is channelled directly into the active site of a second enzyme
where it acts as a substrate..
Being able to precisely describe the overall architecture of these macromolecular assemblies has then become a key to understand the underlying biological mechanisms and for developing new therapeutic strategies.
So far, our investigations focused on an assembly composed by three enzymes considered as key steps in
the biosynthesis of anthocyanins and condensed tannins, namely F3’H, DFR and LAR, in interaction with a model
of membrane. In this presentation, will be discussed the theoretical strategies carried out i) to characterise the enzymatic reaction (QM/MM-MD simulations) ii) to define the way the substrates and the products enter in or are
released from the active site (brut force MD, RAMD protocol…) iii) to design an enzyme complex in interaction
(ATTRACT docking protein/protein protocol) and to decipher the interaction of this assembly with a model of
membrane (OPM protocol).
References
1
BSJ. Winkel, Metabolic Channeling in plants. Annu. Rev. Plant Biol. 55 (2004).85–107
[2]
K. Jørgensen, A.V. Rasmussen, M. Morant, A.H. Nielsen, N. Bjarnholt, M. Zagrobelny, S. Bak, B.L. Møller. Metabolon
formation and metabolic channelling in the biosynthesis of plant natural products. Current Opinion in Plant Biology 8
(2005) 280–291
[3]
L. Ralston, O. Yu Metabolons involving plant cytochrome P450s, Phytochem Rev 5 (2006) 459–472
INV3
Organometallic-promoted radical-polar cascades in aerobic medium
L. Feray
1
Aix-Marseille Université, Institut de Chimie Radicalaire, UMR 7273, Equipe Chimie Moléculaire Organique, service 562,
Campus Saint-Jérôme, av. Escadrille Normandie Niemen, 13397 Marseille cedex 20
Keywords: Dialkylzinc, Radical-polar cascades, Multicomponent reactions, Synthetic applications
Over the last few years, our group has been interested in tin-free methodologies and in this context we have
investigated the synthetic potential of dialkylzincs regarding radical chemistry. More particularly, we have studied
their use as mediators in radical additions to various acceptors. The peculiar behavior of these organometallic reagents resides in the fact that, in the presence of oxygen, they are good precursors of alkyl radicals and, at the same
time they are good partners for bimolecular homolytic substitution reactions that enable to generate polar species
from radical intermediates. Thereby, dialkylzincs are reagents of choice to perform radical-polar cascades in aerobic medium. [1]
This methodology has been applied to the one-pot stereoselective synthesis of tri- and disubstituted γ-lactones
[2] and pyrrolizidines [3] from diethylfumarate and to the original formation of tri- and tetrasubstituted fumaric
derivatives from diethylacetylene dicarboxylate [4]. More recently, the formation of allenylzincs from propargyl
iodides and diethylzinc was shown to proceed through a radical pathway and this process was used for the synthesis
of various cyclic compounds bearing allenic moiety [5].
EtO2C
HO
O
CO2Et
EtO2C
N
CO2Et
CO2Et
EtO2C
O
O
I
O
N
R
O
O
CO2Et
R = Alkyl, Aryl
I
O
95%
R
O
35-98%
ZnR2
(R = Me, Et)
CH2Cl2, air, rt
I
O
2) NH4Cl
I
EtO2C
N
I
I
EtO2C
HO
O
EtO2C
CO2Et
O
CO2Et
H
N
O
N
I
CO2Et
R1 I
I
EtO2C
CO2Et
R1
75-99%
68%
O
OH
N
89%
O
References
1
For selected reviews see : (a) S. Bazin, L. Feray, M. P. Bertrand, Chimia 60 (2006) 260. (b) T. Akindele, K.-I. Yamada, K.
Tomioka, Acc. Chem. Res. 42 (2009) 345.
2
J. Maury, L. Feray, P. Perfetti, M. P. Bertrand, Org. Lett. 12 (2010) 3590.
3
J. Maury, D. Mouysset, L. Feray, S. R. A. Marque, D. Siri, M. P Bertrand, Chem. —Eur. J. 18 (2012) 3241.
4
J. Maury, L. Feray, M. P Bertrand, Org. Lett. 13 (2011) 1884.
5
(a) J. Maury, S. Jammi, F. Vibert, S. R. A. Marque, D. Siri, L. Feray, M. P. Bertrand, J. Org. Chem. 77 (2012) 9081. (b) S.
Jammi, D. Mouysset, D. Siri, M. P Bertrand, L. Feray, J. Org. Chem. 78 (2013) 1589. (c) S. Jammi, D. Mouysset, D. Siri,
M. P Bertrand, L. Feray, J. Org. Chem. 77 (2013) 1589.
INV4
Diamond cutting tools: technological issues and interfacial reactivity
C. Artini1,2,*, F. Valenza2, M.L. Muolo2, G.A. Costa1,3, A. Passerone2
1
DCCI, Department of Chemistry and Industrial Chemistry, University of Genova, Via Dodecaneso 31, 16146 Genova, Italy
CNR-IENI, National Research Council – Institute for Energetics and Interphases, Via De Marini 6, 16149 Genova, Italy 3
3
CNR-SPIN Genova, Corso Perrone 24, 16152 Genova, Italy
(*) corresponding author: [email protected]
2
Keywords: diamond, cutting tools, superabrasive materials, interfaces.
Tools for the machining of difficult-to-cut materials, such as natural stone, concrete, ferrous and non-ferrous alloys, often contain grits of a superabrasive, such as diamond or cubic BN, according to the mechanical and chemical properties of the workpiece.
Diamond cutting tools generally consist of a segment containing the abrasive grits, fixed to the steel core of the
tool. Diamond grits can be embedded by hot-press sintering in a metal powder, often a Co-based alloy (impregnated
tools), or they form a thin layer brazed to the steel core by a filler phase, generally consisting of a Cu-, Ni- or Agbased alloy (brazed tools), or are mechanically entrapped in an electroplated Ni layer forming the matrix (electroplated tools). Alternatively, diamond can be deposited on a proper substrate by chemical vapor deposition; finally,
it can form a compact if many crystals are sintered at high temperature and high pressure on a WC-Co substrate.
In all cases the diamond/matrix interfacial reactivity is a relevant technological issue [1], as a strong adhesion is
essential to avoid early detachment of diamonds; thus, small amounts of active elements (e.g. Cr, Ti or V), are
sometimes added to the matrix to promote the formation of a chemical bond. At the same time, in impregnated tools
the pull-out of diamond grits is desirable when the exposed diamond surface is flattened, so that new grits can come
out. Moreover, to prevent oxidation and graphitization phenomena occurring during the sintering process of the
segment or during the cutting operation, coated diamonds (by Ti, Co, etc.) can be used too [2,3], as a carbide film
forms on the diamond surface avoiding graphitization.
In this lecture, technological issues, such as benefits and drawbacks of each kind of tool related to the material
to be cut, as well as the choice of the proper metallic matrix according to the workpiece and the reactivity towards
diamond, will be discussed, with particular reference to impregnated and brazed diamond tools.
References
1
C. Artini, M.L. Muolo, A. Passerone, J. Mater. Sci. 47 (2012) 3252.
[2]
X. Xu, X.R. Tie, H. Wu, Int. J. Refract. Met. Hard. Mater. 25 (2007) 244.
[3]
Y.H. Wang, J.B. Zang, M.Z. Wang, Y. Guan, Y.Z. Zheng, J. Mater. Process. Tech. 129 (2002) 369.
INV5
(Acyl)thiocarbamates, disulfides and enamines as novel non-nucleoside HIV-1
reverse transcriptase inhibitors
A. Spallarossa
University of Genova, Department of Pharmacy, viale Benedetto XV, 3 16145 Genova
[email protected]
Keywords: non-nucleoside reverse trasnscriptase inhibitors, HIV-1, parallel synthesis, structure-activity relationships
HIV-1 non-nucleoside reverse transcriptase inhibitors (NNRTIs) represent one of the key constituents of the
current anti-AIDS combination therapy. The emergence of drug-resistant viral strains calls for novel compounds
endowed with higher potency and widespread activity against wild-type and mutated viruses. In this regards,
acylthiocarbamates (ATCs), thiocarbamates (TCs) and formimidoester disulfide (DSs) have been identified as novel NNRTIs (Figure 1) [1-3]. The three compound series are structurally related: a molecular simplification strategy
on ATC led to the non acylated TC derivatives that can be viewed as monomeric precursors of DSs. ATCs, TCs and
DSs were prepared by a convergent synthetic approach based on the combination of different building blocks (alcohols, isothiocyanates and acyl chlorides for ATCs; alcohols and isothiocyanates for TCs and DSs). Within each
series, nanomolar or sub-nanomolar HIV-1 inhibitors were identified.
In an effort to identify novel anti-HIV-1 molecules, enamine derivatives emerged as a promising series of antiretroviral compounds (Figure 1) [4]. Enamine derivatives were prepared by condensing amines with ,unsaturated thioureas. These intermediates were obtained by the reaction of iminium salts with active methylene
reagents [5]. The synthetic protocol is versatile and allowed the development of extensive structure-activity relationships (SARs).
N-Acylthiocarbamates (ATCs)
Thiocarbamates (TCs)
X, Y = CN, COOR, COOR, SO 2Ar
R', = H, (cyclo)alkyl, benzyl
2
Formimidoester disulfide (DSs)
Enamine derivatives
Fig. 1. General structures of ATC, TC, DS and enamine compounds.
For each compound series, the synthetic procedure, the SARs and the docking/x-ray crystallography data collected will be presented and discussed.
References
1
A. Spallarossa, S. Cesarini, A. Ranise et al. Eur. J. Med. Chem. 44 (2009) 2190 and references therein
[2]
A. Spallarossa, S. Cesarini, A. Ranise et al. Eur. J. Med. Chem. 44 (2009) 1650 and references therein
[3]
S. Cesarini, A. Spallarossa, A. Ranise et al. Bioorg. Med. Chem. 16 (2008) 6353-6363.
[4]
C. Rotolo. PhD Thesis 2012
[5]
A. Ranise, S. Cesarini, A. Spallarossa, et al. Synthesis 16 (2007) 2495
Comunicazioni Orali
Communications Orales
COM1
A quantitative approach of the interaction between metal triflates and organic
ligands using electrospray mass spectrometry
C. Iacobucci1,2, L. Massi1 , S. Olivero1 , E. Duñach*1 , J.-F. Gal*1
1
Institut de Chimie de Nice, Université Nice Sophia Antipolis, CNRS-UMR 7272, Parc Valrose, 06108 Nice Cedex 2, France
2
Dipartimento di Scienze Fisiche e Chimiche, Università dell'Aquila, Via Vetoio, Coppito, 67100 L'Aquila, Italy
* [email protected]; [email protected]
Keywords: Mass spectrometry, Lewis Acid, chiral recognition
Metal trifluoromethanesulfonates (triflates M(CF3SO3)n) and bis(trifluoromethanesulfonyl)imide salts (triflimides M[(CF3SO3)2N]n) are regarded as Lewis "superacids". This feature is attributed to the specific electronic structure of the anions: a highly delocalized negative charge, and a resulting low coordination power, leaving a highly
reactive cation.[1] Such salts have remarkable catalytic properties and exploration of new methods for their characterization are desirable. The variety and the complexity of such catalytic systems pose a challenge to their rational
use because factors associated with catalysis effectiveness are not completely understood.
Thus, thermodynamic experimental data on organometallic adducts are highly required both directly to gain insight into catalysis rationalization and indirectly as a reference lock for computational organometallic chemistry.
Electrospray mass spectrometry (ESI-MS) has gained widespread acceptance as a technique for mechanistic
studies of organic reaction and catalysis. Under specific conditions (nitromethane as solvent, addition of strong
neutral ligands), electrospray ionization mass spectrometry (ESI-MS) and collision induced dissociation (CID) can
afford useful analytical data on these salts.[2]
For such a system, the formation of positive ions is based on the displacement of one anion in the salt by neutral Lewis bases, such as phosphoryl compounds, amides, ketones, alcohols. The most frequent reaction involved
two neutral Lewis bases (LB) producing a singly charged positive ion by expulsion of one anion from the salt, for
example:
In(CF3SO3)3 + 2 LB --->  [In(CF3SO3)2(LB)2]+ + CF3SO3This kind of adduct ion is often the base peak in the ESI(+) mass spectrum of mixtures of the neutral ligands
and metal triflates in nitromethane. From these observations, with the aim of ranking the ligand affinities for various metal centers, a competition method using mixtures of two different ligands was developed. The relative intensities of the ionic species containing the different combinations of ligands generated an order of ligand relative
affinities for several metal salts.[3]
This qualitative method was recently improved. Modeling the effect of the ligand concentrations on the signal
intensities led us to propose a quantitative parameter describing the relative affinity for the metal center.[4] Under
certain assumptions, our quantitative parameter could be converted into thermodynamic constants of the relative
ligand exchange equilibra in solution.
Interestingly, this new method is sensitive enough to quantify the affinity difference between isomers of certain ligands. We therefore investigated the opportunity to employ the basic concept of our ligand competition method to develop a new stereoisomer recognition technique. This results in new opportunities both to quantify enantiomers in solutions and to gain further insight into the organometallic origin of non-linear effects in asymmetric
synthesis.
Quantum chemical calculations using DFT are currently carried out, in an attempt to better understand the
thermodynamic meaning of affinity scales.
In this communication, this ESI-MS quantitative ligand competition method and the stereoisomer recognition
perspective will be presented.
References
[1] (a) S. Antoniotti, V. Dalla, E. Dunach, Angew. Chem. Int. Ed. 49 (2010) 7860; (b) S. Olivero, J.-F. Gal, C. Iacobucci., I.
Monfardini, L. Massi., E. Duñach, S. Olivero, J. Phys. Org. Chem. 19 (2013) 3270; (c) G. Lemière, E. Duñach, Chem.
Eur. J. 19 (2013) 3270.
[2]
I. Monfardini, L. Massi, P. Tremel, A. Hauville, S. Olivero, E. Dunach, J.-F. Gal, Rapid Commun. Mass Spectrom. 24
(2010) 2611.
[3]
I. Monfardini, L. Massi, E. Dunach, S. Olivero, J.-F. Gal, Chem. Commun. 46 (2010) 8472.
[4]
J.-F. Gal; C. Iacobucci, I. Monfardini, L. Massi, E. Dunach, S. Olivero, J. Am. Soc. Mass Spectrom. 23 (2012) 2059.
COM2
Experimental and thermodynamic study of the conversion of mixtures with
methane up to 1700°C
A. Comite*,1, A. Chiarlone1, R. Di Felice2, V. Marotta1, S. Arata2, P. Pagliai2, P. Petit
Bon3, G. Capannelli4, G. Bruni5
2
1
Department of Chemistry and Industrial Chemistry, University of Genoa, Via Dodecaneso 31, 16146 Genoa, Italy
Department of Civil, Chemical and Environmental Engineering, University of Genoa, Via Opera Pia 15, 16145 Genova, Italy
3
Ireos Laboratori S.r.l., Via Turr 165, 16147 Genova, Italy
4 Ticass S.c.r.l., Via Bartolomeo Bosco 57/4, 16121 Genova, Italy
5
Italiana Coke S.r.l., Via San Vincenzo, 2, 16121 Genova, Italy
Synthesis gas; Tubolar reactor; Pyrolysis; High temperature steam conversion, Equilibrium conversion
Several studies are present in the literature, that describe the application of high process temperatures, up to
1400°C, in order to decompose natural gas and obtain a syngas mixture [1]. In fact, syngas can be appropriately
used to synthetise a broad range of environmentally clean fuels and high value chemicals as well as to produce
electrical energy starting from both fossil and renewable sources.
This project aims to study the effect of high temperatures (1500°C-1700°C) on a typical industrial gas mixture, whose main constituents are hydrogen and methane, that develops from either gasification or pyrolysis processes. For this purpose, a high temperature lab-scale rig was used, which consists of an alumina tubular reactor
placed inside an electrical furnace that is capable to achieve temperatures as high as 1800°C.
Experimental work has been carried out in order to evaluate the effect of several operative variables (temperature, H2O/CH4 ratio, residence time) on a gaseous mixture composed of (% v/v): H2 (60%), CH4 (27%), N2 (6%),
CO (5%) and CO2 (2%).
The outlet gas composition was analyzed by means of a micro-GC; sampling vials have been also used in order
to ascertain the presence of VOCs and PAHs during testing at 1700°C.
Results show that, provided that an appropriate amount of water is mixed with the feed, the resulting outlet
composition is a mixture of hydrogen and carbon monoxide (main components of the Syngas), whereas methane
was completely converted in a range of temperature between 1500°C and 1600°C.
The pyrolysis is also characterized by the formation of solid carbon residue, whose relative amount depends on
both the operative temperature and presence of water.
The theoretical equilibrium gas composition was calculated by employing a dedicated software in a range of
temperatures between 25°C and 1800°C. The experimental results were compared with the equilibrium values.
Acknowledgments
The project was funded under the PO CRO FES Regione Liguria 2007-2013 (Asse IV “Capitale Umano”
ob.specifico I/6) and POR CRO FESR LIGURIA 2007-2013 (Asse I – Innovazione e Competitività Azione 1.2.2
Ricerca Industriale e Sviluppo Sperimentale). We would like to acknowledge for the collaboration Ticass S.c.r.l.
(Innovative Technologies for the Environmental Control and the Sustainable Development which is the managing
body of the "Energy-Environment" Regional Innovation Hub) and all the enterprises involved in the project: IREN
ACQUA GAS S.p.A., Italiana Coke S.r.l., P&T Srl – Port and Territory, E.A.T. S.r.l. and IREOS Laboratori S.r.l. .
References
1
X. Song, Z. Guo, Energy Conv. Manage. 47 (2006), 560–569
COM3
Use of the Morita-Baylis-Hillman reaction in the design of compounds inhibiting
NLRP3 inflammasome signaling pathways
M. Cocco1, D. Garella1, G. Miglio1, E. Borretto1, L. Stevanato1, A. Di Stilo1,
M. Bertinaria*,1
1
Università degli Studi di Torino, Dipartimento di Scienza e Tecnologia del Farmaco, Via P. Giuria 9- 10125 Torino
Keywords: NLRP3 inflammasome, Morita-Baylis-Hillman reaction, pyroptosis, parthenolide, cryopyrinopathies
NLRP3 inflammasome is an intracellular multiprotein complex which mediates pyroptosis (a form of programmed cell death), IL-1β and IL-18 production in response to a range of microbial infections and non-infective
pro-inflammatory stimuli [1]. Abnormal over-activation of NLRP3 inflammasome has been clearly demonstrated in
patients with autoinflammatory syndromes known as cryopyrinopathies (CAPS). In addition, a role for NLRP3
inflammasome activation has been postulated in the pathogenesis of other disorders such as type-2 diabetes mellitus, atherosclerosis, gout and neurodegenerative diseases [2]. Therefore, since NLRP3 inflammasome has shown a
significant therapeutic potential, attention has been focused on the discovery and development of small molecule
antagonists [3].
Few experimental molecules have been found to inhibit NLRP3 activation: parthenolide (PTL), bromoxone
(BRX), Bay 11-7082 (BAY) and recently identified 3,4-methylenedioxy--nitrostyrene (MNS). Such compounds
share a Michael acceptor moiety which might be essential for their pharmacological activities. Since several crucial
cysteine residues have been identified in NLRP3 pathway (e.g. P 2X7 receptor, NLRP3, caspase-1 active site) we
hypothesized that these electrophiles could react with one or more regulatory cysteine residues thus inhibiting
NLRP3 function. Consistently, PTL was found to efficiently alkylate thiol groups both in NLRP3 protein and
caspase-1, thanks to the reactivity of its exo-methylene moiety.
In this communication we describe design and synthesis of a library of simplified PTL-like structures obtained
by Morita-Baylis-Hillman (MBH) reaction. Biological screening, performed in two different inflammasome activating settings (THP-1 cells stimulated with either LPS+ATP or LPS+nigericin), and chemical characterization of their
reactivity toward relevant thiols enabled us to identify some promising lead compounds worth of further development as druggable NLRP3 pathway inhibitors.
Fig. 1. Simplified NLRP3 pathway activation and its small molecule inhibitors
References
1
F. Martinon, K. Burns, J. Tschopp, Mol. Cell. 10 (2002) 417-426.
[2]
A. So, A. Ives, L.A.B. Joosten, N. Busso, Nat. Rev. Rheumatol. 9 (2013) 391-399.
[3]
G.
Lopèz-Castejon,
P.
Pelegrin,
Expert.
Opin.
Investig.
Drugs.
21
(2012)
995-1007.
COM4
Elaboration and microstructural studies of luminescent materials
based on Ca0.5Cd 0.5WO4 tungstate phases.
A.Taoufyq1,2,3,4,(*), L. Patout1, F. Guinneton1, J-C. Valmalette1, A. Benlhachemi2,
S. Villain1, A. Lyoussi3, G. Nolibe4, J-R. Gavarri1
3
1
Institut Matériaux Microélectronique et Nanosciences de Provence,
Aix Marseille Université, CNRS, Université de Toulon, IM2NP UMR 7334, 83957, La Garde, France.
2
Laboratoire Matériaux et Environnement LME, Faculté des Sciences, Université Ibn Zohr, BP 8106, Cité Dakhla, Agadir,
Maroc.
CEA/DEN, Département d‘Études des Réacteurs, Laboratoire Dosimétrie Capteurs Instrumentation, CEA Cadarache, 13108,
Saint-Paul-lez-Durance, France.
4
Société CESIGMA, signals & systems, 1576 Chemin de La Planquette, 83130 La Garde, France.
(*) to whom correspondence must be addressed (e-mail: [email protected], Tel: +33 494 142 309)
Keywords: tungstate, solid solution, X-ray diffraction, Raman spectroscopy, transmission electron microscopy
Abstract
To develop new miniaturized radiation sensors having suficient sensitivity or selectivity, we study new scintillating or luminescent materials susceptible to be integrated in sensing devices in diversified forms, including thin
layers or nanostructured ceramic pellets. The calcium and cadmium tungstate phases CaWO 4, CdWO4 were previously studied for their luminescent properties under X-ray or UV irradiations. In this work, we present studies on
the new substituted phase Ca0.5Cd0.5WO4.
Those materials were elaborated using a classical coprecipitation method followed by a calcination process at
different temperatures. The samples were characterized by X-ray diffraction, scanning and transmission electron
microscopy (SEM, TEM) analyses and Raman spectroscopy. The Rietveld [1] analysis and the TEM images clearly
confirmed the I41/a space group [2] for Ca0.5Cd0.5WO4. The results of vibrational spectroscopy were in good agreements with the XRD, TEM and HRTEM measurements. Luminescence analyses of samples performed under X-ray
and UV radiation excitations are discussed.
1200
0
0
Bg bend.
300
Bg stretch.
300
Ag stretch.
Bg bend.
Eg bend.
Intensity (Cnt)
900
Eg as-stretch.
Bg as-stretch.
modes
600
Internal modes
Ag+Bg stretch.
External
600
900
1200
-1
Raman shift ( cm )
Figure 1. HRTEM processed a,d) and simulated b,c,e,f)
images of Ca0.5Cd0.5WO4, along [100] and [001] zone axes.
Ca (green), Cd(red), W(brown), and O(purple) are pointed
in c,f).
Figure 2. Raman spectra (λ = 514.5 nm) of the Ca0.5Cd0.5WO4 phase.
References
[1] T.Roisnel et al., Proceedings of the 7th European Powder Diffraction Conference, (2000) 118-123.
[2] R.M. Hazen et al., Journal of Physics and Chemistry of Solids, 46 (1985) 253-263.
COM5
Polymerization Studies of a Novel Ammonium-Functionalizated Diacetylene SelfAssembled on Metal Nanoparticles.
M. I. Martinez Espinoza*, M. Alloisio, G. Dellepiane, M. Maccagno, S. Thea
Università degli Studi di Genova, Dipartimento di Chimica e Chimica Industriale, via Dodecanneso 31, 16146
Keywords: nanohybrid, polydiacetylene derivatives, gold and silver nanoparticles
The inorganic/organic hybrids dimensioned at nanoscale provide, in terms of properties and chemical-physical
features, superior performance with respect to traditional composite materials. Recently, an increasing number of
studies have been devoted to design novel types of nanohybrid based on a central inorganic core coated by a protective shell of organic nature for new applications as optical sensors and transducers. Thanks to their defined absorptions in the visible spectral region, the nanoparticles of noble metals such as gold and silver seem to be excellent
candidates for the development of optical probes [1-3]. As for the coating layer, several types of organic molecules
endowed with optical properties have been studied; among them, in particular the diacetylene derivatives.
Since the first report of diacetylene topochemical polymerization in the solid state, diacetylene derivatives
have attracted much attention, since the highly conjugated eneyne backbone and suitably tailored side chains lead to
intriguing optical and electronic properties. This is quite promising in many applications such as non-linear optical
materials semiconductors and photoconductors, sensing devices, and in biological and medical fields [3-5].
Fig 1. Schematic representation of diacetylene self-assembled on metal nanoparticle, the photopolymerization of the monolayer and the blue to red colorimetric transition of polymer.
Diacetylene derivatives can be obtained in several molecular organizations. Recently, they have been used
to cap nanoparticles and very interesting results have been obtained so far also in our laboratory (Fig. 1) [4-5]. The
possibility of tailoring the side chain of polydiacetylene has stimulated the synthesis of novel monomers functionalized with the trimethylammonium end group, with the purpose of investigating the possibility of direct formation of
nanorods (NRs) without the presence of the otherwise indispensable C16TAB [6]. NRs are a very interesting material because their plasmon band is dramatically red-shifted towards the NIR spectral region, suitable for in vivo medical diagnostics and therapeutical applications.
Our initial results concern the synthesis of the novel N,N,N-trimethyl-3-(pentacosa-10,12-diynamido)propan-1aminium bromide (DAAMM), and investigation by UV spectroscopy of photopolymerization of the self-assembled
monomer on both gold and silver nanoparticles. Formation of the blue and red polymer forms was observed to
strongly depend also on the pH of the polymerization reaction media.
The results of this study, together with a description of our efforts to move beyond conventional spherical nanoparticles, will be presented and discussed.
References
K. Lance K., Coronado E., Lin Zhao L., C. Schatz G., J. Phys. Chem. B, 107 (2003), 668
B. Cortie M. M. McDonagh A., Chem. Rev. 111 (2011), 3713
Carpick R., Sasaki D., Marcus M., Eriksson M., R Burns A. J. Phys.: Condens. Matter 16 (2004) 679
Alloisio M., Demartini A., Cuniberti C., Dellepiane G., Sensors Lett. 8 (2010), 405
Dellepiane G., Cuniberti C., Alloisio M. Demartini A., Phys. Chem. Chem. Phys., 12 (2010), 2968
Vigderman L.,P. Khanal B., R. Zubarev E., Adv. Mater., 24 (2012), 4811
COM6
New Pt(IV) antitumour prodrugs for drug targeting and delivery strategies
E. Gabano,1 F. Fregonese,1 S. Tinello,1 M. Ravera,1 D. Osella*,1
1
Università del Piemonte Orientale “A. Avogadro”, Dipartimento di Scienze e Innovazione Tecnologica, Viale T. Michel 11,
I-15121 Alessandria, Italy
Keywords: Pt(IV) complexes, drug targeting and delivery, antitumour drugs
Pt(IV) complexes are believed to act as antitumour prodrugs. Indeed, they can be reduced in vivo in the hypoxic,
reducing environment of the tumour tissue in such a way that the octahedral Pt(IV) complexes turn into their active
square-planar Pt(II) metabolites through a two electron reductive elimination, which leads to the loss of their axial
ligands. Pt(IV) complexes are more inert towards ligand substitution than their Pt(II) counterparts and therefore are
involved in fewer side reactions with biological nucleophiles. The choice of the axial ligands is essential to modulate the water solubility, the lipophilicity (and the related cellular uptake) and the redox properties of these complexes [1].
The axial ligands may have their own biological role as active targeting and delivery vectors or as co-adjuvant
drugs, or may act as linkers for passive targeting and delivery vectors [2].
Pt(IV) complexes are usually prepared by oxidation of the corresponding Pt(II) counterparts, typically using hydrogen peroxide or chlorine. A different way to oxidize the Pt(II) compounds is represented by the use of Nchlorosuccinimide [3].
The reaction between cisplatin (cis-[PtCl2(NH3)2], 1), carboplatin (cis-[Pt(cbdc)(NH3)2], 2), cis-[PtCl2(dach)] (3)
and cis-[Pt(cbdc)(dach)] (4) (cbdc = cyclobutane-1,1’-dicarboxylato; dach = cyclohexane-1R,2R-diamine) with Nchlorosuccinimide in ethane-1,2-diol alias ethylene glycol (glyc) was optimized to produce the asymmetric Pt(IV)
octahedral complexes [PtA2Cl(glyc)X2] (A2 = 2 NH3 or dach; X2 = 2 Cl or cbdc) in high yield and purity (Figure 1).
The two trichlorido complexes (5 and 7) easily undergo a pH-dependent hydrolysis reaction, whereas the dicarboxylato compounds (6 and 8) are stable enough to allow further coupling reactions for drug targeting and delivery
via the ethane-1,2-diol reactive pendant. Therefore, the coupling reaction between the [Pt(cbdc)Cl(dach)(glyc)] and
a model carboxylic acid, a model amine and selectively protected amino acids is reported.
Fig. 1. Synthesis of Pt(IV) complexes through oxidative chlorination of the corresponding Pt(II) complexes with Nchlorosuccinimide in ethane-1,2-diol: dach = cyclohexane-1R,2R-diamine, cbdc = cyclobutane-1,1’-dicarboxylato
References
1
M.D. Hall, T.W. Hambley, Coord. Chem. Rev. 232 (2002) 49.
[2]
J.S. Butler, P.J. Sadler, Curr. Opin. Chem. Biol. 17 (2013) 175.
[3]
SANOFI-AVENTIS, FR 2 954 321 – A1 Patent.
COM7
The First Mixed Ligand Pd-Catalyzed C-S Coupling:A Highly Effective Strategy
for Synthesizing S-Arylthioheteroaryl Derivatives
M. Cong1, Y. Fan1,2, J.-M. Raimundo1, Y. Xia1, G. Quéléver1, F. Qu2, L. Peng*,1
1
Aix-Marseille Université, Centre Interdisciplinaire de Nanoscience de Marseille, CNRS UMR 7325, Campus de Luminy, 13288
Marseille, France
2
State Key Laboratory of Virology, College of Chemistry and Molecular Sciences, Wuhan University, 430072 Wuhan, P. R.
China
Keywords: Mixed ligand Pd catalyst, S-arylthioheteroaryl compounds, C-S cross-coupling, 31P NMR, cyclic voltammetry
We report here for the first time a novel concept of the mixed ligand catalytst (Pd2(dba)3/Xantphos/CyPF-tBu) in
realizing C-S cross-coupling with structurally challenging substrates in extremely high yield and with unprecedently large substrate scope (Figure 1A) [1]. Further investigation on the catalytic mechanism using 31P NMR and cyclic voltammetry revealed that the two mixed ligands cooperated ingeniously in the catalytic reaction with
Xantphos promoting the formation of the active Pd catalyst and CyPF-tBu taking on the majority of the catalytic
role in assisting C-S coupling (Figure 1B). This finding offers us a unique opportunity to rationally combine ligands
with complementary features, in order to exploit the full potential of already well-established catalytic systems and
promote the corresponding reactions with large substrate scope and high product yield [2-4]. Rationally combining
the individual ligands and precisely deciphering how the mixed ligands operate and cooperate in exquisite harmony
to boost the catalysis is an exciting road ahead, and we are working actively in this direction.
A)
B)
Figure. (A) Effective and versatile C-S coupling using the Pd/Xantphos/CyPF-tBu mixed ligand system. (B) Proposed mechanism for the mixed ligand catalytical system to promote C-S coupling reaction.
References
1
M. Cong, Y. Fan, J.-M. Raimundo, Y. Xia, G. Quéléver, F. Qu, P. Rocchi, L. Peng, Chem. Eur. J. 51 (2013) 17267.
[2]
B. P. Fors, S. L. Buchwald, J. Am. Chem. Soc.132 (2010) 15914.
[3]
Y. Fan, Y. Xia, J. Tang, F. Ziarelli, F. Qu, P. Rocchi, J. L. Iovanna, L. Peng, Chem. Eur. J. 18 (2012) 2221.
[4]
Y. Fan, M. Cong, L. Peng, Chem. Eur. J. 20 (2014) 2698.
COM8
Improving portable-XRF analyses on Medieval Limoges enames: opacifiers
control in lead-bearing glasses.
G. Fenoglio1, M. Aceto2, A. Agostino*,1, 3, C. Gamarra1, M. Labate1, L. Operti1,3
1
2
Dipartimento di Chimica, Università degli Studi di Torino, via Giuria, 7 - 10125 Torino
Dipartimento di Scienze e Innovazione Tecnologica (DISIT), Università degli Studi del Piemonte Orientale, viale Teresa Michel, 11 - 15121 Alessandria
3
Interdepartmental Center for Crystallography (CRISDI), via Giuria, 7 - 10125 Torino
Keywords: medieval enamels, XRF, tin-oxide, crystallization
Non-invasive approach is a strategic key to accede to a large amount of artworks otherwise inaccessible to common
analytical techniques. Thanks to the use of portable X-ray Fluorescence (p-XRF), an outstanding amount of data
was collected on 11th-14th century Limoges enamels and their 19th century copies. According to literature [1] and
our results, the opacifier used in the enamel is by itself distinctive of the period of production, while compositional
variations are fundamental to characterize specific manufactures. In particular, while calcium antimonate and lead
arsenate are connected respectively to most ancient artefacts and modern copies, tin oxide is the main opacifier in
medieval Limoges enamels; historical recipes report the addition of a Pb-Sn calx (Pb2SnO4) to a glass frit or glass
powder [2][3].
Though our quantitative approach, which is an intermediate way between fundamental parameters and standard
material calibration, showed a high reliability on silica glass matrices, relevant matrix issues are present when lead
is introduced. Essentially, a very low number of glass standards is available and they do not have comparable compositions in terms if silica to lead rate. Moreover, light matrices usually contain what is called “dark matrix”, ie the
content of elements too light to be detected, whose amount can be correctly quantified only working on the other
detectable elements [4].
A laboratory research was therefore opened in order to produce medieval-like enamels to be used as reference materials in order to overcome the lack of adequate standards. Scientific and historical literature was thoroughly
scanned in search of reference compositions and information on opacifing processes. However, no information on
SnO2 crystallization in similar matrices could be obtained from literature, while a number are present on lead glazes
[5][6]. The production of tin opacified samples required a significant number of experiments. HT-XRD and PXRD
on quenched samples where applied to improve our knowledge respect to SnO2 crystallization behavior, together
with optical and electronic microscopy. Finally, variations on the heating cycle allowed obtaining a proper dispersion of the opacifier in the vitreous matrix such as observed by microscopic inspection on historical enamels (Fig.1)
EDS-microanalysis of the produced samples was then used to calibrate the instrument.
In the end, SEM-EDS data on samples exceptionally collected from medieval and 19 th century enamels will be
presented and discussed respect to data obtained with p-XRF.
Fig. 1. SnO2 dispersion in the glass matrix: Limoges enamels (left) and laboratory samples (righ).
References
I. Biron et al., 1996. In: Enamels of Limoges 1100-1350 John hilip
eill, Metropolitan Museum of Art ( ew ork)
C. Moretti et al., 2004. Ricette vetrarie muranesi: Gasparo Brunoro e il manoscritto di Danzica. Firenze: Nardini.
J. Henderson, 2013. Ancient Glass: an interdisciplinary exploration. Cambridge University Press.
K. Janssens, 2013, Modern Methods for Analysing Archaeological and Historical Glass, Wiley.
J. Molera, T. Pradell, N. Salvadó, M. Vendrell-Saz, 1999, Evidence of tin oxide recrystallization in opacified lead glazes, Journal of the American Ceramic Society 82 (1999) 2871.
M. Tite, T. Pradell, A. Shortland, Discovery, production and use of tin-based opacifiers in glasses, enamels and glazes from the
late iron age onwards: a reassessment, Archaeometry 50 (2008) 67–84.
COM9
Synthesis of cellulose acetate grafted polystyrene copolymers via nitroxidemediated polymerization
E. Fedeli*1, G. Moreira1, L. Charles1, C. Lefay1, D. Gigmes1
1
Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, 13397 Marseille Cedex 20
Keywords: cellulose acetate, polystyrene, grafted copolymers, NMP.
Over the last two decades, an increasing attention has been drawn to polymers from renewable resources, such as
cellulose, for two main reasons: firstly, environmental concerns, and secondly, the awareness of the petroleum resources deplation. Although natural polymers have inherent biodegradability properties, they suffer from major
drawbacks, amongst which moisture sensitivity, which dramatically restricts the environment in which these polymers can be used, and poor mechanical properties which limit their application. In order to overcome these limitations one alternative consists in grafting covalently synthetic polymer chains on the polysaccharide backbone.
In line with this topic, in this communication we will present the grafting of polystyrene chains onto cellulose acetate (CA-g-PS) by Nitroxide Mediated Polymerization (NMP). Typically, the modification of the natural polymer is
obtained in three steps [2], namely: i) grafting of acrylate moieties onto the polysaccharide backbone; ii) Intermolecular 1,2 Radical Addition (1,2-IRA) of a SG1-based alkoxyamine (Blocbuilder® alkoxyamine) onto the acrylate
functions; iii) NMP of the styrene monomer from the polysaccharide backbone. A focus on the chemical characterization of the prepared polymers and the influence of the number of grafted initiators over the quality of control will
be also presented.
Fig. 1. Synthetic route to obtain CA-g-PS using NMP
References
1
J. Nicolas, Y. Guillaneuf, C. Lefay, D. Bertin, D. Gigmes, B. Charleux, Prog. Polym. Sci. 38 (2013) 63.
[2]
C. Lefay, Y. Guillaneuf, G. Moreira, J. Thevarajah, P. Castignolles, F. Ziarelli, E.Bloch, M. Major, L. Charles, M.
Gaborieau, D. Bertin, D. Gigmes, Polym. Chem. 4 (2013) 322
COM10
Polyphenols recovery from olive mill waste waters (OMWW) and synthesis of
unusual hydroxytyrosol derivatives.
E. Tassano*,1, L. Banfi1, A. Alama,2 A. Basso,1 R. Riva,1 A. Comite1
1
University of Genova, Department of Chemistry and Industrial Chemistry, Via Dodecaneso 31, 16146 Genova, Italy
2
IRCCS AOU San Martino-IST, L.go Rosanna Benzi 10, 16132 Genova,Italy
Keywords: olive mill waste waters; hydroxytyrosol; polyphenols; antioxidant.
The disposal of olive mill waste waters (OMWW) represents the mail environmental problem in the olive oil production; indeed this liquid has a high polluting organic load, due to a high content of organic substances, including
sugars, tannins, polyphenols, polyalcohls, pectins and lipids [1].
However, OMWW could be considered as a substantial source of valuable substances, especially for the high content of phenolic compounds.
Among these, the major compound is hydroxytyrosol (3,4-dihydroxyphenyl ethanol), a polyphenol endowed with
very interesting biological activities, as antioxidant [2], antinflammatory[3] and cancer chemopreventive [4].
Samples of OMWW were analyzed using HPLC to estimate hydroxytyrosol and other two phenols content; thereafter, the OMWW were treated with different methods (extraction, ion-exchange resins) in order to achieve the highest recovery of these substances from the raw material.
In addition, hydroxytyrosol was employed as starting material for the synthesis of unusual compounds.
Particularly, a first group of unprecedented hydroxytyrosol ethers was synthesized, paying specific attention to keep
intact the catechol moiety, which is responsible of the antioxidant activity.
Moreover, a second set of new derivatives was synthesized; in this case, hydroxytyrosol was combined by a 1,2,3triazole linker, a privileged scaffold in medicinal chemistry, with a second building block, which could presumptively increase the biological activity.
The pharmacological and antioxidant activity of these compounds is actually under evaluation.
Fig. 1. Hydroxytyrosol recovery and its conversion into unusual derivatives.
The research project is carried out in collaboration with Active Cells Srl and A&A Fratelli Parodi Spa.
References
N. Allouche, I. Fki, S. Sayadi, J. Agric.Food Chem. 2004, 52, 267.
F. Visioli, G. Bellomo, C. Galli, Biochem. Biophys. Res. Commun. 1998, 247, 60.
A. Procopio, S. Alcaro, M. Nardi, M. Oliverio, F. Ortuso, P. Sacchetta, D. Pieragostino, G. Sindona, J. Agric.Food Chem. 2009,
57, 11161.
R. Fabiani, A. De Bartolomeo, P. Rosignoli, M. Servili, G.F. Montedoro, G. Morozzi, Eur. J. Can. Prev. 2002, 11, 351.
COM11
Design of open carbon framework structures: a search for hydrogen adsorbents
P. Boulet*,1, A. MohammadHosseini1, B. Kuchta1
1
Aix-Marseille University and CNRS, MADIREL, St-Jérôme, Avenue Normandie-Niemen, F-13397 Marseille cedex 20
Keywords: Hydrogen storage, open carbon framework, Monte Carlo simulations, density-functional theory calculations
The search for efficient adsorbents able to store large quantity of hydrogen has motivated numerous studies over the
past decade. Ideally, such type of porous adsorbents should be light, and show both high surface area and high volumetric capacity. Among other materials, carbon nanotubes, metal organic frameworks (see e.g. [1,2]) and covalent
organic frameworks (COF) [3,4] have been explored.
In our approach we have combined structural heterogeneity and surface heterogeneity using scaffold type structures
based on polycyclic aromatic hydrocarbons (PAHs). The corresponding, hypothetical structures are named open
carbon frameworks (OCF), an example of which is presented in Figure 1. In this study, we have developed a structure with a theoretical surface area of more than 4000 m2/g which is more than 140% of the infinite graphene-based
structure.
The adsorption of hydrogen in these porous structures has been simulated using two theoretical approaches. Accurate DFT calculations that account for the van der Waals interactions have been performed for a set of common
PAHs as well as PAHs doped with heterogeneous atoms such as phosphorous, so as to obtain the interaction parameters of hydrogen with the heterogeneous surface. The DFT calculations also allow us to select the most attractive PAHs fragment for the construction of scaffold. Subsequently, grand-canonical Monte Carlo simulations have
been performed to simulate the hydrogen adsorption at both cryogenic and room temperatures and medium level
pressure (100 bar). The simulation results show that the doped scaffold structure exhibits more than 200% increase
in the hydrogen adsorption compared to infinite slit-like graphitic structures. The methodology and the outcomes of
this work will be described in details in this presentation.
Fig. 1. Hypothetical open carbon framework structure based on corronene molecules linked with one another.
References
[1]
Sculley, J.; Yuan, D.; Zhou, H.-C. The current status of hydrogen storage in metal–organic frameworks—updated.
Energy Environ. Sci. 2011, 4, 2721–2735.
2
Koh, K.; Wong-Foy, A. G.; Matzger, A. J. A Porous Coordination Copolymer with over 5000 m2/g BET Surface
Area. J. Am. Chem. Soc. 2009, 131, 4184–4185.
[3]
El-Kaderi, H. M.; Hunt, J. R.; Mendoza-Cortés, J. L.; Côté, A. .; Taylor, R. E.; ’Keeffe, M.; aghi, O. M. Designed
Synthesis of 3D Covalent Organic Frameworks. Science 2007, 316, 268–272.
[4]
Furukawa, H.; Yaghi, O. M. Storage of Hydrogen, Methane, and Carbon Dioxide in Highly Porous Covalent Organic
Frameworks for Clean Energy Applications. J. Am. Chem. Soc. 2009, 131, 8875–8883.
COM12
Conjugation of bioactive glasses with organic molecules: a model for the
development of new stimuli-responsive biomaterials for bone tumour treatment
C. Magistris1, V. Aina1, G. Cerrato1, G. Martra1, G. Viscardi1,
G. Malavasi2, G. Lusvardi2, L. Menabue2
2
1
University of Torino, Dep. of Chemistry and Centre of Excellence NIS, Via P. Giuria 7, 10125 Torino, Italy
University of Modena and Reggio Emilia, Dep. of Chemical and Geological Science, via G. Campi 183, 41125 Modena, Italy
Keywords: bioactive glasses, pH-dependent, stimuli-responsive biomaterials, maleic anhydride
Among controlled release systems, stimuli-responsive biomaterials have grown considerable interest as intelligent
therapeutic devices that enable the delivery of drugs at the site of interest by exploiting physiological conditions,
and its release in-situ when the therapeutic effects are needed. An altered metabolic feature, such as the lower extracellular pH of tumour tissue, can be exploited to trigger the release of the drug [1].
Bioactive glasses are silica-based inorganic materials, able to react with body fluids with the formation of an hydroxycarbonate apatite layer, which can assist bone matrix generation and growth. They can be employed to restore
the defects in damaged bone tissues and are widely used in the production of prosthetic devices in orthopaedic and
dentistry fields [2].
The aim of our project is the development of a functionalized bioactive glass that could be used as prosthetic material in the therapy of osteosarcoma, able to release an anticancer drug (such as doxorubicin) only in presence of
tumour cells. Osteosarcoma is the most common primary tumour of bone and the second highest cause of cancerrelated deaths in the paediatric age, and its standard therapy consists of chemotherapy, with surgery as the preferred
means of local control [3,4].
In the present contribution we report the first steps of this work. A series of bioactive glasses containing 3(aminopropyl)triethoxysilane was synthesized and characterized; the most promising bioglass was functionalized
with maleic and cis-aconitic anhydrides, two pH-sensitive spacers commonly used in drug delivery systems. The
bioglass was then conjugated with cysteamine and 5-aminofluorescein, as simple and non toxic models for NH 2containing organic molecules.
H2 N
O
O
O
R
O
O
O
O
OH
O
O
O Si
O
O
NH2
R = H, CH2COOH
O
O Si
O
N
H
HO
R
O
OH
O
O Si
O
O
H
N
O
N
H
R
OH
O
HO
R=H
Fig. 1: Bioglass functionalization with maleic and cis-aconitic anhydride and conjugation with 5-aminofluorescein
In-vitro release tests from the conjugated bioglass were then performed, in simulated biological fluids at different
pH. The materials, before and after the different functionalization steps and release tests, were characterized by
means of X-ray Powder Diffraction (XRPD), Raman, FTIR and fluorescence spectroscopies, N 2 adsorption, thermogravimetric (TGA) and elemental analysis. The release tests clearly show a dependency from pH, a promising
result for the development of a pH-sensitive drug delivery system.
1
al. (2012), Adv. Drug Delivery Rev. 64, 1021-1030
2
Regı´ et al. (2003), Eur. J. Inorg. Chem. 1029-1042
[3]
Dass C. R. et al. (2008), Current Cancer Drug Targets 8, 683-690
[4]
Dennis et al. (2009), Expert Opin. Drug Deliv. 12, 6, 1311-1321
Wang et
Vallet-
COM13
Reactivity studies of nanocatalysts under mild conditions: tandem 1,6-enynes thioacylation / cyclisation with gold and gold-palladium alloy nanoparticles
Irene Notar Francesco,1 Justine Giauffret,1 Fabien Fontaine-Vive,1 Jennifer K. Edwards,2
Graham J. Hutchings,2 Sylvain Antoniotti1*
1
Institut de Chimie de Nice, UMR 7272, Université Nice Sophia Antipolis – CNRS, Parc Valrose, 06108 Nice cedex 2, FRANCE
2
Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Park Place, Cardiff, CF10 3AT, UNITED KINGDOM
Keywords: nanocrystals • S-nucleophile • sustainable chemistry • radical reaction • thiyl radicals
Metal nanoparticles (NPs) have emerged as a novel class of catalysts with physical and chemical properties distinct
from individual mononuclear metals and bulk metal surface.[1] In a quest to fill the gap between homogeneous and
heterogeneous catalysis, nanocatalysts are currently in the spotlight for their ability to catalyse sophisticated reactions while offering great practical advantages such as stability, longevity and recycling capacities.
In this context, we studied the reactivity of 1,6-enynes in the presence of thioacetic acid (AcSH) and small amounts
of supported Au or Au-Pd nanoparticles (NPs) under mild conditions. The 1,6-enynes underwent a tandem thioacylation / cyclisation to original cyclic products featuring either a methylidene and a thioester function or an enol
thioester function depending on the substrate topology. The presence of precious metal NPs seems to stabilise the
formation of free radical intermediates.[2]
.
Fig. 1. Types of products and selectivities observed in tandem cyclisation / nucleophile addition of 1,6-enynes.
Substrates scope and limitations and comments on the reaction mechanism from experimental and theoretical results will be presented.
References
[1]
J. P. Wilcoxon, B. L. Abrams, Chem. Soc. Rev. 2006, 35, 1162-1194.
2
I. Notar Francesco, J. Giauffret, F. Fontaine-Vive, J. K. Edwards, G. J. Hutchings, S. Antoniotti, 2014, submitted.
COM14
3-Cyclopentyloxy-4-methoxyphenyl-isoxazoline derivatives
as new PDE4 inhibitors
C. Rotolo1, M. Massa1, E. Meta1, C. Brullo1 and O. Bruno,1*
1
Department of Pharmacy, University of Genoa, Viale Benedetto XV 3, 16132 Genoa-Italy
Keywords: Phosphodiesterases (PDEs), PDE4D inhibitors,PDE4B inhibitors, isoxazoline derivatives.
Phosphodiesterases (PDEs) are a large family of enzimes which regulate the intracellular level of cAMP and
cGMP. The type 4 (PDE4) is specific for cAMP and exerts a pivotal role in several cellular function. Four different
PDEs isoforms (namely PDE4A, PDE4B, PDE4C and PDE4D) are coded by independent genes. Among them,
PDE4D seems to be most involved in memory function whereas the PDE4B in inflammation processes.
Our recent research on PDE4 inhibitors (PDE4Is) as potential therapeutic agents for memory disorders, gave a series of small molecules (compounds 1) bearing a catecholic moiety and an amino function linked to the aromatic
portion by an imino-ether chain. SAR studies on those compounds evidenced a pivotal role for the chain length and
its spatial direction, particularly in determining the selectivity towards the different PDE4 isoforms [1,2,3].
To confirm these results and to investigate the chemical requirements for high selectivity, we planned to reduce the
linker flexibility of previous compounds 1 introducing an isoxazoline heterocycle between the catecholic moiety
and the terminal amino group. In detail, in position 3 of the isoxazoline ring we introduced an amide function maintaining two or three carbon atoms between the C=N-O- moiety and the cycloamine (compounds 2 and 3) as in the
previous compounds 1. Derivatives 2 and 3 were prepared by cyclization of 3-(cyclopentyloxy)-N-hydroxy-4methoxybenzimidoyl chloride with ethylacrilate or 3-butenoic acid to afford the corresponding isoxazoline ethyl
carboxylate or isoxazoline acetic acid, respectively, which were then subsequently functionalized to obtain the desired amides. On the other hand some of compounds 3 have been prepared also by an alternative convergent synthetic strategy, which involves the cyclization of the same N-hydroxy-benzimidoyl chloride with the suitable 4amine-3-buten-1-one properly prepared.
O
O
N
O
O
a
O
O
N
N
2
O
R
H
N
O
O
R
b
O
N
1a, b
N
O
O
O
3
Fig. 1. General structure of previous compounds 1 and new isoxazoline derivatives 2 and 3.
Synthesis of compounds 2 and 3 and results of the enzymatic test will be reported in the poster session.
References
1
O. Bruno, A. Romussi, A. Spallarossa, J.Med. Chem. 52 (2009) 6546.
2
O. Bruno, E. Fedele, J. Prickaerts, Brit. J. Pharmacol. 164 (2011) 2054.
[3]
C. Brullo, C. Rotolo, M. Rocca, NPCF 7 29-31 maggio 2013 Savigliano (CN) P 3.2 (2013).
N
COM15
CO2 capture and activation in functionalized microporous materials
A. Masala1*, J. G. Vitillo1,3, Jayashree Ethiraj1, Valentina Crocellà1, Gabriele Ricchiardi1, Carlo Lamberti1, Giovanni Agostini1, Bartolomeo Civalleri1, Sachin Chavan2; Sigurd Øien2, Greig. C. Shearer2, Stian Svelle2, Unni Olsbye2, Karl Petter Lillerud2, S.
Bordiga1
1
Department of Chemistry, Università di Torino and NIS-Nanostructured Interfaces and Surfaces-Centre, Torino, Italy
2
Department of Chemistry, University of Oslo, P.O. Box 1033, N-0315 Oslo, Norway
3
Department of Science and high Technology ,Università degli Studi dell'Insubria, Como, Italy
Keywords: CO2 capture, CO2 activation MOFs, Zeolites
The strict correlation between global temperature increase and the anthropogenic greenhouse gases emissions encouraged in the latter years the development of new solutions able to reduce the large CO 2 emissions no longer
maintainable by the atmosphere absorption. The study of a different range of promising CO2 microporous adsorbent
materials is one of the main assignments of U IT ’s Dep. of Chemistry, starting from M Fs and zeolites where
13X constitute the reference materials in both adsorption and separation studies. Costs and carcinogenic nature of
aliphatic amines which have been historically employed as CO2-scrubbers for post-combustion streams, inspired
strong motivations towards the seeking of efficient CO2-adsorbent alternatives: several are the mesoporous systems
which have been synthetized and characterized by our laboratories, but UiO-66 [1] and UiO-67 shown the higher
performances which have been then compared with those of selected derivates [2] and homologue materials with
mixed ligands (4,4’-biphenyl-dicarboxylate (bpdc) and 2,2’-bipyridine-5,5’-dicarboxylic (bpydc)), able to coordinate extra metal sites with coordinative vacancies, such as Pt(II) or Pt(IV). The high stability of UiO-66 and UiO-67
structures coupled with the presence of metal sites with
coordinative vacancies, it is expected to strongly improve the material adsorption capacities towards CO2.
Another good alternative is represented by the alkali
metal oxides as efficient materials for CO2 chemisorption: the high temperature required for their regeneration
or very high working temperature seems to hinder [3] a
reasonable reaction’s yield and yet improvements in the
kinetics and affinity toward CO2 have been shown for
MgO supported on mesoporous materials as HY and
ZIF-8. Different characterization methods are meant to
be use in order to evaluate the volumetric capacity of the
materials and the affinity of their active sites towards
Fig 1: Examples of materials based on Zr6O4(OH)4
CO2 and N2, their surface areas and porosity. Carbon
building block
capture and sequestration (CCS) process is one of the
strategies that have been proposed to actuate the separation of CO 2 from low pressure gas-streams at temperatures
slightly higher than RT but an improvement on the catalyst regeneration’s methods is required in order to lower the
cost and so enhance the sustainability of the entire CCS chain [4]; in order to make the adsorbent material suitable
for the different catalyst regeneration’s methods (like pressure swing adosorption, temperature swing adsorption or
electric swing adsorption) mostly used at the end of a post-combustion gas-stream, a tailoring or modification of the
active phase belonging to zeolites rather than MOFs or oxides has to be taken in account as a possible target for the
next future.
References
Cavka J.H., et al., J. Am. Chem. Soc. 130 (2008) 13850.
Vitillo J.G., et al., ChemSusChem 4 (2011) 1281
S. Wang, S. Yan, X. Ma and J. Gong, Energy Environ. Sci., 4 (2011) 3805.
M. Z. Jacobson, Energy Environ. Sci. 2009, 2, 148.
COM16
Synthesis and antibiofilm activity of bromotyramines analogues.
S. Andjouh1* and Y. Blache1
1
Université de Toulon, Laboratoire MAPIEM, EA 4323, Avenue de l’Université, BP 20132, F-83957 La Garde
Cedex, France
Keywords: natural products, bromotyramine analogues, triazole, antifouling, biofilm.
Inspired by the impressive level of biodiversity in the marine environment, natural product antifoulants have been
extensively investigated recently in search of environmentally benign replacements for tributyltin in maritime coatings applications. Many of the active antifouling compounds identified are bromotyramine derivatives, including
Moloka’iamine [1] (A), 3,5-dibromo-4-methoxy-b-phenethylamine [2] (B) and N-methyl-3-bromotyramine [3] (C)
witch was purified by our group. We felt that the relatively simple structure of these compounds, based on an Oalkylated dibromotyramine core, invited the synthesis of analogues in an effort to probe antifouling structureactivity relationships (SAR).
X
R1
NH3
R
n N N
N
O
Br
R'
O
Br
A : R1 = (CH2)3NH3+ , X=Br
B : R1 =CH3 , X=Br
C : R1 = H , X=H
Figure 1: bromotyramine derivatives
Cu-catalyzed
cycloaddition
n N3
R
O
+
R'
Br
Figure 2: targeted library of analogues
For the present study, a new synthetic plan, based on click chemistry, was devised that would allow for the rapid
and efficient synthesis of libraries of bromotyramine/triazole analogues on a suitably large scale. The click chemistry is a highly efficient process in bond formations among diverse building blocks for chemical synthesis. In addition, a number of compounds containing 1,2,3-triazoles have shown a broad spectrum of biological activities such
as antifouling [4]. The general structures of the targeted library, as well as the retrosynthetic analysis are reported in
figure 2. These compounds were prepared in an efficient way from organic azides and terminal alkynes, and then
investigated for their anti-biofilm performance against marine bacteria isolated on artificial surfaces in Mediterranean Sea to obtain relevant information in terms of SAR.
References
[1]
[2]
[3]
[4]
M. T. Hamann, P. J. Scheuer, M. Kelly-Borges, J. Org. Chem. 1993, 58, 6565.
R. M. Van Wagoner, J. Jompa, A.Tahir, C. M. Ireland, J. Nat. Prod. 1999, 62, 794.
N. Penez, G. Culioli, T. Perez, J.F. Briand, O. P. Thomas, Y. Blache, J. Nat. Prod. 2011, 74, 2304
S. A. Rogers, C. Melander, Angew. Chem. Int. Ed. 2008, 47, 5229.
COM17
Novel size- and shape-controlled silica nanofillers for tires reinforcement
R. Di Legami*, M. Castellano
Dipartimento di Chimica e Chimica Industriale, Università degli Studi di Genova, Via Dodecaneso 31, 16146 Genova, Italia
Keywords: Silica nanoparticles, elastomer compounds, inverse gas chromatography,surface properties
Although carbon black is the most widely used reinforcing filler in rubber compounds, in the last two decades it
was suggested to progressively substitute it with silica. It is known [1, 2] that such a filler leads to a general improvement of the properties of rubber compounds, in excess to those given by carbon black. This works especially
for nanocomposites used in the tyre industry, because silica is able to increase wet grip reducing rolling resistance
at the same time, and, as a result, decrease fuel consumption.
Silica surface is characterized by a high surface energy, due to the presence of OH silanol groups, which give rise to
strong interactions between silica particles and induce a very strong filler networking. This makes the dispersion of
such particles into conventional nonpolar tyre elastomers very difficult; as a consequence, the tread wear becomes
critical. To improve silica dispersion, it is necessary to promote silica-rubber interactions opposite to silica-silica
interactions, in order to reduce the filler agglomeration. Hydrophobation of the silica surface by chemical reaction
with organosilanes has been suggested as the key to achieve this goal [3]. TESPT, (bistrietoxysilylpropyltetrasulfide) is, at present, the most widely used silane modifier because it gives rise both to hydrophobation of silica surface and chemical bonding between filler and matrix [4].
Silica nanoparticles with different aspect ratios (A. R.) have been tested with respect to their effectiveness as reinforcing fillers for s-SBR based nanocomposites for “green tires”, i.e. tires with lower rolling resistance. A commer®
cial fumed silica nanofiller with A.R.=1 (Aerosil 200 from Evonik) has been therefore compared with two nanosilica samples (LB20 and LB17, with A.R. 2 and 4, respectively) synthetized by means of an innovative process [5].
In addition, TESPT was grafted onto their surface, in order to obtain more hydrophobic materials and to enhance
their dispersion in elastomeric compounds.
Pristine and modified samples were then compared. Thermodynamic surface properties were investigated by inverse gas chromatography (IGC), in order to predict the filler-elastomer interactions; then, s-SBR/silica compounds
were prepared and characterized using vulcanization tests, assessing their dynamic-mechanical properties and carrying out morphological observations by TEM.
Overall, IGC measurements demonstrated that the hydrophobation treatment with TESPT results in a reduction of
surface tension of silica, as indicated by a decrease of thermodynamic parameters such as –ΔG°, -ΔH° and –ΔS° of
adsorption. Dynamic-mechanical tests and TEM observations confirmed this results, showing a better dispersion in
rubber composites filled with modified silica.
The authors would like to thank Prof. R. Scotti of Università Milano Bicocca for having kindly supplied LB20 and
LB17 samples, and Dr. Lucia Conzatti of CNR-ISMAC Genova for having carried out TEM analysis.
References
1
H. Mouri, K. Akutagawa, Rubber Chemistry and Technology. 72 (1999) 960.
[2]
L.Conzatti, G. Costa, M. Castellano, A. Turturro, F. Negroni, J. F. Gérard, Macromolecular Materials and Engineering. 293 (2008) 178.
[3]
M. Castellano, L. Conzatti , A. Turturro, G. Costa, G. Busca, Journal Physical Chemistry B. 111 (2007) 4495
[4]
G.Costa, G. Dondero, L. Falqui , M. Castellano, A. Turturro, B. Valenti, Macromolecular Symposia. 193 (2003) 195
[5]
D.
Xin,
H.
Junhui,
Dalton
Transactions.39
(2010)
9063.
COM18
th
JFIC -GIFC,
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7th JFIC
AFM Catalysis: Focus on Spatially Resolved Surface Functionalization
J. Botton1, D. Valyaev1, O. Chuzel*,1, J-L. Parrain*,1,
V.Mesquita2, S. Clair*,2, M. Abel2, L. Patrone2
1
Aix-Marseille Université - Institut des Sciences Moléculaires de Marseille (UMR 7313), Service 532, Faculté de Sciences
et Techniques de St Jérôme, Av. Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France
2
Aix-Marseille Université - Institut de Matériaux Microélectronique et Nanoscience de Provence
(UMR 7334), Service 151, Faculté de Sciences et Techniques de St Jérôme, Av. Escadrille Normandie-Niemen, 13397 Marseille
Cedex 20, FRANCE
Keywords: AFM, Surface Functionalization, Local Epoxidation, Heterogeneous Catalysis, Self-Assembled Monolayers.
Scanning probe (STM and AFM) nanolithography belongs to the most important methods for creation of nanoobjects on the surface with sub-100 nm resolution. It is generally based on the direct diffusion transfer (Dip-Pen
nanolithography) and mechanic or electrical destruction of the surface. Limited reports on the AFM catalyzed
chemical surface modification was achieved using AFM probes coated with metals (Pd and Pt – azide hydrogenation[1] and alkene hydrosilylation[2]), metal oxides (Cu2O, alkyne-azide "click" reaction[3]) and absorbed metal nanoparticles (Pd NPs, Suzuki and Heck cross-coupling[4]).
We report herein the first use of the AFM tip with immobilized homogeneous catalyst for spatially controlled
epoxidation of the surface terminal alkene groups (Fig. 1).[5]
Catalytic AFM probe
[O]
Cat
R'
R'
[O]
N
O
R
R
N
O
OH
OH
RR'NH
n
n
silicon
n
n
n
n
silicon
n
n
LA
n
n
n
n
silicon
Fig. 1. AFM topography image of the surface after local epoxidation of two 1 x 1 μm squares on the alkene terminated SAM
followed by ring opening reaction with a secondary amine
The local epoxidation of terminal alkene Self-Assembled Monolayer (SAM) was carried out in an oxidative liquid
medium at the contact between the catalytic AFM probe and the surface. It was followed by derivatization of the
resulting epoxide with a secondary amine in the presence of a Lewis acid (Fig. 1). AFM topography images showed
unambiguously a well-pronounced surface growth in the epoxidized area only. The height of the objects matched
with the length of the amine indicating the controlled formation of localized aminoalcohol domains on SAM. The
concept used in this work could be attractive for the controlled 3D fabrication of various types of nanodevices.
References
[1] W. T. Mueller, D. L. Klein, T. Lee, J. Clarke, P. L. McEuen, P. G. Schultz, Science 1995, 268, 272.
[2] C. Blackledge, D. A. Engebretson, J. D. McDonald, Langmuir 2000, 16, 8317.
[3] W. F. Paxton, J. M. Spruell, J. F. Stoddart, J. Am. Chem. Soc. 2009, 131, 6692.
[4] J. J. Davis, C. B. Bagshaw, K. L. Busuttil, Y. Hanyu, K. S. Coleman, J. Am. Chem. Soc. 2006, 128, 14135.
[5] D.A.Valyaev, S. Clair, L. Patrone, M. Abel, L. Porte, O. Chuzel, and J-L. Parrain, Chem. Sci. 2013, 4, 2815.
COM19
Chemometric and experimental design approaches to open validation protocols.
Prediction of validation parameters in multi-residue UHPLC-MS/MS methods.
E. Alladio1,2, V. Pirro1, D. Di Corcia2, E. Gerace2, A. Salomone2, M. Vincenti*,1,2
1
2
Dipartimento di Chimica, Università degli Studi di Torino, Via P. Giuria 7, 10125 Torino
Centro Regionale Antidoping “A. Bertinaria”, Regione Gonzole 10, 10043 Orbassano, Torino
Keywords: Open validation, PLS-Regression, multi-residue UHPLC-MS/MS, Validation parameters prediction
Ultrahigh-performance liquid chromatography – tandem mass spectrometry (UHPLC – MS/MS) methods nowadays allow to simultaneously screen and detect tens or even hundreds of target analytes, contained in single biological samples. However, the traditional approach to quantitative method validation presents three major drawbacks,
such as (i) it is extremely laborious, repetitive and rigid; (ii) it does not allow to introduce new analytes without
starting the validation from its very beginning and (iii) it is performed on spiked blank matrices, whose very nature
is significantly modified by the addition of a large number of selected analytes standard solutions.
In the present study, several predictive chemometric models were developed from closed sets of analytes in order to
estimate validation parameters on molecules of the same class, but not included in the original training set. Retention time, matrix effect, recovery effect (i.e. see Figure 1), detection (LOD) and quantification (LOQ) limits were
predicted with Principal Components Analysis (PCA) and Partial Least Squares - Regression (PLS-R) methods. In
particular, Iterative Stepwise Elimination (ISE), Iterative Predictors Weighting (IPW) and Genetic Algorithms (GA)
were exploited and compared together as variables selection techniques. These procedures were initially applied to
data previously reported in validated UHPLC-MS/MS multi-residue methods for human whole blood[1], oral fluid[2], urine[3] and hair[4]samples, proving effective and in accordance with the recommendations of SOFT/AAFS
validation guidelines. Secondly, a new validation procedure was developed for multi-residue methods based on the
robustness parameter, allowing a rapid and full evaluation of the main validation parameters required by international guidelines. Our protocol suggests to investigate samples differently spiked with coeluting and non-coeluting
analytes, in order to evaluate electrospray (ESI) signal suppressions phenomena and interferences in realistic situations, in opposition to fully spiked blank samples at concentrations comprised by standard validation practices. At
last, chemometrically-driven validation protocols are proposed in order to include new analytes into existing validated methods, together during typical validation practices.
Fig. 1. Recovery effect (RE) prediction of Naloxone by the PLS-R model for oral fluid method[2].
References
[1]
M. Vincenti, D. Cavanna, E. Gerace, V. Pirro, M. Petrarulo, D. Di Corcia, A. Salomone, Anal. Bioanal. Chem. 405 (2013)
863.
[2]
D. Di Corcia, S. Lisi, V. Pirro, E. Gerace, A. Salomone, M. Vincenti, J. Chromatogr. B 927 (2013) 133.
[3]
A. Salomone, E. Gerace, P. Brizio, M. C. Gennaro, M. Vincenti, J. Pharm. Biomed. Anal. 56 (2011) 582.
[4]
A. Salomone, E. Gerace, F. D’Urso, D. Di Corcia, M. Vincenti, J. Mass Spectrom. 47 (2012) 604.
COM20
Energy Storage and Conversion at the Nanoscale
L. Assaud*,1,2, M. Hanbücken1, L. Santinacci1
1
Centre Interdisciplinaire de Nanoscience de Marseille, CNRS, Aix-Marseille Université,
Campus Luminy, 13288 Marseille, France
2
Friedrich-Alexander University Erlangen Nuremberg, Department of Inorganic Chemistry,
Egerlandstrasse 1, 91058 Erlangen, Germany
Keywords: ALD, Electrocatalysis, Nanomaterials, Energy
In order to meet the growing needs in today's society that requests more transportation and portable devices, energy
production, conversion and storage systems are now experiencing real changes. In order to fabricate systems able to
generate a controlled, renewable and green energy, nanoscience and nanotechnology are leading research fields.
The present work describes the fabrication of nanosized and large-scale organized structures. These nanostructures
have been functionalized through film and particle synthesis using a chemical vapor deposition method: the Atomic
Layer Deposition (ALD).
Thus, metal/insulator/metal (MIM) systems are fabricated on highly-ordered high-aspect ratio porous alumina
membranes. The materials that have been deposited are TiN and HfO2 as conductive and insulating material, respectively. The aim is to produce high performance nanocapacitors that can be used for data storage application or for
energy storage in small devices such as RFID.
In a second part, metallic catalysts such as Pd, supported on TiO2 nanotubes (figure 1), have been synthesized for
ethanol electrooxidation. This system can be used as anode in direct alcohol fuel cells.
The synthesis and characterization of those systems will be presented and discussed.
Fig. 1 : Bare TiO2 nanotubes (left), Pd nanoparticles supported on TiO2 nanotubes (right)
COM21
Synthetic approaches to the design of efficient MRI probes
L. Tei*,1, M. Botta,1 G. Gambino,1 G. Gugliotta,1 J. Martinelli1
1
Dipartimento di Scienze ed Innovazione Tecnologica, Università degli Studi del Piemonte Orientale ”Amedeo Avogadro”,
Viale T. Michel 11, 15121 Alessandria, Italy
Keywords:Magnetic Resonance Imaging, contrast agents, bifunctional chelates, diazepine, dendrimers.
The synthesis of variously substituted 1,4-diazepines is highly important for their wide spectrum of biological activity and for their use as scaffold for the development of efficient contrast agents (CAs) for Magnetic Resonance
Imaging (MRI). In fact, the Gd(III)-complex based on the polyaminopolycarboxylate ligand AAZTA (6-amino-6methylperhydro-1,4-diazepinetetraacetic acid) is characterized by optimal magnetic properties and by high thermodynamic stability and kinetic inertness essential for an in vivo use.[1] Thus, the preparation of derivatives containing
an appropriate functional group for conjugation to a specific biological vector has widespread utility for the synthesis of MR - Molecular Imaging probes.
A series of derivatives were synthesized from N,N’-dibenzyl-6-hydroxymethyl-6-nitroperhydro-1,4-diazepine via a
novel tandem procedure involving retro-Henry reaction (to obtain the corresponding carbanion/ nitronate) followed
by either Michael or Mannich reactions using several acrylic derivatives and different primary and secondary
amines (Scheme 1a).[2] Moreover, novel bifunctional AAZTA-like agents with hydroxyl, carboxyl, chloro, amino
and isothiocyanate functional groups were prepared and tested by reacting them with biological vectors or inorganic
nanoparticles.[3,4] Mono- and dimeric bifunctional chelators bearing a isothiocyanate group were prepared from the
AAZTA-like chelator with a free hydroxymethyl group and the carboxylates protected as t-butyl esters (AAZTAOH, Scheme 1b) and were used for the synthesis of multimeric and dendrimeric ligands by reaction with ethylendiamine, tris-(2-aminoethyl)amine, and generation-0, I and II PAMAM dendrimers.[4] A 1H NMR relaxometric
characterization was carried out by analysing the 1H relaxivity data as a function of magnetic field strength and
temperature. Remarkable signal enhancement at different magnetic fields was observed in T1-weighted phantom
MR-images of Gd-multimers in respect to commercial agent ProHance ®. The improved efficiency shown by these
Gd-dendrimeric/ multimeric complexes make them potentially useful CAs for both clinical MRI and Molecular
Imaging applications.
a)
NO2
HO
N
O
Ph
N
retro-Henry
Ph
Ph
N
K+
O
N
N
R
N
R'
Mannich
Ph
N
N
Ph
Ph
NO2
Michael
EWG
b)
N
Ph
N
Ph
COOtBu
COOtBu
COOtBu
N
+
N
OCN
COOtBu
N
HO
NO2
tBuOOC
tBuOOC
tBuOOC
N
N
N
NO2
NCO
H
N
O
tBuOOC
AAZTA-OH
H
N
O
O
O
COOtBu
COOtBu
COOtBu
N
N
R = NO2
R = NH2
N
COOtBu
R = NCS
R
Scheme 1. a) Tandem retro-Henry /Mannich or Michael reactions; b) Synthesis of dimeric bifunctional chelates.
References
1
S. Aime, et al., Inorg. Chem. 43 (2004) 7588.
[2]
J. Martinelli, G. Gugliotta, L. Tei, L., Org Lett., 14 (2012) 716.
[3]
G. Gugliotta, M. Botta, G. B. Giovenzana, L. Tei, L; Bioorg. Med Chem. Lett. 19 (2009) 3442.
[4]
G. Gugliotta, M. Botta, M.; Tei, L; Org. Biomol. Chem. 8 (2010) 4569.
COM22
7thth JFIC
JFIC -GIFC,
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
Towards new mesoporous nanomaterials targeted for biological applications:
Sensing of low dose molecules by SERS effect
Déborah Fernand*,1, Virginie Hornebecq1, David Bergé-Lefranc2, Trang Phan3,
Alexandre Merlen4, Cédric Pardanaud5
1
2
MADIREL Laboratory UMR 7246, Aix-Marseille University, Marseille France
IMBE Laboratory UMR 6263, Faculty of Pharmacy, Aix-Marseille University, Marseille, France
3
ICR, UMR 7273, Aix-Marseille University, Marseille France
4
IM2NP, UMR 7334, Aix-Marseille University, Marseille France
5
PIIM Laboratory UMR 7345, Aix-Marseille University, Marseille France
Keywords: Nanocomposites, Porous, Sensing, Raman, SERS
The detection of biological molecules at very low concentrations is an important challenge for biochemists
and one of the solutions foreseen for this purpose is to sense these molecules using SERS (Surface Enhanced
Raman Scattering) effect. Indeed, Raman spectroscopy is a rapid, simple and non-destructive technique.
Furthermore, since its discovery in 1974 by M. Fleischmann et al. [1], SERS effect has been proved to be one of the
most sensitive spectroscopic tools for chemical analysis. SERS effect is evidenced when a Raman active molecule
is adsorbed on nanostructured surfaces containing metals (mainly, noble metals such as gold or silver). SERS
substrates can be prepared using several ways: deposition of metallic nanoparticules onto a glass substrate, electron
beam lithography and electrochemical roughening or physical deposition techniques such as pulsed laser deposition
or sputtering. One of the challenges in the development of biochemical techniques is the design of SERS substrates
presenting the lowest detection threshold that are easy to prepare and to tune.
In this context, porous nanocomposites composed of mesoporous silicas and noble metal nanoparticles
(Ag/Au) with tunable size are studied as SERS substrates for the detection of molecules at low concentrations.
Indeed, these materials present the advantage to combine two properties: the superconcentration of molecules in the
solid related to the high specific surface area and the presence of nanostructured noble metal to generate the SERS
effect. In this way, mesoporous silicas are synthetized using the sol-gel method and Ag nanoparticules are
incorporated via the impregnation of a silver salt followed by its reduction. Then, adsorption isotherms of the probe
molecule on both pure mesoporous silica matrix and nanocomposites are constructed and associated enthalpies of
adsorption are determined using calorimetric measurements. The Raman response of the probe molecule is finally
studied for particular isotherms parts. The coupling between thermodynamics and Raman spectroscopy leads to a
better understanding of SERS effect origin as it allowed the separation between the chemical and electromagnetic
mechanisms. Finally, the influence of several parameters on both thermodynamic properties and the Raman
response is discussed: the nanoparticles size, the chemical nature of the probe molecule, the correlation between
the laser excitation wavelength, the plasmon band position of nanoparticles and the optical properties of the probe
molecule.
References
1
M. Fleischmann, P.J. Hendra, A.J. Mc Quillan, Chemical Physics Letters 26 (1974) 163.
COM23
Development of imidazo-pyrazole derivatives
as potential antimetastatic agents in neuroblastoma
E. Meta1, M. Massa1, C. Brullo1, O. Bruno1*
1
Dipartimento di Farmacia, Università degli Studi di Genova, viale Benedetto XV, 3, 16132 Genova, Italy
[email protected]
* correspondig author : [email protected]
Keywords: neuroblastoma, metastasis, imidazo-pyrazole, chemotaxis
Chemotaxis is a complex process which consists of the neutrophils migration to the site of inflammation; this
patho-physiological event is regulated by downstream signalling molecules, including phosphatidylinositol 3-kinase
(PI3K), phospholipase C, mitogen activated protein kinases (MAPKs) and extracellular response kinases 1 and 2
(ERK1/2). In the last years it has been observed that tumor cells use the same molecular tools (adhesion molecules,
cytokines, chemokines, chemokine receptors) and pathways in order to spread out its anatomical site and to generate metastasis. In particular, the p38MAPK pathway is known to regulate cancer development by modulating not
only angiogenesis, but also cell motility, invasion and metastasis formation.
In pursuing our search on chemotaxis, we recently studied our imidazo-pyrazoles 1 (Figure 1), which are able to
block neutrophil recruitment at nanomolar concentration [1], to assess their effect on specific chemotactic kinases.
Our data demonstrated that they strongly inhibit p38MAPK and different PKC isoforms phosphorylation in neutrophils activated by chemoattractant agents such as fMLP-OMe and IL8 [2].
With the aim of expanding their possible therapeutic applications and taking into account the correlation between
the p38MAPK phosphorylation activation and metastasis onset, derivatives 1 were tested on in vitro invasion metastatic test using an high-risk neuroblastoma cell lines (ACN), being this pediatric tumor highly able to form metastasis.
Interestingly, in this preliminary test we point out that tested compounds can reduce neuroblastoma cell movement,
independently by IL8 or fMLP activation, with an IC50 value in the low micromolar range [3].
To obtain more potent compounds, we designed new derivatives (2, Figure 1) moving the urea function (fundamental for chemotaxis inhibition) from position 1 to position 7 of imidazo-pyrazole scaffold. New compounds 2 were
synthesized using a step by step chemical approach, that firstly involves a nitrosation at position 7 of the imidazopyrazole nucleous, then a reduction to an amino group and finally implicates the amino transformation in a differently substituted urea function. Synthesis and biological evaluation will be reported in the poster session.
O
R
O
F
N
H
N
N
N
X
N
H
HN
1
R = CONH2 , CONR 2
R 2 = piperidino, cyclopropylamino
NH
N
N
2
X = H, F, CF 3
Fig. 1. Chemical structures of compounds 1 and 2.
References
[1] C. Brullo, S. Spisani, R. Selvatici, O. Bruno,. Eur. J. Med. Chem. 47 (2012) 573.
[2] R. Selvatici, C. Brullo, O. Bruno, S. Spisani, Eur. J. Pharmacol. 718 (2013) 428.
[3] C. Brullo, B. Marengo, C. Rotolo, M. Massa, R. Ricciarelli, M. A. Pronzato C. Domenicotti, O. Bruno, XXII Meeting Nazionale della SCI, Roma 10-13 Settembre 2013, P.OE.04.
COM24
Synthesis and photophysical studies of ew Boron Difluoride Complexes of βDiketonates Ligands with Extended Conjugation
Abdellah FELOUAT1*, Anthony D’ALE
1
1*
and Frédéric FAGES1
CINaM UMR 7325, Aix Marseille Université, Campus de Luminy, Case 913, Marseille, 13288 Cedex 9, France
E-mail : : [email protected]
Keywords: Boron difluoride complexes, fluorescence, dyes, curcuminoids
We present the design and the photophysical study of a new family of boron difluoride complexes of βdiketonates with extended π-conjugated systems which belong to curcuminoid family. While cucumine,
which is a natural product extracted from Curcuma, is well know and extensively studied, the curcuminoid derivatives and their boron difluoride complexes have been only scarcely examined.
Figure: A new Boron difluoride complexes
Among these ligands, we devoted particular attention to those which bear an aryl group at the “meso”
position, a family of compounds that has not been reported in literature to date.
The synthetic route that allows the introduction of the meso substituents is presented. Dynamic conformational study using 19F NMR and photophysical (stationary and time-resolved fluorescence emission)
allowed the evaluation of influence of meso-aryl group in fundamental and excited singlet states. The XRay diffraction analysis of those complexes is presented. The presence of a meso-aryl group imparts an
additional solubility in organic solvent and attractive photophysical properties in solution and solid state
to the curcuminoïd skeleton. The results obtained on this first generation of molecules are very encouraging for using such dyes in opto-electronic devices.
References
1
C. Ran, X. Xu, A. Moore, J. Am. Chem. Soc. 2009, 131, 15257–15261.
COM25
2
A. Felouat, A. D’Aléo, F. Fages, J. Org. Chem. 2013, 78, 4446−4455.
“What the cells see”: factors affecting the orientation of proteins adsorbed
on hydroxyapatite nanoparticles
P. Ivanchenko*, Y. Sakhno, F. Catalano, V. Aina, G. Martra
Department of Chemistry and Interdepartmental Centre, ‘‘Nanostructured Interfaces and Surfaces-NIS’’, University of Torino,
via P. Giuria 7, 10125 Torino, Italy;
Keywords: protein adsorption, nanohydroxyapatites, surface structure, IR probes, Z-potential, CD-UV
Since the concept of “biological surface science” has been established [1], the central role of the causal sequence:
structure of the surface of biomaterials/state of adsorbed proteins/response elicited in cells has been recognized.
Such sequence holds also for nanosized hydroxyapatite particles (HA), which are among materials of biomedical
interest as biomimetic counterpart of inorganic phase of bones and teeth [2]. From a structural point of view, the
HA lattice can be described as an A-B-A-A-B-A-A- sequence of Ca3(PO4)2 (A) and Ca4(PO4)2(OH)2 (B) layers
parallel to 010 crystal planes. Hence, for such facets the most exposed layers results as ...-A-B-A, ...-A-A-B, or
...-B-A-A giving rise to the stoichiometric HA(010) and the nonstoichiometric HA(010)_Ca-rich and HA(010)_Prich surfaces, respectively. In this respect, Kandori et al [3] reported that acidic proteins (e.g. bovine serum albumin, BSA) are preferentially adsorbed on Ca-rich sufaces, whereas basic ones (e.g. lysozyme) on P-rich surfaces.
However, besides these otherwise important selectively aspects, which is the effect, if any, of the structure of the
facets in orienting the proteins towards the adsording surfaces? The relevance of such question can be appreciated
by considering that when biomaterials are introduced in a living organism, cells never “see” their suraces, but interacts with the “epitopes” exposed by the adsorbed protein layers (the so-called protein corona).
Here we report the results of an investigation contributing to the elucidation of this matter, carried out by combining i) the recognition of the surface structure of HA nanoparticles, and ii) quantitative and structural study of adsorbed BSA, used as model protein.
As for point i), the use of a theoretical-experimental model recently established by some of us, based on IR features
of CO adsorbed as probe molecule [4] allowed to establish that two types of HA nanoparticles prepared in different
ways (hereafter referred to as HA_1 and HA_2) exposed Ca-rich and P-rich surfaces (representing the overwhelming majority of particles facets) in a 2: 1 and 1:2 ratio (for HA_1 and HA_2, respectively). Accordingly, the two
materials exhibited Z-potentials different in value and sign when suspended in HEPES buffer, being ca. -17 mV for
HA_1 and ca. -12 mV for HA_2.
Passing to point ii), once a monolayer of adsorbed BSA was attained by incubation in a BSA solution buffered with
HEPES (surface coverage also monitored by the appearance of protein-protein interactions effects on the CD-UV
spectra of adsorbed BSA), the Z-potential increased to ca. -11 mV for HA_1/BSA, whereas decreased to ca.
-20
mV for HA_2/BSA. Essentially the same values were obtained when additional protein layers were adsorbed.
The attainment of mono- or multylayers of adsorbed proteins prevents the contribution of HA surfaces to the Zpotential, and then these difference in the potential of the HA/BSA systems should stem from differences in “surfaces” exposed to the liquid medium by adsorbed proteins (Scheme 1). In particular, a Z-potential of ca. -20 mV
corresponds to the value expected for adsorbed BSA molecules keeping their domain III in contact with the incubation medium, whereas the exposure of domains I and II should result in a less negative Z-potential [5].
To our knowledge, this study is the first to report the effect of differences in the structure of surfaces of a biomaterial, even if related to the same type of crystal plane, towards the orientation assumed by adsorbed proteins.
Scheme 1. Orientation of BSA onto
different types of HA surfaces resulting
in different domains exposed to
the environment.
References
[1] B. Kasemo, Surf. Sci. 500 (2002) 656–677.
[2] S. Dorozhkin, S. Mater. Sci. 2 (2009) 1975-2045
[3] K. Kandori, A. Fudo, T. Ishikawa,.Colloids Surf. B 24 (2002) 145−153.
[4] F. Chiatti, M. Corno, Y Sakhno, G. Martra, P. Ugliengo, J. Phys. Chem. C 117 (2013) 25526−25534.
[5] B. Mueller, M. Zacharias, K. Rezwan, Adv. Eng. Mater. 12 (2010) B53-B61.
COM26
The human OR1G1 olfactory receptor is involved in the combinatorial code of
-santalol.
C. A. de March1, N. Baldovini1, A.-M. Lebon2, J. Golebiowski*,1
1
Institut de Chimie de Nice, UMR CNRS, Université de Nice Sophia Antipolis 7272, 06108 Nice Cedex 2, France
2
Centre des Sciences du Goût et de l’Alimentation, UMR 1324, INRA, 21034 Dijon Cedex, France
Keywords: olfactory receptor, sandalwood, molecular modelling, cellular biology, structure odor relationships
With its characteristic woody fragrance and its fixative properties, sandalwood is one of the most precious natural
raw materials used in perfumery. The main odorant components of natural sandalwood are (+)-(Z)--santalol and
especially (–)-(Z)--santalol which shows the most typical and characteristic sandalwood odor. Today, a large
number of synthetic substitutes of -santalol are available for the perfumers in search of affordable sandalwood
odorants, and many of them have a molecular structure completely different from that of -santalol.
Despite many Structure-Odor Relationships studies on sandalwood [1], the action mode of sandalwood odorant
molecules remains to be addressed. In fact, olfactory receptors involved in their perception have not yet been
identified.
In our study, the interaction of a human olfactory receptor, hOR1G1 (Figure 1), with sandalwood odorants has been
investigated. We experimentally show that -santalol is a strong agonist of hOR1G1, contrarily to -santalol and
another closely related compound, III-santalol. An atomic-scale model [2] is then inferred through the use of both a
sandalwood pharmacophore and the prediction of the position of these compounds within the cavity of the receptor.
State of the art molecular dynamic simulations show how the receptor is able to discriminate agonist from nonagonist odorants in spite of their similarities.
Such approaches constitute the first step in the understanding of the sandalwood odor combinatorial code.
Fig. 1. -santalol and two analogs docked in our model of hOR1G1.
References
1.
Chapuis, C., In The Quest for a Virtual Pseudo Receptor for Sandalwood-Like Odorants. Chemistry & Biodiversity,
2004. 1: p. 980-1021.
2.
Charlier, L., et al., Molecular Modelling of Odorant/Olfactory Receptor Complexes, in Olfactory Receptors2013. p.
53-65.
Claire A. de March thanks Giract for a PhD bursary and the Roudnitska foundation for funding her PhD thesis. The
Olfactome project is funded by the région Provence Alpes Côte d’Azur.
COM27
Enantio- and Diastereoselective Synthesis of Highly Substituted
Benzazepines by a Multicomponent Strategy Coupled with
Organocatalytic and Enzymatic Procedures
Lisa Moni, Luca Banfi, Andrea Basso, Andrea Galatini, Martina Spallarossa,
Renata Riva*
Department of Chemistry and Industrial Chemistry, University of Genova, Via Dodecaneso, 31, 16146 Genova (Italy).
(*) corresponding author: [email protected]; [email protected].
Keywords: multicomponent reaction, organocatalysis, benzazepine.
The isocyanide-based multicomponent reactions (IMCRs)1 have been recognized as a very efficient tool to create
collections of small organic molecules with great structural diversity and complexity in a single reaction step.
However, a main drawback of these reactions is the low stereocontrol often achieved in the creation of the new
chirality centre as well as the lack of enantioselective procedures. This hampers the application of the classical
IMCRs in the preparation of chiral collections. Diastereoselective approaches using chiral components are a possible solution.2 Here we present the stereoselective synthesis of a family of functionalized seven-membered nitrogen heterocycles coupling an organocatalytic Mannich reaction with a Staudinger/Aza-Wittig/Ugi process.
Enantiomerically pure 4,5-dihydro-1H-benzazepines 1 with three contiguous stereogenic centers have been prepared exploiting an intramolecular variant of the Ugi reaction (Ugi-Joullié) involving an isocyanide, a carboxylic
acid and the chiral cyclic imine 2, obtained through a Staudinger aza-Wittig cyclization involving the azido aldehyde 3. For the synthesis of this chiral building block we planned to use an organocatalytic Mannich addition of
aldehydes to the azido Boc-protected imine 4, which was synthesized from the azido aldehyde 5. The oazidomethylbenzaldehydes have been prepared employing a simple and efficient chemoenzymatic strategy from
commercially available building blocks.3
References
1
Dömling, A.; Ugi, I. Angew. Chem. Int. Ed. 2000, 39, 3168-3210.
[2]
Banfi, L.; Basso, A.; Guanti, G.; Riva, R. Asymmetric Isocyanide-Based MCRs. In Multicomponent Reactions; Zhu, J. P.; Bienaymé, H., Eds.; Wiley: Weinheim 2005, 1–32.
[3]
Moni, L.; Banfi, L.; Basso, A.; Galatini, A.; Spallarossa, M.; Riva, R. J. Org. Chem. 2014, 79, 339-351.
COM28
Metal Triflate-Catalysed Synthesis of Polycyclic Tertiary Alcohols by Cyclisation
of γ-Allenic Ketones
I. Diaf, G. Lemiere1,*, E. Duñach-Clinet1,*
1
Institute de Chimie Nice (ICN), Université de Nice Sophia Antipolis, CNRS, UMR 7272, Faculté des Sciences, Parc Valrose,
06108 Nice cedex 2, France.
(*) [email protected], [email protected]
Keywords: Carbonyl-ene reaction, allene, cycloisomerisation, metal triflate, tertiary alcohols synthesis.
The ene reaction, classified by Kurt Alder in his Noble Lecture in 1943 as being an indirect substitutive addition, is
the reaction between an alkene bearing an allylic hydrogen (the ene) and an electron-deficient multiple bond (the
enophile) 1. This reaction is a powerful tool for carbocyclic annulations.
Thermal reactions 2 generally require moderate to high temperatures to proceed, however the use of Lewis acids
enables the reaction to proceed under mild conditions. Herein we describe a Lewis acid-catalysed Intramolecular
ene reaction between an allene as the ene component and a ketone as the enophile. Among all tested catalysts, bismuth triflate has been identified as the most efficient for this carbonyl-ene reaction for a variety of γ-allenic ketones. This reaction proceeds at room temperature in dichloromethane using only 1 mol% of catalyst, to afford
mono- and polycyclic dienic alcohols in good yields 3. The resulting dienols can be engaged in highly stereoselective cycloadditions to efficiently afford complex polycyclic systems. (Scheme 1)
O
•
CO2Me
OH
1) Bi (OTf)3 (1 mol%)
H CO2Me
CO2Me
2) Stereoselective
Diels-Alder
single
diastereoisomer
Scheme.1. Synthesis of highly substituted tertiary alcohol from γ-allenic ketones.
References
1
(a) J. Dubac, A. Laporterie, Chem. Rev., 87 (1987), 319-334. (b) K. Mikami, M. Shimizu, Chem. Rev., 92 (1992),
1021-1050. (c) M.L. Clarke, M.B. France, Tetrahedron, 64 (2008), 9003–9031.
2
A. Barbero, F.J. Pulido, M.C. Sañudo, ARKIVOC (IV), (2007), 220-233.
3 I. Diaf, G. Lemiere, E. Duñach-clinet, accepted for Angew.Inter. Ed., 53 (2014), 1 – 5.
COM29
Synthetic Strategies for the Preparation of Lipophilic MRI/GdBNCT Agents
A. Deagostino*.1, P. Boggio1, A. Toppino, S. Geninatti-Crich2, D. Alberti2,
P. Venturello1, S. Aime2
2
1
Università degli Studi di Torino, Dipartimento di Chimica, Via Pietro Giuria, 7 - 10125, Torino.
Università degli Studi di Torino, Dipartimento di Biotecnologie Molecolari e Scienze della Salute Via Nizza, 52 10126,Torino.
Keywords: BNCT, MRI, LDLs, liposomes, theranostic.
BNCT (boron neutron capture therapy) is a binary radiation therapy for the treatment of cancer, based on the
capture of thermal neutrons by 10B nuclei that have been selectively delivered to tumour cells.1 The neutron
capture event results in the formation of excited 11B nuclei that undergo fission to yield highly energetic 4He2+ and
7 3+
Li ions. Cell death is triggered by the release of these charged particles which create ionisation tracks along their
trajectories, resulting in cellular damage. It has been estimated that approximately 10−30 µg of boron per gram of
tumour mass is needed to attain an acceptable therapeutic advantage. Several functionalised carboranes have been
employed to construct boron delivery vehicles for BNCT, because of their high content of boron and their stability
in vivo. In recent years our research group has been working on the preparation of dual agents for BNCT/MRI applications. In these systems a carborane cage is linked to a lipophilic unit, in order to exploit LDLs as biological
vectors, and a MRI probe. In vivo MR image acquisition showed that the amount of B taken up in the tumour region
was above the threshold for successful NCT treatment.2 With the goal of improving the efficacy as theranostic
agents (therapy + diagnostic), new compounds have been prepared and tested. In one case, a triazole unit was as a
linker between the carborane cage, the MRI probe and the lipophilic unit (figure 1).3 The ability of the Gd complex of the synthesised ligand to form stable adduct with LDLs was evaluated and then MRI has been performed on
tumour melanoma cells incubated in the presence of a Gd-complex/LDL imaging probe. In was demonstrated that
the high amount of intracellular boron necessary to perform BNCT can be reached even in the presence of a relatively low-boron-containing LDL concentration. In order to exploit liposomes as biological vectors, a cholesterol
moiety has also been introduced (Gd-B-AC01).4 An in vitro test on IGROV-1-cells demonstrated that this Gd-BAC01 loaded liposomes are efficient carriers for the delivery of the MRI/BNCT probed to the tumour cells. The
BNCT treatment of IGROV cells showed that the number of surviving cells was markedly smaller when the cells
were irradiated after internalisation of the folate-targeted Gd-B-AC01/liposomes.
Fig. 1. Example of MRI/BNCT dual agent where the MRI probe and the lipophilic unit are linked to the carborane cage via a
triazole unit.
In order to reduce the synthetic steps, a new strategy, based on the hydroboration reaction, has been elaborated. In
this way the lipophilic unit will be linked to the carborane by a B-C bond instead of C-C, allowing the desired dual
agent in only four passages to be obtained.
References
1
R. F. Barth; J. A. Coderre,; M. G. H. Vicente,; T. E. Blue, Clin. Canc. Res. 11, (2005) 3987. M. F. Hawthorne, M. W.
Lee, J. Neuroonc. 62, (2003), 33.
2
S. Geninatti-Crich, D. Alberti, I. Szabo, A. Deagostino, A. Toppino, A. Barge, F. Ballarini, S. Bortolussi, P. Bruschi,
N. Protti, S. Stella, S. Altieri, P. Venturello, S. Aime, Chemistry 17, (2011), 8479.
3
A. Toppino, M. E. Bova, S. Geninatti- Crich, D. Alberti, E. Diana, A. Barge, S. Aime, P. Venturello, A. Deagostino,
Chemistry 9, (2013), 1720.
4
D. Alberti, A. Toppino, S. Geninatti- Crich, C. Meraldi, C. Prandi, N. Protti, S. Bortolussi, S. Altieri, S. Aime, A.
Deagostino Org. Biomol. Chem. 12, (2014), 2457.
COM30
Solid-phase photochemistry of acrylonitrile for Titan-like conditions simulated in
laboratory
A. Toumi*,1, I. Couturier-Tamburelli1, N. Piétri1
1
Laboratoire “Physiques des Interactions Ioniques et Moléculaires”, Aix-Marseille Université, Centre Saint-Jérôme,
UMR CNRS 7345, 13397, Marseille, France.
Keywords: Titan, planetary atmosphere, photochemistry, solid-phase, acrylonitrile.
Titan, the biggest Saturn’s satellite discovered by the Dutch astronomer Christiaan Huygens , is known to
possess a dense atmosphere mainly composed of N2 (about 98%). This particularity is very interesting from an exobiological point of view since the scientists consider Titan as a true natural laboratory for prebiotic chemistry that
happened in the Primitive Earth. The spatial mission Cassini-Huygens permitted to increase our knowledge about
this satellite. A rich photochemistry takes place in this atmosphere due to the electronic flux from the Saturn’s
magnetosphere, cosmic and solar rays and induces the formation of longer chain hydrocarbons and nitriles from N 2
and CH4 present in high altitude. The molecules produced can be in gas phase or in solid-phase also called “aerosols” which are sub-micronic particles resulting from the aggregation of molecules.
Gaseous acrylonitrile H2C=C(H)CN has been detected [1] in the upper part of the Titan’s atmosphere (between 900 and 1200 kms) thanks to the mass spectrometer embedded in the Huygens probe during the landing at
the surface of the satellite. Our previous work with this molecule [2] showed that when it is photolyzed in an argon
or N2 matrix at 10K with a microwave-discharge hydrogen lamp (λ>120 nm), isoacrylonitrile, cyanoacetylene (and
some of its isomers), and complexes involving acetylene with hydrogen cyanide or hydrogen isocyanide are formed
during the photolysis. Our experiments are followed by IRTF and mass spectrometries.
Fig. 1. Structure of acrylonitrile.
Because acrylonitrile has not yet been detected in its solid form in Titan, one of the aims of this additive
work is to obtain infrared spectra of solid-phase acrylonitrile at different temperatures (those present in the different
parts of the atmosphere) which could be helpful for a future research of this molecule in the aerosols. We irradiated
our samples with an hydrogen lamp in order to reproduce the solar flux interacting with the aerosols located at high
altitude. The products obtained after photolysis are the same than those obtained during the matrix experiment.
Performing the photolysis in solid-phase makes us able to calculate the implied branching ratios for this experiment
and to do that, we had to determine the band strength of the CN stretching mode of acrylonitrile (3.98x10 -18
cm.molecule-1). We also performed Thermal Programmed Desorption (TPD) studies by means of infrared and mass
spectrometries to be able to calculate the desorption energy (34.19 ± 0.73 kJ.mol-1) and we will discuss the implications of such a value in the case of aerosols present in the atmosphere of Titan.
Another interesting result is the presence of a residue in our surface at room temperature after photolysis.
This residue has spectral characteristics almost similar to that of “Tholins” (analogous of aerosols synthesized in
laboratory) formed in other previous experiments [3].
References
1
J. Cui, R.V. Yelle, V. Vuitton, J.H. Waite Jr., W.T. Kasprzak et al. Icarus. 200 (2009) 581-615.
2
A. Toumi, I. Couturier-Tamburelli, T. Chiavassa and N. Piétri, J. Phys. Chem. , in Press.
3
I. Couturier-Tamburelli, M.S. Gudipati, A. Lignell, R. Jacovi and N. Piétri, Icarus. 234 (2014) 81-90.
COM31
DNP enhanced NMR spectroscopy: design and synthesis of water-soluble stable
free radicals as polarizing agents
C. Sauvée*,1, M. Rosay2, G. Casano1, F. Aussenac3, R. T. Weber2, O. Ouari1, P. Tordo1
1
Aix-Marseille Université, CNRS, ICR UMR 7273, 13397 Marseille cedex 20 (France)
2
Bruker BioSpin Corporation 15 Fortune Drive, Billerica, MA 01821 (USA)
3
Bruker BioSpin S.A.S., 34 rue de l’industrie, 67166 Wissembourg (France)
(*) corresponding author: claire.sauvee@ univ-amu.fr
Keywords: dynamic nuclear polarization (DNP), dinitroxides, synthesis, solid-state NMR spectroscopy
Overcoming the limitations resulting from the intrinsic poor sensitivity of NMR remains nowadays a great challenge. In this perspective, Solid-state Dynamic Nuclear Polarization coupled to NMR (ss-DNP/NMR) is emerging
as a robust and powerful technique. The DNP method exploits the microwave-driven transfer of polarization from
the electron spin of a paramagnetic centre to surrounding nuclei, and its coupling with NMR allows to achieve
breakthroughs in the investigation of previously inaccessible systems. In the recent years ss-DNP/NMR has been
applied to biological samples (membrane proteins or fibrillar proteins) 1 and hybrid materials (mesostructured silica
for instance) 2 with enhancement factors (ε) of about 50 and 100, respectively shortening the experiment acquisiation time of 2500 and 10000 times. Detailled characterization of the studied systems has been possible using 1 and
2-D experiments, which would have been impossible to undertake at natural isotopic abundance in reasonable time
in the absence of DNP.
Among different factors the success of a DNP experiment depends strongly on the efficiency of the polarizing
agent. Based of previous studies towards the development of efficient polarizing agents two new water-soluble
dinitroxides that outperform the already existing compounds have been developed: AMUPol and PyPol (Figure 1).3
O
O
O
O
N
O
N
H
N
N
R
O
O
R = H, PyPol
R = (-CH2CH2O)4Me, AMUPol
Fig. 1. AMUPol and PyPol, 13C CPMAS spectra of 0.25 M U-13C-15N proline with 10 mM AMUPol in glycerol-d8/D2O/H2O
(60/30/10 volume ratio) with (top trace) and without (bottom trace) microwave irradiation at 14 kHz MAS, 97 K sample temperature
Very high D
enhancements (ε) of 235 and 128 were obtained with AMUPol (10 mM) at 100K, 9.4 T and 14.1 T,
respectively. The temperature dependence of AMUPol is almost linear from 100 K to > 180 K (ε= 83 at 160K).
This reduced temperature dependence allows for DNP experiments with AMUPol at sample temperatures that are
significantly higher than typical DNP experiments and up to sample temperatures where spectral resolution may be
improved.
References
1
9244.
V. S. Bajaj, M. L. Mak Jurkauskas, M. Belenky, J. Herzfeld, R. G. Griffin, Proc. Natl. Acad. Sci. U.S.A. 106 (2009)
[2] A. Zagdoun, G. Casano, O. Ouari, G. Lapadula, A. J. Rossini, M. Lelli, M. Baffert, D. Gajan, L. Veyre, W. E. Maas, M.
Rosay, R. T. Weber, C. Thieuleux, C. Coperet, A. Lesage, P. Tordo, L. Emsley, J. Am. Chem. Soc. 134 (2012) 2284.
D. Gajan, M. Schwarzwälder, M. P. Conley, W. R. Grüning, A. J. Rossini, A. Zagdoun, M. Lelli, M. Yulikov, G. Jeschke, C.
Sauvée, O. Ouari, P. Tordo, L. Veyre, A. Lesage, C. Thieuleux, L. Emsley, C. Coperet, J. Am. Chem. Soc. 135 (2013) 15459–
15466.
[3] C. Sauvée, M. Rosay, G. Casano, F. Aussenac, R. T. Weber, O. Ouari, P. Tordo, Angew. Chem. Int. Ed. 52 (2013) 10858.
Poster
Affiches
P1
JFIC -GIFC,
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC
TiO2-chitosan hybrid materials as carriers for the development of stimuliresponsive drug delivery systems
V. Aina*,1, G. Cerrato1, C. Magistris1, G. Martra1, G. Viscardi1, E.Ghedini2, M. Signoretto2
1
2
Dept. of Chemistry and NIS Centre of Excellence, University of Turin, Via P. Giuria 7, 10125 Turin, Italy.
Dept. of Molecular Sciences and Nanosystems, Ca’ Foscari University of Venice, Calle Larga S. Marta 2137,
30123 Venice, Italy.
Keywords: TiO2-chitosan hybrids, sol-gel, drug delivery systems, stimuli-responsive materials.
Biomaterials play a critical role in the success of tissue engineering approaches, as they guide the shape and
structure of developing tissues, provide mechanical stability, and present opportunities to deliver biomolecules to
cells, tissues and organs. The combination of natural and synthetic polymers with various other materials has
demonstrated the ability to enhance cellular interaction, encourage integration into host tissue, and provide tunable
material properties and degradation kinetics. [1] To this purpose TiO2-chitosan hybrid materials have been developed. The combination of TiO2 and chitosan allows to obtain an implantable device, due to the mechanical properties of TiO2 and the presence of chitosan ensures antibacterial properties jointed with an in-situ drug-delivery of
biomolecules physisorbed and/or covalently linked to chitosan. [2] Figure 1 shows a pictorial scheme of the possible molecular structure of TiO2-chitosan hybrid.
OH
NH2 OH
O
HO
O
HO
H3C
NH
OH
OH
O
O
n
O
HO
HO
NH2
O
O
Ti O Ti O
Ti O Ti
O Ti
O Ti O
Fig. 1. TiO2-chitosan hybrid material
Among the synthetized TiO2-chitosan hybrids, due to the high amount of surface chitosan molecules and to its
physico-chemical properties, the sample aged at room temperature is the most promising one to be covalently functionalized with biomolecules. In this preliminary study, 5-aminofluorescein (5-AF), a derivative of fluorescein containing a primary amino group, has been used as model molecule to simulate a drug. This dye is characterized by
low cost and low toxicity, and thanks to its high molar absorptivity it can easily be detected by means of absorption
and emission spectroscopies. [3] The combination of 5-AF and maleic anhydride with TiO2-chitosan materials has
generated a large range of novel hybrid materials tailored to applications in localized stimuli-responsive drug delivery systems. Maleic anhidride has been used as pH sensitive spacer. [4] A covalent functionalization of the TiO2chitosan hybrid has been carried out and a pH-sensitive material was realized by covalently immobilizing 5-AF
molecules with maleic anhydride as linker molecule. The efficiency of the functionalization has been verified by
means of different physico-chemical characterization techniques. To verify the behaviour of the materials after the
covalent functionalization/conjugation procedure, delivery tests in simulated body solution at different pH have
been performed showing a pH-sensitive drug delivery behaviour.
The preliminary results shown that the release of 5-AF is favoured at basic pH. The behaviour of the functionalized
materials is related to different parameters as: i) the ratio between physisorbed and chemisorbed 5-AF, ii) the 5-AF
solubility, iii) the ionic strength of the buffered solution employed in the release tests and iv) the matrix degradations.
References
1
H.E. Davis, J.K. Leach. Multifunctional Biomaterials and Devices Ed. N Ashammakh. 10 (2008) 1.
2
R. Jayakumar, R. Ramachandran, V.V. Divyarani, K.P. Chennazhi, H. Tamura, S.V. Nair. Int. J. Biol.
Macromol. 48 (2011) 336.
[3]
N. Barbero, E. Barni, C. Barolo, P. Quagliotto, G. Viscardi, L. Napione, S. Pavan, F. Bussolino. Dyes and
Pigm. 80 (2009) 307.
[4]
K. Ulbrich, T. Etrych, P. Chytil, M. Jelinkova, B. Rihova. J Contr Rel 87 (2003) 33.
P2
77ththJFIC
JFIC-GIFC,
-GIFC,Turin,
Turin,Italy,
Italy,May
May55thth-6
-6thth,,2014
2014
Copper-doped bioactive glasses: synthesis, characterization and in-vitro bioactivity
V. Aina*,1, G. Cerrato1, G. Martra1, G. Lusvardi2, G. Malavasi2, G.E. Flynn3, F.E. Imrie3 and
I.R. Gibson3
1
Dept. of Chemistry and NIS Centre of Excellence, University of Turin, Via P. Giuria 7, 10125 Turin, Italy.
Department of Chemical and Geological Science, University of Modena and Reggio Emilia, Via Campi 183,
41125 Modena, Italy.
3
Dept of Chemistry and Institute of Medical Sciences, University of Aberdeen, Foresterhill, Aberdeen AB25 2ZD,
United Kingdom.
2
Keywords: Tissue Engineering (TE), Cu-bioactive glasses, bioactivity, angiogenesis.
Tissue Engineering (TE) endeavours to regenerate and repair human tissue by collating the knowledge and techniques from many different scientific disciplines to produce an autologous tissue replacement. [1] As stated, TE is
currently limited by the inability to stimulate vascular ingrowth into constructs. This has resulted in limited application of this technology due to new tissues dying from nutrient starvation. However, traditional methods for tissue
replacement cannot cope with todays demand and therefore new ways for vessel ingrowth must be explored. Current knowledge of the involvement of copper ions in angiogenesis has resulted in these ions being doped into bioactive materials to promote angiogenesis. [2,3] To this purpose bioactive glasses doped with Cu have been studied.
Two inorganic synthesis techniques, melt and sol-gel, were used to produce bioactive glasses, both copper-free and
copper doped samples. Bioactive glasses with varying amounts of copper (0, 0.1, 0.5 1.0 mol.%) have been prepared. The samples were then characterized using various spectroscopic techniques (FT-IR, FT-RAMAN and UVVIS NIR) and the morphological characterization of the samples was obtained through the use of N2 adsorption/desorption analysis, SEM and TEM microscopies and X-ray diffraction. Through the aforementioned techniques, the effect of doping the samples with copper was analyzed and the structure of the different synthesised
materials was analysed. Following this the bioactivity was determined after exposure to cell culture medium solutions. Finally, preliminary tests of the growth of osteoblast cells exposed to bioactive glass-conditioned medium
were performed using the PicoGreen® assay, a highly sensitive means of quantifying the total cellular DNA as a
measure of cell number.
Figure 1 shows a pictorial representation of the pure and Cu-doped bioactive glasses.
Fig. 1. Pure and Cu-doped bioactive glass
The concept of the inclusion of copper into the samples was to address one of the current limitations of tissue engineering, which is the inability to stimulate angiogenesis. Copper ions have been strongly linked to the stimulation
of blood vessel in-growth. [3] It was found that the addition of Cu to both types of synthesised bioactive glasses
affected both the structure and bioactivity of the glasses. Concerning glass structure it was postulated that the Cu2+
ions disrupted the ordered orientation of SiO44- during the self-assembly reaction expecially for the sol-gel samples.
After in-vitro testing, it was found expecially for the melt samples that the inclusion of Cu2+ stimulated the formation of calcite, however an apatite was observed on both undoped and doped samples. For the sol-gel glasses the
inclusion of copper ions stimulated the formation of apatite on the surface of the glass, which was not present after
in vitro testing of the undoped sol-gel sample. Finally, preliminary data on cell growth showed that Cu2+ ions stimulated the proliferation of osteoblast cells as a function of copper concentration.
References
1
2
3
L.L. Hench, J.M. Polak. Science, 295 (2002) 1014.
V. Guarino, F. Causa, L. Ambrosio. Exper Review of Medical Devices, 4 (2007) 405.
Y. Liu, J. Lim, S. Theon. Biotechnology Advances, 18 (2003) 581.
P3
Photocatalytic degradation of Rhodamine B by nanosized Bismuth tungstate
Bi2WO6 powders synthesized by co-precipitation method
H. Ait ahsaine1, A. Taoufyq1,2, M. Ezahri1 , A. Benlhachemi1 , F. Guinneton2 , J-R. Gavarri2
1
Laboratoire Matériaux et Environnement LME, Faculté des Sciences, Université Ibn Zohr, BP 8106, Cité Dakhla, Agadir,
Maroc.
2
Institut Matériaux Microélectronique et Nanosciences de Provence, IM2NP, UMR CNRS 7334, Université du Sud ToulonVar, BP 20132, 83957, La Garde Cedex, France.
Keywords: Degradation, photocatalysis, visible light irradiation, bismuth tungstate, Rhodamine B
Objectives. The general objective of our studies on photocatalytic materials active in aqueous solutions is to degrade molecular pollutants present in water (Rhodamine B in our case), using the photonic activity of catalysts interacting with these pollutants. These materials have to be activated through UV or visible light irradiation, to give
rise to redox reactions. Two main photocatalytic materials have been used to degrade the RhB molecules in aqueous
solutions : the Bi2WO6 (BWO) (1-4) and the NaBiO3 phases (5).
Photocatalytic Bi2WO6 phase. In the present study, we try to establish clear correlations between the microstructure
and the crystallite sizes of materials based on the BWO phase synthesized in different conditions. The BWO polycrystalline materials were first prepared using a coprecipitation process (6) followed by thermal decomposition of
precursors at 300, 600 and 900°C. X-ray diffraction and Transmission Electron Microscopy analyses allowed characterizing each material in polycrystalline form. The degradation process was studied as a function of irradiation
time and the experimental procedure was decomposed in two main steps : (a) irradiation of standard aqueous solutions of RhB without photocatalytic BWO phase ; (b) irradiation of solutions of RhB in presence of powders in
various concentrations. To determine the degradation of RhB, a UV-visible spectrometer was used to analyze the
evolution of absorption bands as a function of irradiation time. At given intervals, a small amount of suspension
was taken out and filtered to remove the solid particles, and the filtrates were collected for analysis.
BWO,300°C
irradiation time
0.40
0 min
15 min
30 min
45 min
60 min
75 min
90 min
105 min
120 min
135 min
150 min
165 min
180min
195 min
0.35
Absorbance
0.30
0.25
0.20
0.15
0.10
0.05
0.00
270
360
450
540
630
wavelength(nm)
Fig. 1. Evolution RhB absorption band after 3 hours of visible light irradiation
References
1. G.K. Zhang, F. Lü, M. Li, J.L. Yang, X.Y. Zhang, B.B. Huang, Synthesis of nanometer Bi 2WO6 synthesized by sol-gel
method and its visible-light photocatalytic activity for degradation of 4BS, Journal of physics and chemistry of solids 71 (2010)
579-582.
2. Z. Zhang, W. Wang, M. Shang, W. Yin, Low-temperature combustion synthesis of Bi2WO6 nanoparticles as a visiblelight-driven photocatalyst, Journal of hazardous materials 177 (2010) 1013-1018.
3.L. Zhang , W. Wang , Z. Chen , L. Zhou , H. Xu, W. Zhu, Fabrication of flower-like Bi2WO6 superstructures as high
performance visible-light driven photocatalysts, Journal of Materials Chemistry, 17 (2007) 2526-2532.
4. M. Shang, W.Z. Wang, S.M. Sun, L. Zhou, L. Zhang, Bi 2WO6 Nanocrystals with High Photocatalytic Activities under
Visible Light, Journal of Physical Chemistry C 112 (2008) 10407-10411.
5. Kai Yu, Shaogui Yang, Huan He, Cheng Sun, Chenggang Gu, Yongming Ju
Visible light-driven Photocatalytic Degradation of Rhodamine B over NaBiO3 : Pathways and Mechanism., J. Phys. Chem.
A, 113, 10024-10032, 2009.
6. A. Taoufyq, H. Ait Ahsaine, L. Patout, A. Benlhachemi, M. Ezahri, F. Guinneton, A. Lyoussi, G. Nolibe, J-R. Gavarri,
Electron microscopy analyses and electrical properties of the layered Bi 2WO6 phase. J. Sol. State Chem., 2013.
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Structural modification of proteins adsorbed on silica nanoparticles: effect of the
surface functionalization
G. Alberto*,1, F. Catalano1, G.Martra1
1
University of Turin, Department of Chemistry and NIS Interdepartmental Centre of Excellence,
via P.Giuria 7 10125 Torino (Italy)
Keywords: silica nanoparticles, BSA, protein adsorption, CD-UV
It is well known that the biological response elicited in cells by a material is strongly affected by the conformation, density and orientation of plasma proteins that adsorb on its surface within few seconds of contact, actually
constituting new “bioactive sites” available for the interaction with cellular receptors [1]. Type and extent of possible conformational changes in adsorbed proteins depend, in turn, on the the peculiar physical-chemical surface
properties of the materials. In these respect the events occurring after the interaction of Bovine Serum Albumin
(BSA), which represent the major constituent (60%) of the serum proteins, with omogeneous spherical pure (hydroxyl-rich) silica and ammine-functionalized silica nanoparticles, both produced by the microemulsion technique,
were investigated by two main complementary approaches: the measurement of the adsorbed amounts and the investigation of the structure of adsorbed proteins.
In order to quantitatively asses the degree of surface covering, the surface area actually available for protein
adsorption for both materials was determined by studying the agglomeration state of NPs when suspended in protein solutions (Dyamic Light Scattering and ζ potential measurements). As for the structural investigation of the
interface layer, complementary spectroscopic techniques sensitive to different levels of the protein structure were
used. In particular, modifications of secondary structures were investigated by CD-UV whereas features of aromatic
aminoacids residues were investigated by photoluminescence spectroscopy both in steady-state and time-resolved
modes. Furthermore, a specific experimental setup was developed for the analysis of CD-UV spectra of BSA adsorbed on nanoparticles in suspension in order to obtain further insights about structural changes of adsorbed proteins. The main results obtained are the following:
(i) the presence of ammino groups leads to the adsorption of multiple BSA layers on the nanoparticle surface,
whereas the irreversible fraction of BSA adsorbed on pure silica nanoparticles does not the theoretical monolayer
(ii) CD-UV and photoluminescence data suggests that proteins adsorbed on pure silica undergo structural modifications (secondary, aminoacidic loci) which are much more severe then in the case of adsorption
on amino-modified silicas. In the latter case it is possible that the major contribution is from the external protein layers, which are less influenced by the interaction with the material [2].
References
1
D. Walczyk, F. Baldelli, M. P. Monopoli, I. Lynch, K. A. Dawson, J. Am. Chem. Soc. 132 (2010) 5761.
2
U. Anand, C. Jash, S. Mukherjee, Phys. Chem. Chem. Phys. 13 (2011) 20418.
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Growth of Forests of Regular-Shaped Carbon Nanofibers Yielded by Acetylene
Thermal Chemical Vapour Deposition at Low Temperatures on Conventional
Copper Foils
Chiara Demaria1, Aldo Arrais2,3*, Enrico Boccaleri2,3, Paola Benzi1, Giorgio Gatti2,3,
Simone Cantamessa2, Lorenza Operti1
1
Dipartimento di Chimica and NIS Centre of Excellence, Università degli Studi di Torino, via P. Giuria 7, 10125 Torino, Italy
Di.S.I.T. and 3 NanoSi.S.Te.M.I. Centre, Università degli Studi del Piemonte Orientale “A. Avogadro”, viale T. Michel 11,
15121 Alessandria, Italy
2
Keywords: carbon nanofibers, acetylene, chemical vapour deposition, electron microscopy, materials characterization
In the scenario of development of innovative chemical strategies and synthetic protocols to obtain low-cost
carbon nanomaterials[1] for high-performance nanocomposite materials applications,[2] carbon nanofibers (CNFs)
are an appropriate smart carbonaceous substrate to match both requirements. In this communication, an innovative
synthesis protocol of standard CNFs and the related supporting materials characterization are reported. The carbon
nanomaterials have been grown by straightforward thermal chemical vapour deposition (CVD) of acetylene at low
temperature (350 °C), on conventional copper foil substrates. The obtained nanofibers were featured with regular
shapes and high aspect ratio (i.e., the length/diameter ratio). Products have been characterized by SEM-EDAX and
TEM electron microscopy techniques, XRPD diffractometry, vibrational FT-IR and Raman and electron UV-VISNIR spectroscopy, hyphenated thermal TGA-DSC analysis. The copper foil substrates were activated by simple
dipping in aqueous solutions acidified with nitric acid. Cu catalytic nanoparticles have been observed embedded
inside carbon nanofibers by atomic X-ray fluorescence spectroscopy in hyphenated SEM-EDAX analysis. Copper
nanoparticles provide the nucleation catalytic sites for CNFs growth, determined by acetylene thermal chemical
reaction. In this context, the deposition temperature in this CVD process is among the lowest observed for CNF
synthesis, by straightforward reaction of the low-cost acetylene gas reactant on a conventional copper foil
substrate.[3,4] Different possible catalytic mechanisms have been explored for CNF growth, by application on the
Cu substrate of a thin layer of an acetone solution of the ferrocene organometal, which can provide production of
catalytic Fe nanoparticles. However, at low deposition temperature of acetylene in the CVD process, the Cu
nanoparticles activated on the surface of copper foil substrates determined the catalytic growth of the carbon
nanofibers. In Figure 1, a standard scenario of CNFs obtained is reported.
Fig. 1. SEM picture of a standard result of CNFs grown on a conventional copper foil at 350 °C by straightforward acetylene
chemical vapour deposition. Catalytic Cu nanoparticles embedded in CNF morphologies (bright spots) can be observed.
The main results of this experimental research are hence presented. In conclusion, the reported synthesis
protocol is an innovative appropriate strategy to obtain low-cost carbon nanofibers for high-quality nano-assembled
host-guest reinforced materials.
References
1
P.J.F. Harris, Carbon Nanotubes and Related Structures. Cambridge University Press (2013), 294 pp.
[2]
C. Demaria, A. Arrais, E. Boccaleri, G. Gatti, S. Cantamessa, M. Zanetti, L. Operti, Manuscript in preparation.
[3]
L.Y. Yu, Y. Qin, Z.L. Cui, Mater. Lett. 59 (2005), 459.
[4]
L. Dussault, J.C. Dupin, N. Latorre, T. Ubieto, L. Noe, M. Monthioux et al., J. Phys. Chem. Sol. 67 (2006), 1162.
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The Reaction of Cinnamaldehyde and Cinnamoyl Derivatves
with Thiols
1
2
2
2
2
O. Taglialatela-Scafati, A. Autelitano, A. Pagani, F. Pollastro, and G. Appendino*
1
Dipartimento di Chimica delle Sostanze aturali, Università di apoli “Federico II”, Via D. Montesano 49, 80131 Napoli,
Italy
2
Dipartimento di Scienze del Farmaco, Università del iemonte rientle “Amedeo Avogadro”, Via Bovio 6, 28100 ovara,
Italy
(*) Prof. Giovanni Appendino: [email protected]
Keywords: Natural products / Michael reaction/ Organocatalysis/ Cinnamaldehyde / Cysteamine assay
Spurred by the alleged relevance of the thia-Michael reaction in the bioactivity of various classes of natural products having a cinnamoyl motif, and by the development of a quick NMR assay to study this reaction, we have
carried out a systematic study of the “native” reactivity of cinnamoly derivatives with two probe thiols, the odorless
dodecanethiol as a representative of simple thiols, and cysteamine as a model of a reactive protein thiol that can
benefit from iminium ion catalysis in Michael reactions. In sharp contrast with what assumed in a large body of
biomedical literature, cinnamoyl esters, amides and ketones, as well as cinnamoyl oximes, did not show any reactivity with the two probe thiols, with chalcones and their vinylogous curcuminoids derivatives being the only compounds of this class giving thia-Michael additions. Cinnamaldehyde reacted spontaneously with cysteamine to afford the expected thiazoline derivative. Surprisingly, it also reacted spontaneously with aliphatic thiols, afford bisdithioacetals in synthetically useful yields, an observation in sharp contrast with the status of this reaction as the
archetypal thia-Michael addition that require organocatalysis and formation of an iminium ion to take place. From a
mechanistic standpoint, a substantial revision of a large body of chemical and biomedical literature on these compounds seems therefore required.
Main Compound Tested:
Detrimental effect of the β-phenyl group on the Michael reactivity of acroleyl derivatives:
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Microfluidic device: development and testing of nanoporous polymeric layers for
membrane technology
P. Avetta1,*, R. Nisticò1,2, P. Calza1,2, G. Magnacca1,2, D. Fabbri1, D. Scalarone1,2
1
University of Torino, Department of Chemistry, Via P. Giuria 7, 10125 Torino, Italy
2
NIS Research Centre, Via P. Giuria 7, 10125 Torino, Italy
Keywords: Microfluidic device, Nanoporous layer, Controlled transport, Block copolymers
Mesoporous membranes with controlled porosity have been recently proposed in the field of microfluidic analysis to obtain switchable interconnects for controlled transport of molecular or ionic species, charged nanoparticles
or biomolecules [1]. These materials have been proposed for the development of selective gates, to be employed in
microchip-based technologies for molecular separation, detection and dosing.
This contribution deals with the synthesis and the testing of nanoporous polymeric layers used as membranes, to
employ them for the controlled transport of organic molecules.
In order to obtain a material with uniform pore size and high pore density, a supramolecular approach was exploited; this approach was based on the complexation by hydrogen-bonding of polystyrene-block-poly(ethyleneoxide) (PS-b-PEO) with small porogen molecules bearing hydroxyl groups, in this study resorcinol [2].
The nanoporous films were prepared via spin coating on selected permeable supports, Si 3N4 microsieves with
spherical pores of 5 m, to obtain thin films with good mechanical resistance.
A microfluidic device was designed for the testing of controlled transport (Fig. 1): it is constituted by two halfcells in Pyrex physically separated by the porous membrane, fixed using two silicone seals covered with teflon.
TOC analysis on aqueous solutions excluded the release of organic impurities from every part of the device.
Preliminary tests carried out with different size molecules (phenol, chlorophenols and dyes) in the presence of
Si3N4 microsieves allowed to check the sealing and the applicability limits of the system.
Therefore, the study was focused on diffusion and migration of the cationic dye methylene blue. Several tests
were carried on in order to verify the effect of the starting dye concentration and the presence of an electric field (9
V), since in the case of charged species the passage can be favoured by a potential difference at the two sides of the
membrane.
The system could allow the selective passage through the porous membrane of different types of molecules on
the basis of their sizes, polarity and charge.
On the basis of the results up to now obtained, in addition to test other types of membranes, it could be interesting to verify the effect of the increase of the electric field voltage and the selecitve capacity of the system (testing
the diffusion/migration of molecules mixtures). Moreover, it can be useful to investigate about the selection of other
types of permeable supports, such as polysulfone filters.
Fig. 1. Microfluidic device
References
[1] R. Schmuhl, J. Sekulic, S. R. Chowdhury, C. J. M. van Rijn, K. Keizer, A. Van den Berg, J. E. ten Elshof, D. H. A.
Blank, Adv. Mater. 16 (2004) 900.
2 J. Tata, D. Scalarone, M. Lazzari, O. Chiantore, Eur. Polym. J. 45 (2009) 2520.
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The interaction of CO with the surface of ZnS and Cu0.01Zn0.99S nanoparticles: a
combined DFT and experimental study
E. Balantseva*, G. Berlier, A. M. Ferrari, S. Coluccia
Università di Torino, Dipartimento di Chimica and NIS Centre of Exellence, Via P. Giuria 7, 10125, Torino, Italy
Keywords: FTIR, CO adsorbtion, DFT, ZnS, metal doping, copper sulfide
Among direct II–VI semiconductors zinc sulfide (ZnS) is a well-known wide band gap material, with energy
gap (Eg) of 3.7 eV at room temperature. ZnS is one of the most important materials in the electronic industry with a
wide range of applications. The key role of morphology, size, and chemical composition in engineering the electronic fine structure of semiconductors was pointed out in many papers. ZnS was therefore prepared and studied in
many structures and morphologies, such as bulk materials, thin films, wires, nano belts and nano particles, depending on the synthesis procedure and desired application.
Notwithstanding the intense research activity on the synthesis and properties of nanostructured ZnS materials,
very few information are available about their surface structure. As recently pointed out by Gilbert et al., surface
chemistry can have an important role in controlling ZnS crystal growth [1]. This includes the presence of defects or
disorder and of surface ligands or adsorbed species, which can determine important properties, including optical
absorption threshold position and photoluminescence efficiency. Moreover, a description of the surface from an
atomic point of view could be crucial for an understanding of photocatalytic processes.
In this work the surface properties of nanostructured ZnS and Cu0.01Zn0.99S samples prepared by a simple synthetic procedure were studied by a combined experimental and computational approach. DFT calculations allowed
to predict the most stable surface of ZnS as the apolar 110. Infrared experiments showed that CO adsorption on the
zinc sulphide nanoparticles gives rise to a single main ν(CO) band (Figure 1, left panel), the intensity and position
of which is slightly modified by ZnS thermal activation temperature in the range 400-700 °C. The band position
depends on CO coverage, and the observed frequencies are in good agreement with predicted one, confirming the
prediction that the 110 surface is the dominant one also on nanostructured materials.
The spectra obtained on Cu0.01Zn0.99S samples (Figure 1, right panel) show additional bands in the 250 -2075
cm-1 range, which can be ascribed to the presence of Cu+ ions dispersed on the ZnS surface, formed upon activation in vacuum.
Fig. 1. Infrared spectra of CO desorption on pure (left) and doped (right) ZnS samples previously outgassed at 400°C.
References
1
B. Gilbert, F. Huang, Z. Lin, C. Goodell, H. Z. Zhang and J. F. Banfield, Nano Letters. 6 (2006) 605.
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Pd/SnO2 layers grown by Atomic Layer Deposition onto TiO2 nanotubes:
effect of the substrate for ethanol electrooxidation catalysis
M. Barr1, N. Brazeau2, L. Assaud1, M. Hanbücken1, E. A. Baranova2 and L. Santinacci*,1
1
2
CINaM-CNRS, Aix-Marseille University, Campus de Luminy, Marseille, France
Dept Chemical and Biological Engineering, Centre for Catalysis Research & Innovation, University of Ottawa, Ottawa,
Canada
*[email protected]
Keywords: ALD, eclectrooxidation, TiO2 nanotubes, SnO2, Pd
Direct Ethanol Fuel Cells (DEFC) is a promising system for energy storage since ethanol is non-toxic and has
a high power density. A great deal of interest has recently appeared on efficient catalysts for ethanol electrooxidation. This reaction breaks ethanol C–C bonds and allows the release of protons and electrons to the external circuit,
in the same time CO2 is produced. In a previous report, we have investigated electrocatalytic properties of Pd clusters grown by Atomic Layer Deposition (ALD) onto anodic TiO2 nanotubes (TiO2-nt). Such Pd/TiO2-nt system has
exhibited a high and stable electroactivity in alcaline medium.
In the present work several improvements are proposed. It is known that the activity of the Pd nanoparticles is
closely related to the nature of the substrate. We have therefore investigated the influence of two types of modifications of the support. One one hand, annealing of as-grown TiO2-nt was performed in air at 450°C for 2 hours. After
annealing amorphous TiO2-nt is transformed into polycrystalline anatase structure. On the other hand, the chemical
composition has been changed by SnO2 ALD on TiO2-nt, because SnO2 is known as an efficient instigator for organic compounds electrooxidation. The deposition was achieved with tetrakis(dimethylamino)tin as first precursor
and H2O2 as oxygen source at 200°C.
The SnO2 deposit within TiO2-nt is now entirely controlled. The morphology was identified by scanning electron microscope and transmission electron microscope (TEM). A thin film of SnO2 covers the whole surface of the
tubes, until the bottom (Fig. 1). The crystalline structure was characterized by x-ray diffraction and chemical composition was determined by Energy-dispersive x-ray spectroscopy and x-ray photoelectron spectroscopy. Pd deposition by ALD on the SnO2 layer is aslo fully controlled. The electrochemical performances were studied by cyclic
voltammetry in 1 M KOH + 1 M C2H5OH.
A comparison between electrocatalysis behaviors for ethanol electrooxidation of those Pd/TiO2-nt and
Pd/SnO2/TiO2-nt systems will be presented.
TiO2
SnO2
Fig. 1. TEM images of SnO2 thin film on TiO2 nanotubes
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A physical interpretation of “spurious” drift velocity in diffusive systems with
position dependent friction
Michele Battezzati
Associated to: Istituto Nazionale di Astrofisica, Osservatorio Astrofisico di Torino, via P. Giuria 1, 10125 Turin Italy
[email protected]
Keywords: Stochastic mechanics, Adiabatic elimination of variables, Position dependent friction
Diffusive systems with position dependent frictional coefficient (q) have recently been the object of renewed interest and intensive investigation, either from the experimental point of view or by numerical simulations [1,2].
Since the problem was solved theoretically long time ago [3,4], there arose a controversy about interpretation of
experimentally measured quantities in the light of theoretical developments, especially with regard to reduction of
the equations of motion in phase space to a first-order-in-time equation in configuration space, that is a Langevin
equation. Actually an approach limited to the constant friction problem was proposed by this author [5-7], based on
a separation of velocity into a purely Markovian component in configuration space and a rapidly fluctuating part. In
order to show how the same procedure can advantageously be extended to variable friction problems, it is defined
p(q, t)  p(q)  p(q, t)
where p, q, t are usual phase space and time variables. The velocity q  p(q, t) / m , where m is the mass, is thus
obtained by solving a Hamilton-Jacobi-Yasue equation obtained from a variational principle [8].
The fluctuating component of velocity in configuration space is multiplied by a -function of position and averaged
over realizations of random force and initial conditions so as to obtain functions of final configuration and time,
according to a well established procedure based upon Novikov theorem. It is thus obtained, by successive integrations by parts, an expansion in inverse powers of frictional coefficient, which is presumably asymptotic. To this end
an expansion of the response function has been used, which is suitable for separating successive orders in 1/.
The arbitrariness inherent in eq. (1) demands some further specifications, such that:
i) The function p(q) should be independent of the particular realization of random force, and related to a singular
solution of the deterministic HJY equation by an appropriate limiting procedure.
ii) The average of p(q(t), t) over configuration space and all realizations of random force should vanish. This average is evaluated taking full account of all correlations included. There results that the term proportional to the
density of particles in this average, which has the form of convolution in time, vanishes identically provided that in
the modified HJY equation for drift there appears an additional force term g(q) which is, to leading order, the average of resistance opposed to fluctuating velocity:
g(q)   q(t)  q   mD(q)(q)  q(t)  q   T(q)(q) 1  q(t)  q   (q) p q(t).t   q(t)  q 
where T is the temperature, D(q) the diffusion coefficient. The last equality follows by integration by parts, interpreted in the sense of distribution theory. In the following orders, terms containing higher derivatives of drift would
appear, so that the modified equation admits a wider class of solutions with respect to the deterministic one. The
drift is the singular solution which is the limit of the other solutions for large time, after initial velocity has decayed,
being free of any parameter. It is representable as an asymptotic series of positive powers of 1/
The equation obtained by this procedure is not new, since an identical equation was obtained in ref. [3] by “adiabatic elimination of fast variables”. The splitting of the velocity into components proposed by these authors is different from the one introduced here, but fits into the present scheme upon defining g(q)=U’(q), where U(q) is the
potential energy function. But subsequent developments in ref. [3] make use of a kind of anticipating dynamics, in
which some correlations required by Novikov theorem for evaluation of averages are thoroughly neglected. Actually, in spite of the fact that evaluation of correlations in their approach manifesrly contradicts the present one, either
procedure leads surprisingly to exactly the same equation governing the evolution of probability density, at least to
leading order. It would therefore be interesting to evaluate subsequent terms of the expansion in 1/, which can be
obtained by a somewhat lengthy calculation along these lines. This calculation is presently in progress.
[1] R.Mannella, P.V.E.McClintock, Phys.Rev.Lett. 107, 078901 (2011)
[2] R.Mannella, P.V.E.McClintock, Fluct. Noise Lett. 11, 1240010-1-1240010-10 (2012)
[3] J.M.Sancho, M.San Miguel, D.Durr, J. Stat. Phys. 28, 291-305 (1982)
[4] J.M.Sancho, arXiv:1112.3449v1 [cond-mat-stat-mech] (2011)
[5] M.Battezzati, Phys. Lett. A 172, 119-126 (1992)
[6] M.Battezzati, Trends Chem. Phys. 4, 167-190 (1996)
[7] M.Battezzati, Arch.Mech. 64, 177-206 (2012)
[8] M.Battezzati, Nuovo Cimento B 125, 333-345 (2010)
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Toward a better understanding of cloud aqueous phase oxidant capacity: relation
with hydroxyl radical precursors characterization and concentration
A. Bianco1, M. Passananti1, L. Deguillaume3, G. Mailhot1,2, M. Brigante1, 2*
1
Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448,
F-63000 Clermont-Ferrand (France)
2
CNRS, UMR 6296, ICCF, BP 80026, F-63177 Aubière
3
Clermont Université, Université Blaise Pascal, OPGC, Laboratoire de Météorologie Physique, BP 10448,
F-63000 Clermont-Ferrand (France)
4
CNRS, UMR 6016, LaMP/OPGC, BP80026, F-63177 Aubière
Keywords: atmospheric photochemistry, therephtalic acid, hydroxyl radical formation rate.
The physico-chemical composition of cloud aqueous phase collected at the Puy de Dome (pdD) station (1465m
a.s.l.) in France was studied during October and November 2013. During this period only oceanic air masses were
investigated. Total Organic Carbon (TOC), four carboxylic acids, hydrogen peroxide as well as major inorganic
anions and cations concentrations were determined. This work was focused on the quantification of oxidative capacity trough production rate of hydroxyl radical (HO●) using terephtalic acid (TA) probe technique [1]. The main
aim is to correlate the contributions of nitrate, nitrite and hydrogen peroxide to the formation rate of hydroxyl radical as function of their concentration. Moreover irradiations in the presence of TA have been performed on synthetic cloud aqueous solutions, in which chemical composition is closed to the real samples. The contribution to the
HO● formation rate due to nitrites and nitrates is lower than 10% for oceanic water while the hydrogen peroxide
contribution grows up to 80%. This work shows that hydroxyl radical formation rate in oceanic cloud water is
mainly due to the hydrogen peroxide photolysis while contribution of nitrate, nitrite, complexed iron (via Fenton
and PhotoFenton processes) and dissolved organic matter is lower. This work reports, for the first time, a correlation between physico-chemical parameters and oxidative capacity of atmospheric aqueous phase. In a second step
experimental data will be compared to those obtained using a dynamic air parcel model that was developed to simulate tropospheric cloud events (M2C2) [2] as a function of different air masses origins.
References
1 T. Charbouillot, M. Brigante, G. Mailhot, P. Reddy Maddigapu, C. Minero, D. Vione, Journal of Photochemistry and Photobiology A: Chemistry 222 (2011) 70-76
[2] Y.Long, T. Charbouillot, M. Brigante, G. Mailhot,A-M. Delort, N. Chaumerliac, L. Deguillaume, Atmospheric Environment
77 (2013) 686-695
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Molecular Modelling Study of the Active Sites of Enzymes involved in Flavonoid
Biosynthesis.
E. Bignon, J. Diharce, S. Antonczak*
ICN-UMR CNRS 7272 Faculté des Sciences, Université de Nice-Sophia Antipolis
28 av. Valrose 06108 Nice Cedex 2
Keywords: molecular modelling, flavonoids biosynthesis, anthocyanidin reductase
Flavonoids are natural products synthesized by numerous plants, daily eated by Human beings. So far, about
several thousands different flavonoids have been characterized and are distributed in sub-families. In addition to
their recognized organoleptic properties (proanthocyanidins) or the role they play in the coloration of flowers and
fruits (anthocyanins), these compounds (flavonols) show various anti-radical and anti-oxidant biological activities
[1]. Thus, the biosynthetic pathways leading to their production are complex and involve many steps, each of them
associated to the action of a specific enzyme. In this study, we focus on two particular steps leading to flavan-3-ols,
which are the last before proanthocyanidins biosynthesis. The latter, also called tannins, play a role in the
organoleptic perception of food and beverages by inducing astringency and bitterness sensations, as can be
perceived by eating some fruits or by drinking tea or red wine, for example [2].
To better understand the way these precursors of tannins are produced, we focus our investigations on two
enzymes, namely the Anthocyanidin Synthase (ANS) that transforms leucocyanidins into cyanidins and the
Anthocyanidin Reductase (ANR) that catalyses the reduction of cyanidins compounds into flavan-3-ols. So far, the
tridimensionnal organisations of the active sites, involving the presence of cofactors and substrate, are not totally
elucidated. [3] Thus, in order to decipher the enzymatic mechanisms, we first have to obtain a clear description of
these active sites.
Anthocyanidin reductase active site model,
in presence of NADPH (red) and cyanidin (green).
To that end, we realised a series of theoretical investigations by means of molecular modelling tools, either
classical mechanics or quantum mechanics. Several homology modelling, docking and molecular dynamics
simulations protocols have been applied leading to fine structural and energetic analyses.
References
1
M. de Lorgeril, P. Salen, F. Paillard, F. Laporte, F. Boucher, and J. de Leiris, Mediterranean diet and the French paradox,
Cardiovasc. Res. Vol. 54, Issue 3 (2002) 503-515.
[2]
R. Ferrer-Gallego, J. M. Hernández-Hierro, J. C. Rivas-Gonzalo, and M. T. Escribano-Bailón, Multivariate analy-sis of
sensory data of Vitis viniferaL. cv. Graciano during ripening. Correlation with the phenolic composition of the grape skins,
CyTA –J. Food. Vol. 9, Issue 4 (2011) 290-294.
[3]
M. Gargouri, C. Manigand, C. Mauge, T. Granier, B. Lan, and B. Gallois, Structure and epimerase activity of anthocyanidin reductase from Vitis vinifera, Acta. Crystallogr. D. Biol. Crystallogr. Vol. 65, Issue 9 (2009) 989-1000.
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Nb(V)-CONTAINING SAPONITE CLAY: A CATALYST FOR THE OXIDATIVE ABATEMENT OF CHEMICAL WARFARE AGENT SIMULANTS
C. Bisio,a,b* F. Carniato,a and M. Guidottia,b
a
Dipartimento di Scienze e Innovazione Tecnologica, Università del Piemonte Orientale “Amedeo Avogadro”, Viale T. Michel
11 – 15121, Alessandria
b
CNR-Istituto di Scienze e Tecnologie Molecolari, Via C. Golgi 19, 20133 Milan, Italy. Fax: +39 02 50314405 Tel: +39 02
50314405
Keywords: Niobium, Clay, Heterogeneous catalyst, Chemical warfare agent, Oxidative abatement
[CEES] / mol L-1 x 102
Chemical warfare agents (CWA) and, in particular, nerve and blistering agents have been considered, in various situations in contemporary history, among the most deadly tools humankind has ever invented deliberately.
The oxidative abatement of pollutants and toxic chemical warfare agents (CWA) is conventionally achieved via
stoichiometric reactions based on the use of strong oxidants with high environmental impact and/or via thermal
degradation. The goal of this work is to prepare a class of heterogeneous catalysts able to promote selectively
oxidation reactions in order to transform toxic organosulfur chemical agents in non-noxious products with reduced
environmental impact. To this aim, a novel Nb(V)-containing saponite clay was identified as potential catalyst for
the CWA oxidative abatement. The conventional synthetic protocol used to obtain saponite materials was modified
to allow the inser-tion of Nb(V) ions within the inorganic
1.50
framework of the clay, thus obtaining a bi-functional catalyst with strong oxidizing properties (due to the presence
1.25
of Nb(V) centers)1 and acid character.2,3 Nb(EtO)5 was
selected as metal source. This solid was compared to a
1.00
Nb(V)-modified saponite material that does not contain
0.75
Brønsted acid sites (Na/Nb-SAP). Structural, morphology
and textural properties of Nb-SAP samples were investi0.50
gated by a multidisciplinary approach. X-ray analysis
showed that the introduction of Nb ions in the synthesis gel
0.25
did not alter the structure of saponite clays. In addition, the
0.00
layered morphology was preserved for all the materials
0
6
12
18
24
studied in this work. XANES, FTIR and DR-UV-vis specTime
/
h
troscopy provided information about the chemical nature
Fig.1: Oxidative abatement of CEES with hydroand the delocalization of Nb(V) sites and allowed to study
gen peroxide over Nb-SAP (red), Na/Nb-SAP
the redox properties of the final catalysts. Finally, the cata(blue), H-SAP (green), Na-SAP (yellow) and with
lytic properties of these solids were evaluated at room
no catalyst (black). Reaction conditions: CEES (14
temperature in the oxidative degradation, with hydrogen
mM), H2O2 (70 mM), catalyst (20 mg), n-heptane,
peroxide, of (2-chloroethyl)ethyl sulfide (CEES), an orgaroom temperature (298 K).
nic sulfide whose chemical structure and reactivity is similar to that of sulfur mustard (blistering HD agent), but with reduced toxicity (LD 50 values for rat subcutaneous are
566 and 3.4 mg kg-1, for CEES and HD, respectively). The catalytic reactions were carried out at room temperature
and the decomposition reaction of CEES was followed by UV-Vis analysis (Fig. 1) and the preformances of NbSAP are compared with those of parents samples (Na-SAP, acid saponite (H-SAP) and Na/Nb-SAP). The copresence of Nb(V) centers and acid sites in the saponite clay was essential to have an effective and very fast decomposition of the sulfide substrate. CEES was selectively oxidized to (2-chloroethyl)ethylsulfoxide and (2chloroethyl)ethylsulfone without detectable formation of intermediates or by-products of cyclization/oligomerization of the sulphur species. Nb-Saponite prepared by using Nb(OEt)5 precursor resulted very promising, being able to transform 80% of CEES in less than 8 h.
References
[1]
A. Gallo, C. Tiozzo, R. Psaro, F. Carniato, M. Guidotti, J. Catal. 298 (2013) 77.
2
F. Carniato, C. Bisio, G. Gatti, S. Roncoroni, S. Recchia, L. Marchese, Catal. Lett. (2009) 131.
[3]
L. Ostinelli, S. Recchia, C. Bisio, F. Carniato, M. Guidotti, L. Marchese, and R. Psaro, Chem. Asian J. 7 (2012) 2394.
th
7th JFIC
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Turin,
Italy,
May
5th-6
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7th JFIC
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Turin,
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May
5thth-6
, 2014
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New Synthetic Strategy of MRI/BNCT Agents Based on Hydroboration Reaction
P. Boggio1, A. Toppino, S. Geninatti-Crich2, D. Alberti2, S. Aime2, A. Deagostino1
2
1
Department of Chemistry, University of Torino, via P. Giuria 7, 10125, Torino, Italy.
Department of Molecular Biotechnology and Health Sciences; University of Torino, via Nizza 52, 10126, Torino, Italy
3
Keywords:BNCT, hydroboration, dicarba-closo-dodecaborane, MRI, theranostic
Boron neutron capture therapy (BNCT) is a binary strategy for cancer treatment based on nuclear 10B interaction
with a thermal neutron flow. This therapy requires the introduction within cancer cells of 15-30 µg B per gr of tumor tissue with high selectivity. These boron amounts are necessary for an efficient treatment, while a selective
introduction in tumor preserves other cells from damages. Another aspect is the importance of following in vivo 10B
distribution to check the tumor position [1]. In order to reach these aims, several BNCT agents have been functionalized with different biological vectors (to improve their selective absorption in tumour cells) and with different MRI
probes (to follow the in vivo boron distribution). In this work a new sinthetic strategy for dicarba-closododecaboranes (RR’C2B10H10) is reported. Starting from decaborane (B 10H14), these molecules show good in vivo
stability and powerful versatility, allowing the boron cage with different biological vectors and MRI probes to be
functionalized. Hydroboration reaction is the main synthetic step to functionalize decaborane with terminal alkenes,
achieving 6-alkyldecaboranes (6-R-B10H13) [2]. Starting from these B-substituted alkyldecaboranes, dehydrogenative insertion reaction with terminal alkynes allows dicarba-closo-dodecaboranes to be synthetized [3]. On one
side the carborane cage has been functionalized with a lipophilic moiety by hydroboration reaction with 1hexadecene (PB01, figure 1), in order to allow the interaction with LDLs or liposomes (the real biological vectors).
On the other side the carborane cage has been functionalized by dehydrogenative insertion reaction with a terminal
alkyne, like 3-butyn-1-ol, subsequently joined with a Gd-DOTA complex as MRI probe. Few synthetic steps are
required to achieve the basic structure of BNCT agents, in contrast with previous strategies that need several steps
and a lot of time. Furthermore the different reactivity between boron and carbon atoms allows to functionalize decaborane without using protector groups. Preliminary relaxometric tests on PB01interaction with LDLs have
showed an interesting Nuclear Magnetic Relaxation Dispersion (NMRP) profile in comparison with other BNCT
agents, for example AT101 (Figure 1).
Figure 1. Comparison between PB01-LDLs and AT101-LDLs NMRP profiles
References
1 R. F. Barth; Journal of Neuro-Oncology; 2003, 62, 1
2 U. Kusari, P. J. Carrol, L. G. Sneddon; Inorg.Chem.; 2008, 47, 9203-9215
3 O. Bondarev, Y. V. Sevryugina, S. S. Jalisatgi, M. F. Hawthorne; Inorg.Chem.; 2012, 51, 9935-9942
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Structural geometries of halogen…halogen synthons.
G. Gervasio1, E. Bonometti*,1
1
Università di Torino, Dipartimento di Chimica, Via P. Giuria 7)
Keywords: halogen bonding, x-ray diffraction data, crystal engineering
Halogen bonding is the well-known non-covalent interaction where halogen atoms function as electrophilic
and nucleophilic species. This strong, directional and selective interaction, highly electrostatic in nature, has been
used in crystal engineering of solid state materials for various applications : e.g. to direct the selfassembly of nonmesomorphic component into supramolecular liquid crystals, to control the structural and physical properties o
conducting and magnetic molecular materials, to separate mixture of enantiomers, to afford and tune the second
order non-linear optical responses and for biomimetic reactions [1]. Quantum chemical investigations have shown
that the electron density around covalently bound halogens is anisotropically distributed with a belt of charge density in the equatorial region and an area of its depletion ( the σ hole) at the top of halogen atom (Figure 1).
This charge density distribution explains why the nature and the strength of halogen···halogen interaction
strongly depends on its geometry. According to earlier studies, there are two types of angular preferences for CX1···X2-C(X=halogen)interactions : type I interaction in which C-X1···X2 ≈X1···X2-C≈140°-180° and type II halogen bond with C-X1···X2≈ 180° and X1···X2-C≈90°. The type II is the true halogen bond and is clearly responsible of the triangular X3 interaction.
The X2 and X3 synthons have been widely studied while few results on Xn (n>3) are reported [2].The geometries of the Xn (n>3) synthons have been examined using the Cambridge Structural Database (CSD), in order to
characterize the type of halogen interactions involved. On the basis of the whole X-ray crystal data, the X4 and X6
synthons will be reported and discussed.
.
Fig. 1. Scheme of the C-X(X=halogen) charge distribution and of the halogen···halogen interaction type II in X2 synthon..
References
1
P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, G. Terraneo, Angew. Chem. Int. Ed.. 47 (2008) 6114.
[2]
A. Mukherjee, G. R. Desiraju, IUCrJ,1 (2014),49.
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2014
7thth JFIC
Improved Nitroxide Mediated Photopolymerization process: An unique tool to
combine Surface Micropatterning and Tailored Polymer Properties
Julien Bosson1*, Yohann Guillaneuf1, Jean-Louis Clément1, Jacques Lalevée2, Didier
Gigmes1*
1
2
Aix-Marseille Université, Institut de Chimie Radicalaire, UMR 7273, Av. Esc. Normandie Niemen, Service 542, 13397
Marseille
Institut de Sciences des Matériaux de Mulhouse, LRC CNRS 7228, ENSCMu-UHA, 15 rue Jean Starcky 68057 Mulhouse
*[email protected], [email protected]
Keywords: photosensitived alkoxyamines, NMP2, dissociation
Photopolymers represent a rapidly emerging field in material science. In fact, the photochemical process is
characterized by important advantages since thin films can be polymerized very rapidly using a UV lamp irradiation. For coatings, inks, photoresists,..., the photopolymerization reaction is now recognized as particularly interesting (modification of patterning sufaces) and powerful. This is also an ecological alternative to thermal processes
since no volatile organic compounds are used in this technology1. Even if the use of dithiocarbamate compounds
lead of encouraging results for such applications these compunds suffer from severe limitations (generation of
dithicarbamyl radicals)2. Indeed, these radicals that are supposed to play the role of controller are also able to either dimerize and/or initiate extra chains leading to a dramatic loss of control and livingness. Therefore, in order to
fulfil the growing need in the elaboration of photoinduced modification or micro/nano patterned surface the development of alternative techniques to dithiocarbamate is highly desired.
a)
b)
Fig 1. a) The Nitroxide Mediated Photopolymerization process b) Example of photosensitized alkoxyamines
In this context, we recently proposed various photosensitive alkoxyamines, which decomposes under UV irradiation to generate the corresponding alkyl radical and a nitroxide; Depending on the nature of the alkoxyamines we
obtained very encouraging results in Nitroxide Mediated Photopolymerized (NMP2) process for n-butyl acrylate
polymerization and the preparation of covalently bound multy-layers coatings3.
The first part of my project is to synthesize a wide range of structures to reach optimal alcoxyamines. The first
structures are obtained from alkoxyamines TIPNO-like (tert-butyl-isopropyl-phenyl-bromide). Modifications of
chromophores and alkyl substituants are studied to observe their photochemical properties under radiation (half-life
t1/2, absorption radiation, dissociation). The best structures will be then used for processes of spatially controlled
photopolymerization.
References
1
2
3
K. T. Haraldsson, J. B. Hutchison, R. P. Sebra, B. T. Good, K. S. Anseth, C. N. Bowman, Sensors and Actuators BChemical 113 (2006) 454
J.D. Manga, M. Tardi, A. Polton, P. Sigwalt, Polym. Int.45 (1998) 243
a) Y. Guillaneuf, D. Bertin, D. Gigmes, D.-L. Versace, J. Lalevée, J.-P. Fouassier, Macromolecules 43 (2010) 2204. b) Y.
Guillaneuf, D.-L. Versace, D. Bertin, J. Lalevée, D. Gigmes, J.-P. Fouassier, Macromol. Rapid Commun. 31 (2010) 1909
c) D.-L. Versace, J. Lalevée, J.-P. Fouassier, D. Bertin, Y. Guillaneuf, D. Bertin, D. Gigmes, Macromol. Rapid Commun.
31 (2010) 1383 d) D.-L. Versace, J. Lalevée, J.-P. Fouassier, D. Gigmes, Y. Guillaneuf, D. Bertin, Pol. Sci. Part A-Polym.
Chem. 48 (2010) 2910
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Cs2O/BEA catalytic systems - perspective materials for the production of fine
chemicals: CO2 and alcohols activation.
M. Botavina*, G.Martra
University of Torino, Department of Chemistry and Interdepartmental Centre “Nanostructured Interfaces and Surfaces – NIS”
via P. Giuria 7, 10125 Torino,Italy
Keywords: basic zeolites, carbon dioxide, alcohols
Zeolites BEA are characterized by three-dimensional 12-membered ring channel system and their large pores allow an easy diffusion of a wide number of the various reactants into the zeolite structure. Modifying BEA zeolites with
both Cs+ exchanged ions and Cs-oxide like nanospecies it is possible to increase their basic properties [1].
Cs/BEA catalysts were prepared by ion exchange of acidic BEA zeolites H-BEAENI (Si/Al = 13) and H-BEARIPP
(Si/Al = 16). Obtained materials were than impregnated with an additional amount of Cs [2]. At the end two series
of BEA zeolites (ENI and RIPP) with different Cs contents (0.92 after ion exchange and 1.6 after impregnation)
were obtained.
BET data shows that the increase of cesia content was accompanied by some decrease in a specific surface
srea and increase of the average pore diameter.
FTIR analysis verify that after the introduction of Cs+ ions by ion exchange Brønsted acidic frameworkbridged OH groups were not presented on the zeolite surface any more. The following impregmation with CsOH
and subsequent Cs2O formation resulted in the almost compleate disappearence also of nonacidic terminal silanols.
Introduction of Cs signigicantly increased catalyst basicity, especially in the presence of strongly basic Cs-oxide-like
species. On the surface of the impregnated samples CO2 adsorbtion with the formation of carbonates (interacting with
basic centres) was observed.
The first attampts to activate alcohols indicated that 1-butanol was adsorbed on Cs/BEA surfaces with the
formation of alcolates.
Now we are gowing to test other types of alcohols, such as phenol and catecol and compare their adsorption spectra with thouse obtained for the water solutions of the corresponding alcohols (with different pH if necessary).
References
1
D. Barthomeuf, Catal. Rev. Sci. Eng. 38 (1996) 521.
2
C. Bisio, G. Martra, S. Coluccia, and P. Massiani, J. Phys. Chem. C, 112 (2008) 10520
P18
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2014
Synthesis of push-pull enamines as anti-HIV-1 agents
1
C. Caneva , S. Alfei1, C. Rotolo1, S. Alloisio1, F. Logiacco1, R. Loddo2, A. Spallarossa*,1
2.
1
Università di Genova, Dipartimento di Farmacia, Viale Benedetto XV 3, 16132, Genova, Italy
Università di Cagliari, Dipartimento di Scienze e Tecnologie Biomediche, Cittadella Universitaria, S.S. 554, Km 4,500, I09042 Monserrato, Cagliari, Italy
Keywords: Enamines, Iminium Salts, Knoevenagel-type Compounds, HIV1, Reverse Transcriptase
In the last years, a new two-steps synthetic strategy to obtain unknown push-pull enamines was developed in
our laboratory [1]. The first step consisted in the condensation of iminium chloride Im1, obtained by reacting imidazolidin-2-thione (1) with benzoyl chloride and DMF, with active methylene reagents (AMRs) to synthesize
Knoevenagel-type five-membered N-(α,β-unsaturated)thioureas 2 [2]. These compounds, in a second step, were
condensed with amines at room temperature overnight leading to the preparation of the push-pull enamines 3
(scheme 1). The work up was easy and the compounds were purified by crystallization. No chromatography was
needed and the thiourea by-product can be easily washed away by water. The reaction procedure is highly parallelizable and the yields are good. The stereochemisty of the prepared enamines was elucidated; the majority of the
compounds were obtained as mixture of E and Z isomers, being the E isomers predominant in almost all the mixtures.
C6H5COCl
TEA
H2N-R
DMF
r.t.
DMF
120°C
DMF
r.t. overnight
1
Im1
2
3
Scheme 1. Synthesis of Push-pull enamines.
The synthesized enamines were tested on highly HIV-1 infected MT-4 cells. Cytotoxicity (CC50 values) and growth
inhibition of wild-type HIV-1 (EC50 values) were evaluated and some of the obtained products were found to have a
micromolar activity against HIV-1. The most interesting results were established when EWD1 and EWD2 were
respectively a phenylsulfonyl group and a cyano group and R was a benzyl group, as reported in table 1.
Cpds
3A
3B
3C
3D
3E
EWD1
-SO2C6H5
-SO2C6H5
-SO2C6H5
-SO2C6H5
-SO2(4-CH3C6H4)
Table 1. The most relevant activity data.
EWD2
R
-CN
-CH2C6H5
-CN
-CH2(4-Cl-C6H4)
-CN
-CH2(2,4-Cl-C6H3)
-CN
-CH2(3,4-OCH3-C6H4)
-CN
-CH2(3,4-OCH3-C6H4)
CC50 (μM)
> 100
> 100
> 100
> 100
> 100
EC50 (μM)
1
1.1
1.2
2.5
0.1
Moreover, the most active molecules were further tested, in cell based-assays, against clinically relevant HIV-1
variants bearing mutation on RT. On the basis of the obtained results, we hypothesized RT to be the target of
enamines. To further support this hypothesis and rationalize the SARs, docking simulations (Autodock 4.2) were
carried out on the most active compounds.
1
C. Rotolo. PhD Thesis 2012
2
A. Ranise, S. Cesarini, A. Spallarossa, F. Sancassan, F. Bondavalli, O. Bruno, S. Schenone, G. Menozzi, P. Fossa, L. Mosti, Synthesis 16 (2007), 2495.
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A general entry into Helichrysum cannabinoids
D. Caprioglio1, D. Cantoni1, G. Appendino1 and A. Minassi1*
1
Department of Pharmaceutical Sciences, Università del Piemonte Orientale A. Avogadro, L.go Donegani 2, Novara
Keywords: Helicrysum, synthesis, cannabinoids, biological activity, PPAR-γ
Plants of the genus Helicrysum are well known as a source of medicinal agents, fregrances and natural deys. 1
Remarkably, some South-African Helichrysum species could also contain psychotropic agents, being used as
trance-inducing agents in ritual ceremonies.2 Indeed, Helicrysum umbraculigerum has been reported to contain the
hemp cannabinoid cannabigerol,3 and phenylethyl and stiryl analogues of phytocannabinoids have been reported in
other South African Helichrysum species. Remarkably, nothing is known on the biological profile of Helichrysum
cannabinoids, also because of their limited availability from natural sources, where they generally occur as complex
mixtures.
With the aim of elucidating the biological profile of Helichrysum cannabinonids, we have started a project of total
synthesis to complement the obtaining of natural members of this class of compounds by isolation. The biological
end-points taken into consideration for the pharmacological evaluation are not only the classic metabotropic (cannabinoid receptors, CBs)- and ionotropic (TRPs) targets of phytocannabinoids, but also PPARγ, recently identified
as a transcription-factor receptor sensitive to hemp phytocannabinoids.4
A general synthesis of these compounds, capable to provide not only the natural products but also analogues, was
developed according to Fig. 1. The key feature of the synthesis is the isoprenylation of a suitably protected resorcinol derivative, a reaction whose subtleties will be discussed.
Fig. 1 Heli-CBG and rational for the synthesis
References
[1]
Appendino, G., Ottino, M., Marquez, N., Bianchi, F., Giana, A., Ballero, M., Sterner, O., Fiebich, B.L., Munoz, E.,
Journal of Natural Products 70 (2007), 608–612.
[2] A.C.U. Lourens, A.M. Viljoen, F.R. van Heerden, Journal of Ethnopharmacology 119 (2008) 630–652
[3] F. Bohlmann, E. Hoffmann, Phytochemistry 18 (1978), 1371-1374.
[4] A. G. Granja, F. Carrillo-Salinas, A. Pagani, M. Gómez-Cañas, R. Negri, C. Navarrete, M. Mecha, L. Mestre, B. L. Fiebich,
I. Cantarero, M. A. Calzado, M. L. Bellido, J. Fernandez-Ruiz, G. Appendino, C. Guaza, E. Muñoz, J Neuroimmune Pharmacol
7 (2012) 1002–1016
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The effect of Yb3+, Eu3+, Dy3+, Ho3+ on the luminescence performances of
gadolinium oxycarbonates
V.Caratto1,2* L.Panzeri3,4, M. Fasoli3, M. Martini3,4, I. Miletto5, E. Bottinelli5, E. Gianotti6, F.Locardi1, E. Sanguineti1, R. Masini7, E. Franceschi1, G. A. Costa1
1
1Department of Chemistry and Industrial Chemistry, University of Genova, Genoa, Italy.
Department of Earth, Environment and Life Sciences, University of Genova, Genoa, Italy
3
Department of Material Science, University of Milano-Bicocca, Milan,Italy.
4
INFN section of Milano-Bicocca, Milan, Italy
5
Department of Chemistry, University of Torino, Turin, Italy.
6
Department of Science and Technological Innovation, University of Piemonte Orientale, Alessandria, Italy
7
CNR-IMEN, Genoa, Italy
2
Keywords: Oxycarbonate, rare earth, luminescence, phosphor, bioimaging
Persistent luminescence is an interesting phenomenon in which the long-lasting phosphorescence of material persists for a long time after the removal of the excitation source; it would be very interesting to address the research in
the development of persistent phosphors in the NIR region (700-2500nm) due to the possible applications as optical
probes in bio-imaging [1]. The rare earth oxycarbonates doped with suitable optically active lanthanide ions are
promising systems for application as optical probes due to the prolonged afterglow in the NIR region. Oxycarbonate (RE2O2CO3, RE=rare earth) can exist in three forms: monoclinic, cubic, hexagonal. Hexagonal form has
chemical stability and it is the most suitable form to host doping ions; but its synthesis is strictly correlated with the
synthetic route especially for temperature, atmosphere and treatment time. To date we successfully synthesized
Gd2O2CO3 in hexagonal form, doped with Eu3+, Dy3+, Yb3+, or Ho3+, which presents interesting optical characteristics. The synthesis consisted in a thermal treatment of raw materials (mixed oxalates or oxides) in a fluent CO2
atmosphere with a flux of molten salts [2]. All the samples were characterized by X-ray powder diffraction to confirm the obtainment of the hexagonal form for each composition. The target of the study was the disclosure of the
structure-properties relationship, with regard to the influence of i) size, ii) surface features and properties (defects,
etc.), iii) crystalline phase, iv) nature of the host material, v) nature and concentration of the dopant ion, on the UVVis-NIR absorption and luminescence properties of the materials. The gadolinium oxycarbonate doped with Yb3+
showed the phenomenon of persistent luminescence measurable up to 140 hours; moreover, the decay was independent of temperature [3]. The gadolinium oxycarbonate doped with Yb 3+ was tested in vitro with biological molecules.
Fig. 1. Luminescence under Uv lamp and XRD analysis of Gd2O2CO3:Eu3+
Acknowledgements.This work was funded by MIUR financing: PRIN 2009, prot. 2009MBZ9Z and PRIN 2012 prot.
2012ZELHLE.
References
1 Z. Pan, Y-Y. Lu, F. Liu, Nature Mater. 11 (2012) 58-63
[2] Y. Mayana, T. Masui, K. Koyabu, N. Imanaka, J. Alloys Compd. 451 (2008) 132-135
[3] Italian Patent: MI2013A000908
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Alloying behaviour of the rare earth metals with aluminum and silicon:
the Nd-Al-Si, Sm-Al-Si and Dy-Al-Si systems
Anna Maria Cardinale, Daniele Macciò, Adriana Saccone
Dipartimento di Chimica e Chimica Industriale, Università di Genova, Via Dodecaneso, 31 - 16146 Genova (*) corresponding
corresponding author:[email protected]
Keywords: Phase diagrams, intermetallic compounds, aluminum alloys, rare earth alloys, silicon alloys
Technological properties, such as thermal, mechanical and corrosion resistance, of the Al–Si alloys can be improved by the addition of rare earth elements (R) through the formation of ternary phases [1, 2]. Therefore, the
knowledge of the phase relationships and the constitutional properties of the R-Al-Si is relevant to improve the
understanding of the rare earths influence on the setting up of the Al-Si alloys
The investigation of the R-Al-Si systems is part of an ongoing research project by our research group with the
aim to clarify their constitutional properties [3-5]. In this communication the results obtained in the experimental
investigation of the phase relationships of the Nd-Al-Si, Sm-Al-Si and Dy-Al-Si systems, at 500°C, are shown.
These systems have been experimentally studied by differential thermal analysis (DTA), X-ray powder diffraction (XRPD), metallography, scanning electron microscopy (SEM) and electron probe microanalysis based on energy dispersive X-ray spectroscopy (EDX). The alloys were generally synthesized by arc melting high purity metal
ingots of Sm, Si and Al under a stream of pure Ar. Al-poor alloys were prepared in an induction furnace in sealed
Ta-crucibles. The most part of the alloys were annealed at 500°C for 350 h and quenched in water. A number of
alloys were subjected to differential thermal analysis carrying out the measurements, both on heating and on cooling, at different rates (5–10 K min ).
The three systems present a high number of intermetallic compouds and complex phase relationships. The new
ternary intermediate phases having R4Al3Si3 stoichiometry have been found and their crystal determined (orthorombic oS20, isotypic with Pr4Al3Ge3).
Comparison among the three isothermal sections will be discussed highlighting the regular trend of the number
and stoichiometry of the phases by moving from the light rare earths (Nd) to the heavy rare earths (Dy).
-1
References
[1]. Ye HJ.. J Mat Eng Performance.2003;12:288–97.
[2]. Zhu M, Jian Z, Yao L, Liu C, Yang G, Zhou Y.. J Mater Sci. 2011;46:2685–94.
[3] Cardinale AM, Macciò D, Delfino S, Saccone A., J. Therm. Anal. Calorim. 2011; 103: 103-109.
[4] Cardinale AM, Macciò D, Delfino S, Saccone A. J. .Therm. Anal. . Calorim. 2014; 116, 1: 61-67.
[5] Cardinale AM, Macciò D, Delfino S, Saccone A. J. Therm. Anal. Calorim. 2012; 108: 817-823.
P22
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7thth JFIC -GIFC,
Melt spinning and open die pressing effects on mechanical properties of the
Zn4Sb3 thermoelectric compound
R. Carlini1, A. Castellero2, C. Fanciulli3, F. Passaretti3, M. Baricco2, P. Mele4,
G. Zanicchi1
1
Dipartimento di Chimica e Chimica Industriale - Università di Genova and INSTM, Via Dodecaneso 31 - Genova,
2
Dipartimento di Chimica e Centro NIS - Università di Torino – via P. Giuria 9 - Torino
3
CNR – Istituto per l'Energetica e le Interfasi, C.so Promessi Sposi 29 - Lecco
4
ISSD, Institute for Sustainable Sciences and Development, Hiroshima University, Kagamiyama, Higashi-Hiroshima, Japan
Keywords: Thermoelectric materials, intermetallic compounds, melt spinning, open die pressing, mechanical properties
The unexpected low thermal conductivity of some semiconducting intermetallic compounds, belonging to the
Zintl’s hases, have attracted much attention in the research of new thermoelectric materials. The Zn4Sb3 is one of
the most studied compounds in the thermoelectric field due to its glass-like thermal conductivity originated in the
framework Zn position. [1-3] The reduction of grain size can lead to an improvement of Figure of Merit-ZT although causes an increase of material brittleness. This behavior is a heavy obstacle for its application in thermoelectric modules.
Here a new approach, aimed to obtain an improvement of the Zn 4Sb3 thermoelectric properties associated to
mechanical performances, is proposed. The intermetallic Zn4Sb3 was obtained through a simple synthesis route and
processed using Melt Spinning (MS) on bulk material and/or Open Die Pressing (ODP) technique on bulk and melt
spun samples. ODP, successfully applied for fast chalcogenides powders sintering, guarantees a low temperature
involved and a short time required for sintering leading to reduce the negative processing effects on grain size enlargement.
The pure β-phase Zn4Sb3 phase was investigated in terms of crystal structure, phases composition, microstructure, thermal stability, mechanical resistance and thermoelectric properties after both melt spinning and ODP processes
A high improvement in mechanical behaviour of the material after ODP processing was achieved preserving
thermoelectric properties of the material: mechanical resistance of the bulk increased up to 11 times as respect to
the starting as-cast bulk.
References
[1] R. Carlini, D. Marré, I. Pallecchi, R. Ricciardi, G. Zanicchi, Intermetallics, 45, (2014), 60
[2] R. Carlini, M. M. Carnasciali, F. Soggia, S. Campodonico, G. Zanicchi, J. of Alloys and Compounds, 588, (2014), 361
[3] D. M. Rowe, “Thermoelectric handbook – macro to nano”, CRC, Boca Raton Fl, USA, (2006)
P23
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2014
7thth JFIC -GIFC,
ORGANO-MODIFIED GADOLINIUM FLUORIDE NANOPARTICLES AS
DUAL OPTICAL AND MR- IMAGING
F. Carniato,* L. Tei and M. Botta
Dipartimento di Scienze e Innovazione Tecnologica, Università del Piemonte Orientale “Amedeo Avogadro”, Viale T. Michel
11 – 15121, Alessandria
Keywords: Gadolinium fluoride, Nanoparticles, MRI contrast agents, fluorescence, dual probe
Gd-based MRI nanoprobes have the ability to carry a high payload of imaging reporters enabling a significant
signal amplification.1 Moreover, the paramagnetic nanoparticles (NPs) can incorporate different functionalities,
such as a vector for specific targeting, dyes or drugs for multimodality imaging or therapeutic delivery. Among the
large number of inorganic NPs, we have recently investigated citrate coated GdF3 NPs (~2 nm size) which showed
high chemical stability and high relaxivity (r1p per particle = 470 mM-1s-1 at 1.5 T and 298K), (Fig. 1).2 Other organic caotings can be also used to stabilize GdF3 NPs surface, leading to an improvement of the water suspendibility
and to a modification of their relaxometric behaviour. To reach this gaol, GdF3 NPs with EDTA and EDTA functionalized with a free carboxylic group (EDTA-COOH) or PEG2000 molecules (EDTA-PEG) were synthesized. In
addition, further functionalization with fluorescein or rhodamine dyes was explored, aiming to develop novel dual
imaging nanoprobes for optical and MR- imaging applications.
GdF3 NPs were prepared in aqueous solution by reacting NaF and GdCl3 in the presence of the different ligands. The solutions were stirred at 348 K (3h) and mixed with ethanol to promote precipitation of the NPs (Fig. 1).
X-ray diffraction patterns, HRTEM images, IR spectra, TG, DLS and spectroscopic analysis data were measured
for the characterization.
GdF3 functionalized with EDTA-COOH and EDTA-PEG
show enhanced hydrophilicity, whereas EDTA-based GdF3
tends to aggregate in aqueous suspension as a consequence of
the reduced charge density. NMRD profiles, measured in water
at 310K, of GdF3 NPs functionalized with EDTA-COOH and
EDTA-PEG present a shape typical of slowly tumbling systems,
with a peak centred at 20 MHz, as consequence of a significant
contribution from the second sphere water molecules H-bonded
to the organic coating. Instead, EDTA-based GdF3 shows a
completely different profile, characterized by a decrease of r1p
value with increasing frequency. The chemical stability of GdF3
NPs was also evaluated in SeronormTM and in aqueous suspension in the presence of an excess of a strong chelating agent (i.e.
DTPA). GdF3-EDTA-CCOH and GdF3-EDTA-PEG were finally functionalized with modified fluorescien and rhodamine
dyes, respectively, bearing in the structure a terminal NH 2
group. The idea was to promote a classical amide coupling betFig.1: Schematic view of the GdF3-EDTA NPs
ween the carboxylic groups exposed on the NPs surface and the
synthesis. The 1/T1 NMRD profile at 310 K for
amino functionality introduced in the organic dyes. The final
GdF3 NPs functionalized with citrate molecules,
NPs were then incubated in ovarian carcinoma cells (SKOV-3)
considering only the metal ions exposed on the
surface of the NPs, is reported below.
and tested as dual MRI/optical probes. MRI and confocal fluorescence microscopy analyses carried out on the incubated
SKOV-3 cells indicated that NPs were well incubated in the cytosol and that no alteration of the cells membrane
occurred at low NPs loading.
References
1
M. Botta and L. Tei, Eur. J. Inorg. Chem. (2012) 1945.
[2]
F. Carniato, K. Thangavel, L. Tei, and M. Botta, J. Mater. Chem. B 1 (2013) 2442.
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TiO2/graphene composites for Lithium-ion batteries with high-power application:
a comparison among several synthesis methods
D. Versaci1, S. Casino2,*, M. Minella1, F. Di Lupo2, C. Minero1, S. Bodoardo2
2
1
Chemistry Department and NIS Centre of Excellence, University of Torino, Via P. Giuria 5, 10125, Torino, Italy
GAME Lab, Dept. of Applied Science and Technology, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129, Torino, Italy
Keywords: Titanium oxide; Graphene oxide, Anode, Lithium-ion battery
The attention on TiO2 – especially its crystallographic form anatase – as anode material for Li-ion batteries has
recently increased due to its low cost, low environmental impact and intrinsic safety, combined to interesting electrochemical performance. Indeed, anatase presents a relatively high theoretical capacity (335 mA h–1 g–1) close to
that of graphite, negligible lattice changes during Li ion insertion/extraction (<4%), and a relatively high Li + ion
insertion/deinsertion potential ( 1.5–2.0 V vs. Li+/Li), which makes it intrinsically safer than graphite so reducing
the possibility of Li electroplating[1]. However, its use for high power applications, e.g. in electric vehicles, is hampered by the poor ionic and electronic conductivity: in order to overcome this problem, TiO 2 powders can be synthesized with a conductive coating[2-4]. The present contribution focuses on the development of a simple way to
prepare several TiO2 /graphene hybrids by using commercial TiO2 anatase as raw material, aiming for the optimisation of a low cost and easily scalable method. Graphene oxide (GO), synthesized from high purity graphite by the
modified Hummer and Staudemaier’s method [5] proposed by Huang et al.[6] , was adsorbed on nanoscale TiO2 anatase powder and successively reduced to the so called Reduced Graphene Oxide (r-GO) in order to restore the electrical conductivity and obtain the desired high conductive composite. Different loading of GO and several reduction
strategies (hydrothermal, photocatalytic, chemical and thermal) have been tested and the electrochemical performances of the synthesized hybrids evaluated, with the aim to individuate the best synthetic conditions. Thus, all the
prepared samples have been characterized from the structural-morphological and electrochemical viewpoint, assessing the cycling performances in lab-scale Li-based cells. As reported in Fig.1, an outstanding increase of the
electrochemical performances at high C-rate is obtained for the sample with 5 wt. % of r-GO obtained by photocatalytic reduction. We can conclude that this new composite materials can be used for high power applications.
Fig. 1.
Specific charge capacities with cycling of commercial TiO2 and a TiO2/graphene composite (reported in black and red
respectively). The insets report a cyclic voltammetry (scan rate = 0.010 mV s −1) and a FESEM image of the same
composite sample.
References
[1] S. Casino, F. Di Lupo, C. Francia, A. Tuel, S. Bodoardo, C. Gerbaldi, J. Alloys Comp. 594 (2014) 114.
[2] D. Wang, D. Choi, J. Li, Z. Yang, Z. Nie, R. Kou, D. Hu, C. Wang, L. V. Saraf, J. Zhang, I. A. Aksay, J. Liu, ACS Nano 3
(2009) 907.
[3] Z. S. Wua, G. Zhoua, L. Yina, W. Rena, F. Li, H.-M. Chenga, Nano Energy 1 (2012) 107.
[4] X. Xin, X. Zhou, J. Wu, X. Yao, Z. Liu, ACS Nano 5 (2012) 11035.
[5] W. S. Hummers, R.E. Offeman. J. Am. Chem. Soc. 80 (1958) 1339
[6] N. M. Huang, H.N. Lim, C.H. Chia, M.A. Yarmo, M.R. Muhamad, Int. J. Nanomed. 6 (2011) 3443
P25
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2014
7thth JFIC -GIFC,
Serum proteins adsorption on engineered silica nanoparticles, spectroscopic
investigation of the interface events and their influence on cell uptake
Federico Catalano1, Gabriele Alberto1, Lisa Accomasso2, Clara Gallina2, Stefania Raimondo2, Stefano Geuna2, Claudia Giachino2 and Gianmario Martra1
1
Department of Chemistry and NIS Centre of Excellence, University of Torino, via Giuria 7 10125 Turin, Italy
2
Department of Biological and Clinical Science, Regione Gonzole 10 10043 Orbassano (Turin), Italy
(*) corresponding author: E-mail addres: [email protected]
Keywords: fluorescent silica nanoparticles, protein corona, cell uptake, mesenchymal stem cells.
What cells “see” when are contacted with nanoparticles? [1, 2] The correct answer must consider the formation of an
hybrid solid/protein interface, that results in the formation of a “corona” layer. As for biomaterials, also for nanoparticles, the nature of the biological responses are determined by the protein layer covering the material surface
immediately after the contact with physiological environments. In this work, the investigation of the role of serum
proteins on the interaction of fluorescent silica nanoparticles (50 nm in size), with human mesenchymal stem cells
(hMSCs) is reported. The suspension of NPs in bare Dulbecco-Modified Eagle’s Medium (DMEM) results in the
formation of large agglomerates (ca. 2 m, by dynamic light scattering), which become progressively smaller by
progressively increasing the protein content in the incubation medium. As a consequence of the limited diffusion of
proteins in the inter-NP spaces, the surface of NP agglomerates is coated by a protein corona independently of the
agglomerate size and of the protein concentration (-potential and UV circular dichroism measurements). The protein corona appears to be not particularly relevant for the internalization of silica NPs by hMSCs, whereas the presence/absence of serum proteins in DMEM appeared to have the main role in determining the NPs internalization
rate and amount by hMSCs (monitored by fluorescence confocal microscopy).
Fig. 1. Scheme representative of how the presence of serum in colture media influence the diameter of the agglomerates seen by
cells and their internalization rate and amount.
References
1 D. Walczyk, F. B. Bombelli, M. P. Monopoli, I. Lynch,K. A. Dawson, Journal of the American Chemical Society 2010, 132,
5761-5768.
[2] A. Lesniak, A. Campbell, M. P. Monopoli, I. Lynch, A. Salvati,K. A. Dawson, Biomaterials 2010, 31, 95119518.
P26
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2014
7thth JFIC -GIFC,
CeO2-TiO2 Photocatalytic Mixed Oxides for Pollutants Reduction In Drinking Water
G. A. Mutch1, J. A. Anderson1, M. Shand1, S. Morandi2, V. Aina2, G. Cerrato*,2
1
School of Natural and Computing Sciences, University of Aberdeen, Dept. of Chemistry, Meston Building, Meston Walk, AB24
3VE Aberdeen (United Kingdom)
2
University of Torino, Dept. of Chemistry & NIS Interdept. Centre & INSTM-RU Torino, via P. Giuria 7, 10125 Torino, (Italy)
corresponding author: [email protected]
Keywords: CeO2-TiO2, photocatalysis, nitrate reduction, water purification
The quality and safety of water is a world-wide concern that is gradually becoming more important with increasing disruption of nature by the activities of man. Global and national organisations such as the World Health
Organisation (WHO) and the United States Environmental Protection Agency (US-EPA) set levels for pollutants in
drinking water that have negative impacts on the health of the environment and those that live within it [1].
Methods currently used to remove nitrates from water include reverse osmosis, ion exchange and electrodialysis, but all of these suffer from a common failing; they produce concentrated solutions of the pollutant, known as
brines, which have to be disposed of in an environmentally friendly way.
To avoid the production of brines, techniques which convert nitrates to harmless N 2 gas are favourable and as
such, two methods of promise are biological denitrification and heterogeneous catalysis. The latter approach can be
broadly split into two categories, classical supported metal hydrogenation and photocatalytic degradation: as for the
second, TiO2 materials have been studied since the beginning of the XXI century, but to modify their visible light
activity in recent years coupling of photocatalytic systems has been proposed as it can lead to improved properties
of the final material [2].
In this respect, the present work was aimed to study a mixed oxide systems based on TiO 2 promoted by the
addition of small amounts of CeO2 in order to obtain a potential photocatalytic material useful for nitrates removal
from drinking water.
CeO2–TiO2 mixed oxides and reference TiO2 were prepared using the sol-gel technique followed by testing
for photocatalytic nitrate reduction in drinking water.
Samples were prepared with 1, 5, 10, 15 and 20 % CeO 2 loading and calcined at 673 and 873 K. Morphological and structural properties were investigated using N 2 adsorption (BET), XRD, FT-Raman and TEM-EDX and
were found to be highly dependent on both calcination temperature and CeO2 loading.
The addition of CeO2 led to the stabilisation of anatase phase titania after calcination at 873 K, compared to
the blank TiO2 reference where phase transformation to rutile occurred. High loading of CeO 2 led to segregation of
cubic CeO2 on the surface of anatase crystallites. After calcination at 673 K crystallisation of titania occurred in
samples with less than 5% CeO2, with loading of 5% CeO2 and above leading to amorphous materials.
Figure 1 reports the main morphological features relative to
the parent undoped TiO2 and to the 10% CeO2, confirming the
above statement about the delay in the crystallization process
brought about by high % of promoting agent.
The effect of CeO2 inclusion on the band gap value of the
parent oxide was investigated using UV-VIS-NIR spectroscopy
and it was found that CeO2 loading led to band gap modification.
Surface acidity and propensity for adsorbed water was investigated using FT-IR by means of CO adsorption and high temperature
treatment in vacuo respectively.
Photocatalytic testing showed that conversion of nitrate was
possible, albeit at low conversion values and that selectivity to N 2
and NO2- varied with CeO2 loading, with no selectivity to NH4+
observed.
Fig. 1. a-b: plain TiO2; c-d: 10% CeO2
References
1
S.Karavoltsos, A.Sakellari, N. Mihopoulos, M. Dassenakis, M. J. Scoullos, Desalination, (1-3) 224 (2008) 317.
[2]
Y. Paz,: Appl. Catal. B: Environmental, 99 (2010) 448-460
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
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2014
7thth JFIC -GIFC,
P27
Sonochemistry and Photocatalysis: Surface Decorated TiO2 Materials Employed in the Photodegradation of Indoor and Outdoor Pollutants
M. Stucchi1, C. L. Bianchi1, C. Pirola1, D. Kanellopoulou2, C. Argirusis2, G. Sourkouni2,3, P. M. Sakkas2, S. Morandi4, G. Cerrato*,4, V. Capucci5
1
Univerisity of Milan, Dept. of Chemistry& INSTM-RU Milan, via Golgi, 19, 20133 Milan (Italy)
2
National Technical University of Athens, Athens, Greece
3
Clausthal University of Technology, Clausthal-Zell, Germany
4
University of Turin, Dept. of Chemistry & NIS Interdept. Centre & INSTM-RU Turin, via P. Giuria 7, 10125 Turin, (Italy)
5
GranitiFiandre SpA, Castellarano (MO), Italy
corresponding author: [email protected]
Keywords: Photocatalysis, Micro-sized TiO2, Promotion by Metals, Surface Decoration
The industrial society produced a wide variety of pollutants [1]: in order to reduce them, among many advanced oxidation processes (AOPs), TiO2 photocatalysis has received a lot of attention as one of the most viable
environmental cleanup technologies; indeed, alternative photocatalytic materials that are as “versatile, economical,
stable, abundant, and non-toxic” as TiO2 are hard to be found [2-3]. The wide band gap of TiO2 is a problem in
particular when the material must be activated by solar light and not by UV light. One of the most viable and practical approaches in developing better photocatalysts is to modify TiO 2 [4]: although the traditional doping proceedings require the insertion of either non-metal or metal atoms in the TiO2 structure, it is also possible to enhance its
photocatalytic activity acting on its surface. The most frequent method is to load nano-sized compounds on TiO2
surface via impregnation [1]. Surface nanoparticles (NPs) can affect the photochemical properties of TiO2 support
in different ways: for example, because of the presence of a metal, the Fermi level of TiO2 can shift to the metal
level inducing the absorption to shift to longer wavelengths. Secondly, metals or metal-oxides can act as electrontraps and they can inhibit the electron-hole recombination, improving the photocatalytic activity, also promoting the
charge separation [1,5].
In this work, the use of sonochemistry to obtain metal or metal oxides NPs (namely Mo, Re, Cu and W) located at the surface of the TiO2 substrate has been employed as a new approach. The sonochemical method described
in this paper has been already used e.g. for the SOFC decoration of SOFC anode materials. [6].
A combined process of deposition and ultrasonication has been used in aqueous or organic solution, where the
support has been dispersed. The solution containing the nanoparticles (stating from the precursors as follows:
Mo(CO)6, W(CO)6, CuCl2*2H2O, and Re2(CO)10) is co-sonicated with a commercial micrometric TiO2 powder
(1077 by Kronos) to obtain decorated TiO2 particles [7]. All powders have been then washed, centrifuged and calcinated to completely remove the organic scents.
All samples were characterized by means of XRD, SEM, TEM and FT-IR (OH rating) analysis and surface
decoration with either metal NPs or metal oxide species has been confirmed in all cases.
Furthermore, the photocatalytic properties all these materials have been tested in the degradation of a selected
series of pollutants, namely two V C’s (acetone and toluene) and NOx, using both UV light and LED light.
The results we obtained indicate that some of the decorated samples possess an interesting photocatalytic activity. Although the surface decoration of TiO2 can not be defined as a “doping” and no changes in the TiO2 structure, leading to lowering the band-gap, is evident, certainly it affects to some extent the photocatalytic activity of
TiO2 itself. For this reason, the possibility to obtain a controlled surface decoration of the TiO 2 is very interesting
and the sonochemical method can be considered a novelty.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
S. Wang, H.M Ang, M.O. Tade, Env. International, 33(5) (2007) 694-705.
H. Park, Y. Park, W. Kim, W. Choi, J. Photochem. Photobiol. C: Photochemistry reviews, 15 (2013) 1-20.
C.L.Bianchi, S.Gatto, C.Pirola, A.Naldoni, A.Di Michele, G.Cerrato, V.Crocellà, V.Capucci, Appl. Catal. B: Environmental, 146 (2014) 123-130.
A.Zaleska, Recent Patents on Engineering, 2 (2008) 157-164.
D.M. Tobaldi, A. Sever Skapin, R.C. Pullar, M.P. Saebra, J.A. Labrincha, Ceram. Intern., 39 (2013) 2619-2629.
P.M. Sakkas, O. Schneider, G. Sourkouni, C. Argirusis, Ultrason. Sonochem., 2014, in press.
C. L. Bianchi, C. Pirola, G. Cerrato, S. Morandi, V. Capucci, Chem. Eng. J., 2014, in press
P28
77ththJFIC
JFIC-GIFC,
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Turin,Italy,
Italy,May
2014
Conducting/piezoresistive wires and tracks based on 1-D and 2-D carbon polymer
composites
S. Cravanzola, L. Muscuso, F. Cesano*, D. Scarano and A. Zecchina
Department of Chemistry, NIS (Nanostructured Interfaces and Surfaces) Centre of Excellence and INSTM Centro di Riferimento, University of Torino, Via P. Giuria, 7, 10125 Torino (Italy),
Keywords: Carbon nanotubes, Exfolitated Graphite, Few-layer graphene, Polyolefins, Localized electrical percolation.
Composites materials based on carbon conducting fillers (carbon nanotubes, exfoliated graphite and few-layer
graphene), dispersed in insulating polymeric matrices, are attracting a considerable interest for their use in many
applications fields, such as polymer and flexible electronics, anti-static, sensoring and structural applications. As a
matter of fact, the conventional fabrication of conductive tracks and wires, which is usually tackled with metals (i.e
Cu, Ag, Au), needs new conductive materials for the reciclyng, the efficient transport and the low-weight materials
issues.
For composite materials based on conducting fillers, the resulting electric properties are mainly determined by
the filler nature and concentration. Depending on the polymer and on the conductive fillers, an insulator-toconductor transition occurs at a specific concentration of the conductive filler (percolation threshold), which is associated with the formation of a continous conductive network. Furthermore the electrical conductivity is stressstrain dependent: this implies the occurrence of piezoresistive properties, which can be used for sensing deformations. As the conductivity in composites is usually an unisotropic property at the macroscale, it is of particular interest to obtain electrical properties along segregated paths in bulk materials [1], or along tracks [2] and wires [3].
In this contribution we report the fabrication of metal-free wires and conductive tracks on the surface of polyolefins (polyethylene, PE, polypropylene, PP) cointaining CNTs /exfoliated graphite (EG) below the percolation
threshold.
As for conductive wires, fibres, 1.5 mm and 3 mm in diameter, were prepared by melt blending the raw materials (PP, EG and/or MWCNTs) in different proportions (1-15wt% MWCNTs and/or 1-5wt% EG), which were then
placed in a extruder under a selected screw speed (2,5-10 rpm).
As for the conductive tracks on polymers, they were obtained by laser irradiation on non-conductive
MWCNT/PE composites. The resulting effect is the local polymer melting, with the formation of an accumulation
layer of MWCNTs, where percolation of nanotubes is occurring. This leads to formation of tracks characterized by
an enhancement of conductivity of several orders of magnitude [Fig.1].
The investigation of the materials has been made by means of several techniques, including microscopies (SEM,
AFM) and electrical characterizations.
Fig. 1. SEM lateral view of a laser-irradiated region of CNTs/composite; b) and c) high-resolution SEM images
taken along the profile of the track and in a region far from the laser track, respectively.
References
[1]
H. Hu, G. Zhang, L. Xiao et al., Carbon 50 (2012) 4596.
[2]
F. Cesano, I. Rattalino, D. Demarchi et al., Carbon 61 (2013) 63.
[3]
S. Cravanzola, G. Haznedar, D. Scarano et. al., Carbon 62 (2013) 270.
P29
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2014
7thth JFIC -GIFC,
Amphiphilic poly(amido)amine dendrimers for efficient siRNA delivery
and gene silencing in prostate cancer model
C. Chen1, X. Liu1,3, T. Yu1,2, P. Rocchi1, L. Peng*,1
1
Aix Marseille Université, CINaM, CNRS UMR 7325, Campus Scientifique de Luminy, Case 913, 13288 Marseille Cedex 9,
France
2
Wuhan University, College of Chemistry and Molecuar Sciences, 430072 Wuhan, P.R.China
3
Aix-Marseille Université, Centre de Recherche en Cancérologie de Marseille, INSERM UMR 1068 Institut Paoli-Calmettes, 27
Boulevard. Leï Roure, BP 30059, 13273 Marseille, France
Keywords: amphiphilc dendrimers, self-assembly, siRNA delivery
Dendrimers have became prominent synthetic macromolecules for drug delivery thanks to their unique properties of high drug payload confined within a compact nanoscale volume and their well-defined structure, regular
branching units as well as the possibility to have different terminal functionalities to impart various physicochemical properties [1]. Amphiphlic dendrons are able to self-assembly spontaneously into non-covalent supromoelcuar
dendrimers, which can resemble to the conventional covalently constructed dendrimers in multivalency, cooperativity and high drug payload while with much ease for preparation. Therefore, supromoelcuar dendrimers formed with
amphiphilic dendrons are emerging as novel nanovectors for drug delivery in nanomedicine [2]. We have previously demonstrated structurally flexible poly(amidoamine) dendrimers for nucleic acid delivery [3]. Here, we will present the self-assembly of amphiphilic poly(amidoamine) dendrons into nanosized supra-molecular dendrimer structures [4] and their resulting capacity to effectively deliver siRNA [5]. Our dual in vitro/in silico investigation strategy highlighted that an optimal balance between the hydrophobic alkyl chain length and the hydrophilic dendron
component plays a crucial role in the self-assembly of these dendrimers for effective siRNA delivery and gene silencing.
Fig. 1. Amphiphilic dendrons self-assemble into large supramolecular dendrimers, which are able to act as nanocarriers to deliver siRNA therapeutics and produce gene silencing in the view to achieving potent anticancer activity in prostate cancer models.
References
1
M. A. Mintzer, M. W. Grinstaff, Chem. Soc. Rev. 40 (2011) 173.
2
V. Percec, D. A. Wilson, Science 328 (2010) 1009.
3
(a). J. Zhou, J. Wu, N. Hafdi, J. P. Behr, P. Erbacher, L. Peng, Chem. Commun. 22 (2006) 2362; (b). X. Liu, P. Rocchi, F.
Q. Qu, S. Q. Zheng, Z. C. Liang, M. Gleave, J. Lovanna, L. Peng, Chem. Med. Chem. 4 (2009) 1302; (c). J. Zhou, C. P.
Neff, X. Liu, J. Zhang, H. Li, D. D. Smith, P. Swiderski, T. Aboellail, Y. Huang, Q. Du, Z. Liang, L. Peng, R. Akkina, J. J.
Rossi, Mol. Ther. 19 (2011) 2228; (d). X. Liu, C. Liu, E. Laurini, P. Posocco, S. Pricl, F. Qu, P. Rocchi, L. Peng, Mol.
Pharmaceutics 9 (2012) 470.
4
C. Chen, P. Paola, X. Liu, E. Laurini, C. Liu, Y. Wang, V. Dal Col, T. Yu, M. Fermeglia, F. Qu, P. Rocchi, S. Pricl, L.
Peng, submitted.
5
T. Yu, X. Liu, A-L Bolcato-Bellemin, Y. Wang, C. Liu, P. Erbacher, F. Qu, P. Rocchi, J. P. Behr, L. Peng, Angew. Chem.
Int. Ed. 51 (2012) 8478.
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CT complexes of DDQ with amino molecules in polar solvents
V. Ribotta, E. Chiavazza1,*, S. Berto1, M. Malandrino1
1
University of Turin, Department of Chemistry, via P. Giuria 7, 10125 Turin, Italy
Keywords: CT complexes, DDQ, Procaine, Atenolol, Spectrophotometry
The charge-transfer (CT) complexes formed from the reaction of electron acceptors with donors containing
heteroatoms, such as nitrogen, sulphur or oxygen, have seen a growing importance in recent years. In particular,
they can play an important role in analytical chemistry because they can be used in the quantitative estimations of
drugs [1-6]. The CT complexes formed between the drug and the acceptor absorb radiations in the visible range and
the absorbance values at the maxima absorption wavelengths are used for the quantification of the drugs. The linear
range of the response and the sensitivity of the detection system are related to the stoichiometry and to the stability
of complexes formed. The acceptors more used with this aim are the 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
(DDQ), tetracyanoethylene (TCNE), 2,3,5,6-tetrabromo-1,4-benzoquinone (bromanil), 2,3,5,6-tetrachloro-1,4benzoquinone (chloranil).
In this work the interaction of the acceptor DDQ with molecules containing nitrogen atoms in acetonitrile and
ethanol was studied. We evaluated that the DDQ preferentially interacts with not aromatic amines, therefore the
attention was focused on the study of the interaction of DDQ with two molecules containing these functional
groups: a -adrenergic blocking drug, the atenolol, and a synthetic local anaesthetic drug, the procaine. In order to
obtain stable and coherent results we evaluated preliminarily the stability of DDQ in the two polar solvents and the
time necessary to obtain a stable and high response with the drugs. The stability of DDQ is not excellent and the
deteriorated solution absorb in the same range of CT complexes. In order to allow the complex formation but to
avoid an eccessive degradation of free DDQ, the solutions were prepared in inert atmosphere and the signals of the
complexes were recorded after 15 minutes from the solutions preparation. The experiments were conducted at 25 ±
0.1°C. For both the systems, the stoichiometries of the complexes were defined with the Job’s plot method and the
stability constants were calculated from spectrophotometric titration data using the software Hyspec [7]. The suitable concentration working range for the quantification of each drug was determinated and the quantification of
procaine and atenolol in a wastewater derived from a pharmaceutical laboratory were performed.
In accordance with the previous works, the CT complexes formed show spectra with 6-7 bands in the range
350-600 nm. The stoichiometry of the complexes are in all cases 1:1 and logK ranging between 3 and 5. A good
linearity was obtained for the two systems in the range between 50 and 200 mg/l of drugs. The linearity range is
linked to the stoichiometry of the complexes and the signals increase linearly with the concentration of the drugs
until the excess of DDQ has been reached.
References
[1]
M. Pandeeswaran, K.P. Elango, Spectrochimica Acta Part A 75 (2010) 1462
[2]
M. Pandeeswaran, K.P. Elango, Spectrochimica Acta Part A 65 (2006) 1148
[3]
H. H. Salem, Journal of Pharmaceutical and Biomedical Analysis 29 (2002) 527
[4]
A. Fathima, S. Rao, G.Venkateshwarlu, International Journal of Chem Tech Research 3 (2011) 1769
[5]
M. S. Refata, A. M. El-Didamony, Spectrochimica Acta Part A 65 (2006) 732
[6]
T. Veeraiah, G. Anjaiah, P. Kista Reddy, Journal of Scientific & Industrial Research 64 (2005) 504
[7]
P. Gans, A. Sabatini and A. Vacca, Talanta 43 (1996) 1739
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Tailoring new adhesives for Cultural Heritage conservation (poster)
D. Cimino1, C. Riedo1,2, R. Ploeger3, A. Colombo4, R. Simonutti4, B. Lavedrine5,
R. E. de la Rie6, O. Chiantore1,2, T. Poli*,1
1
University of Turin, Chemistry department, via Pietro Giuria 7, Turin, Italy
Nanostructured Interfaces and Surface (NIS), via Pietro Giuria 7, Turin, Italy
3
National Gallery of Art, Washington, D.C, USA
4
Department of Material Science, University of Milano-Bicocca, via Cozzi 53, Milan, Italy
5
Centre de recherche sur la conservation des collections, Muséum National d’Histoire Naturelle, Paris, France
6
University of Amsterdam, Amsterdam, The Netherlands
2
Keywords: adhesive, conservation, characterization, cultural heritage
New consolidating adhesives, specifically tuned for painted works of art such as easel paintings, polychrome
wooden sculptures and decorations where adhesion failures may occur among different paintings or between the
layers and the support, are being investigated in this work. The critical issues to be considered for a consolidating
adhesive are:
- Chemical. The formulations should be easily soluble in the largest range possible of solvents in order to
exploit their properties. The control of penetration, tack time and wetting capacity of the solution is very important
in the conservation complex operations, in particular considering the extreme variety of the materials involved
(canvases and textiles, drying oils, protein based binders, acrylics, wood, etc). Good solubility permits to avoid
“chromatographic” separation effects when a penetration of the product is required. The possibility of mixing the
polymer with other components can extend the applicability in all those cases where particular properties are
required. Ideally, the adhesives should be applicable both with solvents and through heat activation.
- Mechanical. At room temperature (20°C) the adhesive must present adequate “flexibility”. This is very
important in order to absorb dimensional variations induced by temperature and humidity, phenomenon very
common in materials such as wood or canvas and in particular when heterogeneous materials are coupled together.
- Physical. The tack strength should guarantee that, in case of major stresses, any eventual failure is
addressed to the adhesive and not to the consolidated painted fragment/layer. .
- Long term stability. Chemical, physical and mechanical properties should be guaranteed as long as
possible, taking into account the influence of the ageing factors acting on the works of art in the usual display or
storage conditions (oxygen, light, heat, humidity, biodeterioration).
Furthermore, the adhesive must be transparent when pure and apt to be colored with dyes and pigments without
losing significantly the chemical, physical and mechanical properties.
One or more consolidating adhesives are being developed starting from ethylene vinyl acetate (EVAc), butyl
acrylate (EBA) and acrylic triblock structures (PMMA-BA-PMMA) as base polymers for the formulation. These
copolymers possess interesting features in terms of hydrophobicity, adhesion to low surface energy substrates and
adhesion/cohesion balance, resistance to alkali treatments and to UV radiation. Tuning of functional properties is
done by controlling the monomer compositions and by the selection of suitable tackifiers. Formulations applicable
both with solvents and through heat activation are investigated, for wide applications possibilities on damaged artworks. The components interactions and their roles are being investigated in order to design affordable formulations
capable of enhancing the chemical-physical properties and the durability in comparison with the products commonly used by restorers. Long term stability of the different components together with their miscibility characteristics
will be correlated with the adhesive performances. For fine tuning of the properties addition of other additives such
as plasticizers, stabilizers or thickeners is also evaluated.
References
[1]
M.L. Barrueso-Martinez, T. Del Pilar Ferrándiz-Gómez, C.M.Cepeda-Jiménez, J. Sepulcre-Guilabert, J.M. MartínMartinez, Journal of Adhesion Science and Technology. 15 (2012) 243-263
[2]
G.A. Berger, International Institute for Conservation of Historic and Artistic Works. 17 (1972) 173-194
[3]
C. W. McGlinchey, R. Ploeger, A. Colombo, R. Simonutti, M. Palmer, O. Chiantore, R. Proctor, B. Lavédrine, E.R. de La
Rie, Symposium 2011: Adhesives and consolidants for conservation: research and applications. Ottawa. (2011) 1-20
[4]
R. Ploeger, E.R. de la Rie, C.W. McGlinchey, M. Palmer, C.A. Maines, O. Chiantore, Polymer degradation and stability.
(2014) DOI: 10.1016/j.polymdegradstab.2014.01.031
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P32
Characterization and study of chromic properties of thermochromic pigments for
artistic and design applications
G.Rollo*,1, D.Cimino1, C.Riedo1,2, O.Chiantore1,2
1
2
University of Turin, Chemistry department, via Pietro Giuria 7, Turin, Italy
Nanostructured Interfaces and Surface (NIS), via Pietro Giuria 7, Turin, Italy
(*) corresponding author: [email protected] (font style: Times 9pt)
Keywords: smart materials, thermochromic pigments, color measurement, design, art
Thermochromic (TC) materials belong to the class of the “smart materials”, because of their capacity to react to
external stimuli. A color changing in TC compounds takes place when materials are heated up to an activation (or
switching) temperature, while the color reverts to the original on cooling. The thermochromic property is this characteristic reversible dependence of color on temperature [1]. TC color changing pigments have been mostly experienced and used for wide commercial applications in the Nineties, but since several years a new interest in these
materials has been shown. TC pigments are generally used in paints, inks and dyed fabrics, mainly with the purpose
of developing smart packagings and “high technology” fibers for fashion industry [1,2]. TC colors are also used for
everyday objects like toys, dolls, recording media, and in novelties such as seals on beverage mugs, mostly as temperature indicators [3]. Potentialities of these materials have been also experimented by artists and designers during
the last twenty years, leading to the creation of design furnitures, interactive surfaces for architectures and site
specific installations [4].
This work focuses on the chemical characterization of a blue TC commercial paint and of two blue TC pigments
based on leuco dyes -both in form of powder and aqueous dispersion, as provided by the supplier- as well as on the
ageing and the study of chromic behavior of coatings prepared in laboratory from those materials. The paint is characterized by an activation temperature of 31°C, while each pigment of 31°C and 47°C, respectively. For these values, the fading of blue color should be almost achieved. Samples of the commercial paint and of TC powders have
been preliminary analyzed using IR Spectroscopy and Pyrolysis Gas chromatography/Mass Spectroscopy. Two series of mock-ups constituted by thin films on aluminum substrates have been prepared. The first one has been realized applying the commercial paint on metal, while the second one mixing the TC slurries with an acrylic binder
and after layering the formulation on the supports. Some of these coatings have been covered with different light
stabilized polymeric transparent films. The color changes with temperature and exposure to light is monitored. The
color measurements are taken at regular time intervals using a spectrophotometer, at ambient temperature and in
combination with a hot stage.
The research is aimed at a better understanding of the relationships between chemical composition and the
chromic properties of these smart materials, by comparing the commercial product with the laboratory prepared
formulations, in order to provide a scientific support to their use in artistic and design applications.
References
[1] D. Aitken, S.M. Burkinshaw, J. Griffiths, A.D. Towns, Review of Progress in Coloration and Related Topics. 26 (1996) 1-8
[2] R. Kulčar, M. Friškovec, . Hauptman, A. Vesel, M. Klanjšek Gunde, Dyes and Pigments. 86 (2010) 271-277
[3] M.A.White, M.Le Blanc, Journal of Chemical Education, 76 (1999) 1201-1205
[4] D.van der Maas, M. Meagher, C. Abegg, J. Huang, in: Computation: The New Realm of Architectural Design (2009) 491496
G.R. acknowledges ISI Foundation and CRT Foundation for the support through The Lagrange Project 2013-2014.
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P33
Optimization by PCA and DOE of intercalation yield into hydrotalcites by liquid
assisted grinding
Eleonora Conterosito,1* Marco Milanesio,1 Claudia Barolo,2 Valentina Toson,1 Valentina
Gianotti,1
1
Università del Piemonte Orientale “A. Avogadro”
Dipartimento di Scienze e Innovazione Tecnologica and Nano-SiSTeMI Interdisciplinary Centre
Viale T. Michel 11, I-15121 Alessandria, Italy
2
Università degli Studi di Torino, Dipartimento di Chimica and NIS Interdepartmental Centre, Via P.Giuria 7,10125 Torino,
Italy
Keywords: Hydrotalcite, Mechanochemistry, Intercalation, X-ray Powder Diffraction, Design of experiment.
The liquid assisted grinding (LAG) method of fast and facile preparation of organic-intercalated LDH nanocomposites developed in our previous work, [1] for the production of low cost, stable and efficient functional materials,
based on organic molecules inserted into hydrotalcite (LDH) is here employed to produce new photoactive hybrid
materials and to screen the organic compounds that most likely undergo easy intercalation. The intercalation of
dyes for DSSC cells and of materials for light downshifting to improve photovoltaic module yields was explored.
Two novel molecules, 5-[({[5-(dimethylamino)naphthalen-1-yl]sulfinyl}oxy)amino]pentanoic acid and a squaraine
dye, and (2E)-2-cyano-3-[4-(dimethylamino)phenyl]prop-2-enoic acid (Dye B) were intercalated. Moreover SDS
and 2-naphtalenesulfonic acid (NSA), that can be used for dye dilution, were intercalated into LDH. LAG method
was exploited to determine in short time if a number of molecules can be successfully intercalated into LDH. The
tests performed on a quite large number of molecules allowed on one side to determine whether that particular molecule can be intercalated and on the other side to collect general data on the molecular features that favour the intercalation using Principal component analysis (PCA) and molecular descriptors to classify molecules. A total of about
ten molecules were tested and 5 were successfully intercalated, while a partial intercalation was observed for some
of them. These novel materials were characterized by X-ray powder diffraction and thermogravimetric analysis. To
improve reaction yields, design of experiment (DOE) techniques were employed to find the optimal intercalation
conditions for the partially successful cases and reach at least a 70-80% yield. Finally multivariate principal component analysis (PCA) was carried out to rationalize the success of the intercalation as a function of chemical descriptors, considering all the new molecules prepared by LAG method in current and in previous works [1].
References
[1] E.Conterosito, W.Van Beek, L. Palin, G. Croce, L. Perioli, D. Viterbo, G. Gatti, M. Milanesio Cryst. Growth. Des. 2013, 13,
1162.
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P34
Modelling the carbonate substitution in hydroxyapatite towards bone composition
M. Corno1,*, M. Delle Piane1, F. Peccati2, G. Ulian3, G. Valdrè3, P. Ugliengo1
1
Dipartimento di Chimica and NIS (Nanostructured Interfaces and Surfaces Centre), Università di Torino, Via P. Giuria 7,
10125 Torino, Italy
2
Departament de Química, Universitat Autònoma de Barcelona, Bellaterra, 08193, Spain
3
Dipartimento di Scienze Biologiche, Geologiche e Ambientali, Centro di Ricerche Interdisciplinari di Biomineralogia, Cristallografia e Biomateriali, Università di Bologna “Alma Mater Studiorum”, Piazza di Porta San Donato 1, 40126 Bologna, Italy
Keywords: biomaterials, hydroxyapatite, DFT calculations, bone composition, molecular dynamics
Hydroxyapatite [HA, Ca 10(PO4)6(OH)2] is the main constituent of the inorganic phase of bones and teeth and is
widely studied and applied as a biomaterial for tissues repairing and reconstructing. The biological HA is characterized by the presence of vacancies and defects, the most relevant being the carbonate ion substitution in the lattice
(about 6% in weight). The CO 32- ion can be accommodated either in place of the hydroxyl groups (type A defect) or
of the phosphate group (type B) of the unit cell. The detailed knowledge of these possible HA defective structures
has recently gained great interest, in order to design improved prosthetic materials, since the carbonate incorporation can influence the adsorption processes at the mineral surface in the biological environment. In this context,
theoretical methods can be successfully applied to provide structural information and surface properties at an atomistic level and be compared with experimental measurements.
In this contribution, some recent results of our computational study on the role of carbonate ion in both fully
(see Figure 1) and partially carbonated hydroxyapatite will be presented. Static calculations at the DFT level have
been run to simulate structural, electronic and vibrational bulk properties of the A-, B- and AB-type defects [1,2,4].
Moreover, ab initio molecular dynamics simulations have been employed to provide insights on the CO 32− mobility
[3]. Work is in progress to model and characterize different surfaces of carbonated apatite, both plain and in interaction with biologically interesting molecules.
Fig. 1. Fully carbonated HA unit cell [Ca10(PO4)6CO3] viewed along the c (left) and a (right) axes.
References
[1]
G. Ulian, G. Valdrè, M. Corno, P. Ugliengo, Amer. Miner. 98 (2013) 410.
[2]
[3]
F. Peccati, M. Corno, M. Delle Piane, G. Ulian, P. Ugliengo, G. Valdrè, J. Phys. Chem. C 118 (2014) 1364.
[4]
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P35
NOVEL NO-DONOR DOXORUBICINS.
1
1
D. Cortese , K*. Chegaev1, C. Riganti2, B. Rolando1, R. Fruttero1, A. Gasco1
Dipartimento di Scienza e Tecnologia del Farmaco, Università di Torino, via P. Giuria, 9, 10125 Torino, Italy;
2
Dipartimento di Oncologia, Università di Torino, via Santena 5/bis, 10126 Torino, Italy.
Keywords: doxorubicin, NO-donor, Multidrug Resistance, multitarget drugs.
Doxorubicin (DOX), is an antibiotic belonging to the class of antracyclines, used for the treatment of a wide
range of cancers, including hematological malignancies, many types of carcinoma, and soft tissue sarcomas. However there are some serious limitation to DOX efficacy in cancer therapy. The one of them is the easy development
of the resistance through different mechanisms, the main of which is the overexpression of ATP-Binding Cassette
(ABC) transporters, such as P-glycoprotein (Pgp), Multidrug Resistance Related Proteins (MRPs) and BreastCancer Resistance Related Protein (BCRP), that actively extrude the drug from tumor cells. Resistance to DOX is
often part of a cross-resistance towards several anticancer drugs known as Multidrug Resistance (MDR) [1]. The
identification of new MDR-reversing agents selectively targeting drug-resistance cells is a field of active investigation, but until now no satisfactory reversing strategies have been identified [2].
Some exogenous NO-donors like S-nitrosopenicillamine, sodium nitroprusside and S-nitrosoglutathione, are
able to reduce the activity of Pgp and MRPs by nitration of tyrosine residues, crucial for protein functions with
consequent increase of intracellular DOXO concentration and toxicity in MDR tumor cells [3]. In previous works
we demonstrated that a class of NO-donors, 1,2,5-oxadiazole 2-oxides (furoxans), was able to inhibit Pgp and
MRP1 transporters in MDCK cells [4]. Lately, our group showed that some NO-donor linked to DOXO through an
ester linkage can reduce MDR in human cancer cells [5]. These compounds were studied on doxorubicin-resistant
human colon cancer cell populations (HT29-dx). This experimental model have highlighted the ability of NO-donor
DOXO to trigger anticancer action and to overcome the drug resistance of the cells, demonstrating that the design
of NO-donor antitumor drugs could be a useful strategy to improve efficacy against drug-resistant tumors.
Here we report an extended series of new NO-donor D X ’s where different
-donor moieties are linked to
DOXO via ester or amide linkers. All these compounds have been tested for their metabolic stability and their activity on HT29 and HT29-dx cell lines, i.e. human colon cancer cells that are respectively sensitive and resistant to
doxorubicin.
O
O
OH
OH
O
OH
OH
OH
O
O
O
O
OH
NH2 HCl
HO
NH
NO-donor
O
References
[1]
[2]
[3]
[4]
[5]
K. Takara et al., Curr. Pharm. Des. 12 (2006) 273-286.
D. Türk et. al., Cancer Res., 69 (2009) 8293-8301.
C. Riganti et al., Cancer Res., 65 (2005) 516-525.
R. Fruttero et al., J. Med. Chem., 53 (2010) 5467-5475.
K. Chegaev et al., ACS Med Chem Letters, 2 (2011) 494-497.
O
O
O
HO
O
NO-donor
O
O
OH
O
P36
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May 55thth-6
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2014
7thth JFIC -GIFC,
Porous and Layered Solids for the development of Innovative Quasi-Solid
Electrolytes for DSSC Applications
D. Costenaro1*, C. Bisio1, G. Gatti1, L. Marchese1, L. Etgar2,3, M. K. Nazeerudin3,
M. Graetzel3, F. Oswald4, T. B. Meyer4
1
Università del Piemonte Orientale “A. Avogadro”Dipartimento di Scienze e Tecnologie Avanzate and Nano-SISTEMI
Interdisciplinary Centre;, Alessandria, 15121, Italy
2
The Hebrew University of Jerusalem, Institute of Chemistry, Jerusalem 91904, Israel
3
Ecole Polytechnique Fédérale de Lausanne, Institut des Sciences et Ingénierie Chimiques, Laboratoire de Photonique et Interfaces, Station 6, CH-1015 Lausanne, Switzerland
4
SOLARONIX SA, Aubonne, 1170, Switzerland.
Keywords: Porous Material, Layerd Solid, Quasi-Solid Electrolytes, Dye Sensitized Solar Cell
Dye-sensitized solar cells (DSSC) are attracting the interest of the scientific community due to their potential
advantages of high efficiency and low cost[1]. Recent studies showed that the use of a quasi-solid electrolytebased DSSC, commonly obtained by adding to nitrile-based electrolytes or ionic liquid mixture solid particles
with different chemical nature, led to a significant increase in energy-conversion efficiency and long term stability. Quasi-solid electrolytes were obtained by adding to liquid electrolyte mixture solid particles with different
chemical nature[2]. In our approach, solids with controlled properties and chemical composition have been selected to understand the role of nanoparticles in the final performances of DSSC devices. Interesting results
were obtained by using synthetic saponite clays as additives for DSSC devices. Synthetic saponite-clay materials with homogeneous particle size, were prepared by properly adapting the synthesis conditions. The obtained
solids were used for the preparation of electrolytes for DSSC purposes by dispersing 5wt.% of clays into a 3methoxyproprionitrile-based electrolyte. The electrochemical characterization showed that the addition of the
saponite sample with the largest particles does not influence the solar cell efficiency, whereas the use of electrolyte having saponite suspension with the smallest particle size led to an increase of solar cell efficiencies of 8%
with respect to the reference cell. It was proved that this behavior is associated to the fact that saponite with
smaller particles favors scattering phenomena inside the electrolyte suspension, thus having a positive effect on
the cell short circuit current. Tests of the stability of DSSC prepared by using saponite-based electrolytes indicated that the addition of layered solids increases the solar cell long term stability up to 1200 h under solar soaking [3]. In addition, a quasi-solid electrolyte ionic liquid based was prepared by dispersing 15wt.% of commercial amorphous silica F5 particles and modified silica particles. Commercial bare silica F5 particles and modified silica F5 by NH2 and NH3+ groups were prepared, and fully characterized. The modification of the silica
particles by NH2 groups increases the open circuit voltage (Voc) from 699 mV for the pure ionic liquid electrolyte reference cell to 815 mV after the introduction of modified silica particles[4].
Fig. 1. Left side: J-V curves of DSSCs devices prepared by using Z946 reference electrolyte (-■- and 5wt% electrolyte suspensions prepared by adding different saponite samples prepared by using variable H 2O/Si ratio (ranging from 20 to 150). TEM
images of these samples with by different particles size are reported in the inset. Right side: J-V curves for the DSSCs with
reference electrolyte Z952 (curve a) and electrolyte prepared by adding 15wt% of F5 silica (curve b), and modified silica materials (NH2_F5 (curve c), NH3+_F5 (curve d)).
References
1 B. ’Regan, M. Grätzel, Nature. 353 (1991) 737
[2] P. Wang, S.M. Zakeeruddin, P. Comte, I. Exnar, M. Grätzel, JACS, 125 (2003) 1166
[3] D. Costenaro, C. Bisio, F. Carniato, G. Gatti, F. Oswald, T.B. Meyer, L. Marchese, Solar Energy Materials & Solar
Cells,117 (2013) 9
[4]
L. Etgar, G.Schuchardt, D. Costenaro, F. Carniato, C. Bisio, S.M. Zakeeruddin, K.M. Nazeeruddin, L. Marchese, M.
Gräzel, J. Mater. Chem. A, 1 (2013) 1014
-GIFC, Turin,
Turin, Italy,
Italy, May
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P37
Assessment of the photoreactivity of Dissolved Organic Matter DOM: A comparison between three different types of ecosystems.
E. De Laurentiis*1, S. Berto1, M. Isaia2 and D. Vione1, 3
2
1
University of Turin, Department of Chemistry, Via P. Giuria 5, 10125 Turin
University of Turin, Department of Life Science and Systems Biology, Via Accademia Albertina 13, 10123 Torino
3
University of Turin, Centro Interdipartimentale NatRisk, Via L. Da Vinci 44, 10095 Grugliasco (TO)
(*) Corresponding author: [email protected]
Keywords: Lake water photochemistry, Dissolved Organic Matter, sensitized photolysis, subterranean environments
In natural water systems, photochemical processes can be important transformation pathways for organic compounds of both natural and anthropic origin. Sunlight (λ> 290 nm) represents the driving force of all such processes; in surface waters, photochemical reactions take place in the photic zone where many other biotic and abiotic
processes also occur. Many of the xenobiotics released into the environment (e.g. polycyclic aromatic hydrocarbons, pesticides and pharmaceuticals) are refractory to biological degradation and, in these cases, abiotic processes
(including most notably photochemical reactions) can represent major removal pathways [1-2].
The Dissolved Organic Matter (DOM) is the main actor in the photochemistry of freshwater systems and its chromophoric fraction (CDOM) is directly responsible for radiation absorption and for the production/consumption of
the main reactive transients: the triplet states of chromophoric dissolved organic matter ( 3CDOM*), the hydroxyl
radicals (•OH) and singlet oxygen (1O2) [3].
Despite the DOM complex structure and chemical reactivity, some key information can be obtained by combining
the study of the relationship between the typology of CDOM and its photochemical activity, through the assessment
of reactive species photogeneration, with the investigation of spectral features and fluorescence emission. The
chemical composition of samples should be investigated, too.
We assessed CDOM photoreactivity in three different types of ecosystems: alpine lakes [4] (characterized by
CDOM with different composition), Antartic lakes [5] and subterranean waters [6] (ponds located in mines and
caves). For each sample, the photoproduction of 3CDOM*, 1O2 and •OH was assessed.
By comparing the photochemical activity of CDOM in the different samples, it is highlighted that allochthonous
CDOM from soil runoff is considerably more photoactive than CDOM arising from in-water biological processes
or atmospheric deposition. Furthermore, by studying samples from Antarctic lakes and subterranean environments,
it was possible to infer that pre-exposure of CDOM to sunlight plays a key role in defining its photochemical activity.
References
[1] G. Grabner and C. Richard in Environmental Photochemistry Part II (The Handbook of Environmental Chemistry), Vol. 2M
(eds P. Boule, D. Bahnemann, and P.J.K. Robertson), (2005), Springer, Berlin, 161.
[2] R. M. Pagni and R. Dabestani in Environmental Photochemistry Part II (The Handbook of Environmental Chemistry), Vol.
2M (eds P. Boule, D. Bahnemann, and P.J.K. Robertson), (2005), Springer, Berlin, 193.
[3] M.Czaplicka, J. Hazard. Mater. 134 (2006) 45.
[4] E. De Laurentiis, M. Minella, V. Maurino, C. Minero, M. Brigante, G. Mailhot and D. Vione, Chemosphere 88 (2012) 1208.
[5] E. De Laurentiis, S. Buosio, V. Maurino, C. Minero and D. Vione, Environ. Sci Technol, 47 (2013) 14089.
[6] S. Berto, M. Isaia, B. Sur, E. De Laurentiis, F. Barsotti, R. Buscaino, V. Maurino, C. Minero and D. Vione, J. Photochem.
Photobiol. A: Chemistry 251 (2013) 85.
P38
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Sustained dark formation of hydroxyl radicals upon aeration of anoxic lake water
E. De Laurentiis*1, M. Minella1, V. Maurino1, C. Minero1 and D. Vione1, 2
2
1
University of Turin, Department of Chemistry, Via P. Giuria 5, 10125 Turin
University of Turin, Centro Interdipartimentale NatRisk, Via L. Da Vinci 44, 10095 Grugliasco (TO)
(*) E-mail: [email protected]
Keywords: hydroxyl radicals, anoxic lake water, summer stratification, lake overturn, carbon biogeochemistry, climate change.
The hydroxyl radical (·OH) is a highly reactive transient causing the degradation of most dissolved organic
and inorganic substrates [1]. Moreover, ·OH affects nutrient cycling by producing biodegradable species (low molecular weight acids, amino acids and ammonia) from biorefractory compounds, which favours the mineralization
of organic matter and affects the carbon cycle. The ·OH radical is formed photochemically in surface waters, by
irradiation of photosensitisers such as chromophoric dissolved organic matter (CDOM), nitrite and nitrate [2-3].
Here we report for the first time that ·OH can be produced in the dark by aeration of anoxic lake water. Many
lakes located in temperate environments are stratified during summer, as the warmer and oxygenated surface layer
(epilimnion) floats above the colder and often anoxic deep water (ipolimnion). Lake overturn in late summer – early
autumn ensures oxygenation of the water column. Dark formation of ·OH was assessed in anoxic water (taken from
ipolimnion during summer stratification) upon exposure to the atmosphere, using terephtalic acid (TA) transformation into hydroxyterephtalic acid (TAOH) as ·OH probe reaction. The possible ·OH formation pathways are
Fenton and Fenton-like reactions, induced by FeII and most notably by hydroquinones or semiquinone radicals [4].
The importance of the process can be assessed by comparing dark ·OH formation with photochemical processes taking place in the sunlit epilimnion. To have the same cumulated ·OH concentration produced in a few
hours in air-exposed ipolimnion samples, surface water should be illuminated by fair-weather sunlight for up to 4
months in spring-summer. This is equivalent to about one-half of the year-round sunlight energy received by lake
water, and to even more when considering weather-related issues. Dark ·OH production by aeration of anoxic lake
water, here described for the first time, is thus a new environmental process that could be very important in the
yearly ·OH budget of lake environments. It could play a key role in the self-depollution potential of the lakes and in
carbon biogeochemical cycles, by increasing the bioavailability and mineralisation of dissolved organic matter.
This is an exciting new discovery that could deeply modify the current understanding of the processes that
take place in lake water and that lead to the transformation of natural organic matter and of xenobiotics. Interestingly, the expected modifications of lake dynamics brought about by climate change would initially favour, but could
eventually prevent the overturn-related generation of ·OH radicals.
Fig. 1. Time trend of TAOH formed from 1 mM TA in ipolimnion samples exposed to the atmosphere. Insert: highest TAOH
concentration reached in the experiments (Surf: surface samples; B1, B2: anoxic samples from the ipolimnion). AV: Lake Avigliana; CA: Lake Candia; SdS: Lake Sottano della Sella; VI: Lake Viverone.
References
1 G. V. Buxton, C. L. Greenstock, W. P. Helman, A. B. Ross, J. Phys. Chem. Ref. Data 17 (1988) 513.
[2] J. V. Goldstone, M. J. Pullin, S. Bertilsson, B. M. Voelker, Environ. Sci. Technol. 36 (2002) 364.
[3] M. A. Tarr, W. Wang, T. S. Bianchi, E. Engelhaupt, Wat. Res. 35 (2001) 3688.
[4] S. E. Page, M. Sander, W. A. Arnold, K. McNeill, Environ. Sci. Technol. 46 (2012) 1590.
-GIFC, Turin,
Turin, Italy,
Italy, May
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2014
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P39
Formation and self-assembly of biopolymers on oxide surfaces:
possible insights on prebiotic chemistry
C. Deiana*, Y. Sakhno, I. Barberis, M. Fabbiani, M. Pazzi, M. Vincenti, G. Martra
University of Torino, Department of Chemistry and Interdepartmental Centre “Nanostructured interfaces and surfaces – NIS”
Via P. Giuria 7, 10125 Torino (Italy)
Keywords: amino acids, catalytic polymerization, silica, titania, self-assembly
The study of reactivity of biomolecules on oxides surfaces (intended as actual or model minerals) is of great
interest for the disclosure of peptide bond formation mechanism in prebiotic conditions [1], and, in this respect,
significant advances have been attained [2]. However, open problems are the limited extent of the catalytic oligomerization [3] and the possibility for the mobility of the oligomers on surfaces to form organized structures [1].
In this study, carried out by combining in-situ IR spectroscopy and high-resolution mass spectrometry, the formation of long polypeptides (up to 16 terms) as result of the adsorption of glycine vapors on SiO2 and TiO2 surfaces, consistently with the Bernals’s hypothesis [4], have been obtained for the first time. Glycine is often regarded as
a model for the study of reactivity of amino acids on mineral surfaces [1], and silica and titania have been considered because of their importance in abiotic polymerization of amino acids [1, 5]. TiO2 was also sequentially exposed to glycine (Gly) and glycine-1-13C (13Gly) vapour, and the detection of (Gly)n-(13Gly)m oligomers clearly
indicated the effectiveness of successive monomer "feedings". A similar process was also reported by Ferris et al.
[6], but in that case, the polymerization was achieved by adding an excess of carbonyl diimidazole as an activator.
By subsequent hydration, self-assembly of polyglycines in helical and -sheet-like structures has been detected. Interestingly, peptide chains with β-sheet structures have been reported as being more resistant to hydrolysis, a
difference that likely results in an extended lifetime and may have been utilized by primordial life [7].
These occurrences can provide useful insights into the general problem of the surface reactivity of amino acids, and in particular, into the formation of biopolymers in prebiotic times and their subsequent self-organization as
a consequence of changes in environmental conditions [8].
Scheme 1. Schematic representation of glycine polymerization and self-assembly on mineral surfaces.
References
1
J. F. Lambert, Origins Life Evol. Biospheres 38 (2008) 211.
2
D. Costa, C. Lomenech, G. Bery, L. Stievano, J.-F. Lambert, ChemPhysChem 6 (2005) 1061.
3
J. Bujdák, B. M. Rode, J. Mol. Evol. 43 (1996) 326.
4
J. D. Bernal, The Physical basis of life, Routledge and Kegan Paul, London, 1951.
5
H. J. Cleaves, A. M. Scott, F. C. Hill,J. Leszczynski, N. Sahai, R. Hazen, Chem. Soc. Rev. 41 (2012) 5502.
[6]
P. Ferris, A. R. Hill, R. H. Liu, L. E. Orgel, Nature 381 (1996) 59.
[7]
A. Brack, Chem. Biodiversity 4 (2007) 665.
8
G. Martra, C. Deiana, Y. Sakhno, I. Barberis, M. Fabbiani, M. Pazzi, M. Vincenti, Angew. Chem. Int. Edit.
DOI:10.1002/anie.201311089.
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Turin, Italy,
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P40
Synthesis and biological evaluation of dietary triterpenoid conjugates of biogenic amines and alcohols.
D. Del Prete*,1, C. Bardelli2, C. Avonto1,3, G. Appendino1, S. Brunelleschi2, L. G.
Fresu2
1
Dept of Pharmaceutical Sciences, University of Piemonte Orientale “A Avogadro”, ovara, Italy;
2
Dept of Health Sciences, University of iemonte rientale “A Avogadro”, ovara, Italy.
3
National Center for Natural Products Research, University of Mississippi, United States.
(*)[email protected]
Keywords: triterpenoid conjugates, biogenic amines, biogenic alcohols, biological effects
Oleanolic acid (OA) and ursolic acid (UA) are the major triterpenoid acids of dietary relevance, occurring in olive oil and in culinary herbs like rosemary and sage (1). OA and UA are pleiotropic agents, that target a host of end
point involved in inflammation, cancerogenesis, and glucose control (2). The pharmacokinetics of these compounds
is poorly known, both in terms of absorption and metabolism. Since OA and UA are lipophilic carboxylic acids, the
possibility exists that they are conjugated in vivo with biogenic alcohol (e.g. ethanolamine) and amines (e.g. dopamine), in a mechanism somewhat similar to the formation of bioactive endolipids (endocannabinoids, endovanilloids) from fatty acids (4). To explore this possibility, a series of conjugates of OA and UA with various biogenic
alcohols and amines were synthesized using various coupling strategies to overcome the inherent sluggish reactivity
of the neopentylic carboxylic group of the triterpenoid acids and the ambident nucleophilicy of many biogenic alcohols and amines, that often also contain phenolic hydroxyls. Overall, 20 conjugates were synthesized, and evaluated in a battery of bioassays of nutritional relevance (modulation of NF-B activation and PPAR expression,
production of superoxide anion on human monocytes/macrophages), showing that conjugation can critically affect
the biological profile of dietary triterpenoid acids, providing a rationale for evaluating their formation in vivo.
References
[1] Liu J (2006), J Ethnopharmacol 49:57-68
[2] Genet G et al. (2010), J Med Chem 53:178-90
[3] Brunelleschi S et al. (2007), Pharmacol Res 56:542-549
[4] Di Marzo V. et al (2010), Pharmacol Res 61(6):531-6
P41
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7thth JFIC -GIFC,
Tailored properties of hematite cool pigments with different size and shape
L. Demarchis(*), F. Sordello, M. Minella, C. Minero
Department of Chemistry, University of Turin, via Pietro Giuria 7, 10125, Turin (TO), Italy
Keywords: hematite, pigments, cool properties, solar reflectance, controlled syntheses
Urban heat island (UHI) is a phenomenon which leads to a temperature increase in urban city centres. It is related to a wide variety of problems [1] and in recent years several studies have been performed about the mitigation
of its effects. Among the solutions picked out there is the development of smart cities with buidings made
of/covered by the so called cool materials [2]. These materials show high NIR reflectance and low sunlight absorption and they can be used to produce building materials that reflect more sunlight than conventionally pigmented
products.
In this work, we report the synthesis and investigation of hematite based cool red pigments. Optical properties
depend on size, morphology and cluster aggregation of the pigment particles. Different syntheses were performed
to obtain hematite particles with different size and shape. Control on shape is obtained following two synthetic
methods; i) a gel-sol method [3] which allowed us to obtain hematite particles larger than 300 nm with cubic and
spherical morphology (see fig. 1); ii) a catalytic phase transformation process [4] that leads to spherical particles
with a diameter lower than 500 nm. Size control on hematite particles is obtained by varying experimental parameters: the synthesis temperature in the case of the gel-sol method and the reagent concentration for the catalytic phase
transformation.
We evaluated the “cool properties” of the synthesized nano/micro particles calculating the Solar Reflectance
(SR). SR represents the capability of a material to reflect sunlight and it can be estimated through the following
formula:
2500
SR 
 SIr ( )  % R( )
280
2500
 SIr ( )
280
in which SIr is the solar irradiance and %R is the experimental total reflectance for the investigated material.
SR is directly proportional to the cool properties and its value for the synthesized hematite was used to determine
which pigment shows the higher cooling features. This could be used in urban application for the mitigation of
UHI.
.
Fig 1. Scanning electron micrographs of a) cubic and b) spherical hematite particles obtained through the gel-sol
method.
References
[1]
C Cartalis, A Synodinou, M Proedrou, A Tsangrassoulis, M Santamouris, Energy conversion and management , 14 (2001)
1647.
[2]
A. Coutts, J. Beringer, N. Tapper, Urban Policy and Research 28 (2010) 27.
[3]
T. Sugimoto, K. Sakata, J. Colloid Interface Sci. 152 (1992) 587.
[4]
H. Liu, Y. Wei, P. Li, Y. Zhang, Y. Sun, Mater. Chem. Phys. 102 (2007) 1.
P42
Microwaves Assisted Synthesis Of Functionalized Ionic Liquids With
Long Chain Of Carbon Starting From Imidazole
Samia Amirat and Ahmed Djellal
Department of chemistry, Faculty of Sciences,
University of Annaba,
BP 12, Annaba -23000- Algeria.
Corresponding author: [email protected]
Key words: Ionic liquid, imidazole, microwave, lipophilicity, hydroboration.
The microwave assisted synthesis of 3 - (3-hexadecylimidazolium)-propylboronic acid (3a) and 3 - (3decylimidazolium)-propylboronic acid (3b) is described starting from imidazole 1 in three steps. The
starting material is converted to respectively N-alkyl imidazole (1a-b) [1] and N-alkyl, ’-allyl
imidazolium (2a-b) [2] which by hydroboration in standard conditions [3] give the target
compounds. They possess at the same molecule three properties: the complexing power with e.g
sugars or alcohols, the phase transfer catalyst propriety and the lipophilicity thanks respectively to their
boronic acid function, their imidazolium nucleus and their long chain of carbon. Recently they have
been used to transport some sugars [4].
3 steps
HO
NH
N
R
N
B
HO
1
3 a-b
a:R= C16H33 b: R= C10H21
Figure 1: Synthesis of ILs.
Complexing
power propriety
Phase transfer
catalysis propriety
Lipophilicity
Figure 2: 3D model of synthesized ILs 3b and their properties.
References
[1]
[2]
[3]
[4]
A. Loupy, Microwaves in Organic Synthesis; Wiley-VCH: Weinheim, (2002).
J.S. Buck, Ferry, C. W.; Org. Syn. Coll. Vol. 2, (1943) 290.
H. C. Brown, Organic Synthesis via Boranes. Ed John Wiley & Sons (1975).
S. Amirat,, A. Djellal, Inter. J. of Engineering Research & Technology, IJERT,
Vol. 2 (2013) Issue 6, June.
N
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7thth JFIC -GIFC,
Discovery and optimization of new OvCHT1 inhibitors based on the 4-hydroxy1H-1,2,3-triazole ring.
A. Ducime,*1 A. C. Pippione,1 A. Moreo,1 A. Piccinelli,1 M. Gooyit,2 K. D. Janda,2
D. Boschi1 and M. L. Lolli1
1
MEDSynth, Department of Drug Science and Technology, University of Turin, via Pietro Giuria, 9, 10125 Torino, Italy.
Departments of Chemistry and Immunology and Microbial Science, The Skaggs Institute for Chemical Biology, and The Worm
Institute of Research and Medicine, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037,
United States.
2
Keywords: Onchocerca volvulus, OvCHT1 inhibitors, closantel, bioisosterism
Onchocerciasis, also known as river blindness, is a neglected tropical disease caused by infection with the
parasitic worm Onchocerca volvulus. About 17 to 25 million people are infected with river blindness, mostly in
developing countries including Yemen as well as many nations in sub-Saharan Africa and Central and South
America.1
Onchocerca volvulus chitinase (OvCHT1) is a larval-stage-specific chitinase that was recently identified as a
potential biological target for affecting nematode development. 1,2 Compound 1 is a potent and specific OvCHT1
inhibitor with an IC50 value of 1.98 ± 0.13 µM. In the absence of any crystallographic data of OvCHT1, a ligandbased drug design approach was applied to 1 to improve its potency against OvCHT1. In this work, modulation of
the phenolic substructure of 1 using a non-classical isosteric replacement approach is reported. From a small library
of compounds, the hydroxytriazole scaffold (as in compound 2) was shown to be a good isostere of the phenolic
group. Subsequent modulation of compound 2 was then performed to determine the relevance of the hydroxyl
group at position 4 and N-alkyl substitution of the triazole ring (general structure 3), for OvCHT1 inhibition.
Modification of the terminal phenyl ring was also investigated to further optimize its activity against OvCHT1. The
synthesis and pharmacological properties of the hydroxytriazole-based OvCHT1 inhibitors are herein discussed.
4
5
3
1
2
1
2
3
References
1
2
J. E. Allen, O. Adjei, O. Bain, A. Hoerauf, W.H. Hoffmann, B. L. Makepeace, H. Schulz-Key, V. N. Tanya, A. J. Trees,
S. Wanji, D. W.Taylor, PLoS Neglected Trop. Dis., 2008, 2, No. e217.
A. L. Garner, C. Gloeckner, N.Tricoche, J. S. Zakhari, M.Samje, F. Cho-Ngwa, S. Lustigman, K. D. Janda, J. Med.
Chem., 2011, 54 (11), 3963–3972.
JFIC -GIFC,
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Turin, Italy,
Italy, May
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2014
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P44
Indole-based squaraine dye: a preliminary pH ratiometric study
S. Ellena*,1, C. Magistris1, S. Prosperini1, R. Buscaino1, C. Barolo1,2
2
1
University of Turin, Department of Chemistry, Via P. Giuria 7, 10125 Turin, Italy
University of Turin, NIS Interdepartmental Centre, Via P. Giuria 7, 10125 Turin, Italy
Keywords: pH, squaraine, microwave synthesis
Intracellular pH is an essential factor that regulates many cellular behaviors, including proliferation and apoptosis as well as enzyme activity and protein degradation. High acidity levels have been implicated in a number of
systemic pathologies, such as renal acidosis, metabolic disorders, intoxications, diabetes and emphysema, as well as
localized hyperacidity such as infections, inflammation and cancer. This significant difference in pH provides a
unique opportunity to image the metabolic status of the cancerous tissue. A number of methods, such as H +permeable microelectrodes, 31P NMR spectroscopy, and optical microscopy, have been used to measure pH [1].
Optical imaging techniques, with a suitable pH indicator, are the most powerful tools for assessing intact and
subcellular pH, owing to their high sensitivity and unrivaled spatiotemporal resolution.
To be used in vivo, the indicator should preferably be optically active within a relatively narrow near-infrared
(NIR) region and possess a suitable pKa.
There are several different mechanisms by which an optical probe can indicate a change in environmental pH
but the measurements are difficult to quantify in heterogeneous tissue and recorded intensity changes may be due to
a concentration gradient instead of differences in tissue pH values. Ratiometric probes can eliminate most or even
all of the interferences by measuring the ratio of fluorescence intensities at two different wavelengths.
It is known that bis(indole)-squaraine dyes can be susceptible to the pH [2] but they show a low water solubility. Moreover the quantum yields and fluorescence lifetimes of squaraines are significantly decreased in polar or
protic solvents such as water or aqueous buffers. A hydrophobic microenvironment, e.g. upon binding to proteins,
in non-polar solvents or in micelles, was expected to have a positive effect on the quantum yields and photostabilities which can be mostly attributed to a reduced aggregation tendency.
In this work we report the synthesis and optical characterization of three indole-based squaraines: SQ-H, SQBr and SQ-I see Figure 1.
The adsorption/emission squaraine spectra were recorded at difference pH in presence of a surfactant (cetyltrimethylammonium bromide, CTAB) at critical micellar concentration (cmc). These squaraines show a ratiometric
behavior over 4 pH units.
This is the first step for the application of these squaraines in living cells for ratiometric pH imaging.
Fig. 1.
References
1
J. Srivastava, D. L. Barber, M. P. Jacobson Physiologically 22 (2007) 30.
[2]
S. Miltsov, C. Encinas, J. Alonso Tetrahedron Lett. 40 (1999) 4067.
P45
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2014
77thth JFIC
INDOLENINE-BASED SQUARAINES for PDT: MICROWAVE SYNTHESIS
and STRUCTURE-ACTIVITY RELATIONSHIPS
S. Ellena*,1, F. Foglietta2, N. Barbero1, C. Barolo1,3, R. Canaparo2, L. Serpe2, S. Visentin4
1
University of Turin, Chemistry Department, Via P. Giuria 7, 10125 Turin, Italy
Science and Technology of the Drug Department, Via P. Giuria 9, 10125 Turin, Italy
3
University of Turin, NIS Interdepartmental Centre, Via P. Giuria 7, 10125 Turin, Italy
4
University of Turin, Molecular Biotechnology Center, Via Nizza 52, 10126, Turin, Italy
2
Keywords: PDT, Photodynamic Therapy, squaraine, microwave synthesis, singlet oxygen
The PhotoDynamic therapy (PDT) is a new method for the cancer and other diseases treatment. PDT is a multimodal approach for the living cells (eukaryotes, prokaryotes, fungi...) inactivation based on three elements: a photosensitizer (PS), light at a suitable wavelength and oxygen.[1]
Squaraines (SQ) are one of the most studied class of potential PSs because they show a high absorption in the
NIR region, a simple modifiable structure and a good stability.[2]
The aim of this work was the synthesis and characterization of a library of indolenine-based squaraines. All
the squaraines are symmetric with two indolenine moiety functionalized in 5 and on the nitrogen atom (Figure 1) A
monomodal microwave reactor was used for the squaraine synthesis allowing a general purity and yield increasing
and synthesis time reducing. [3, 4]
A preliminary structure/activity study was performed with a chemical approach. In an air saturated phosphate
buffer PS and the 1,3-diphenyl-isobenzofuran (DPBF) as singlet oxygen probe were dissolved. The solution was
exposed to a suitable light and the DPBF consumption was analysed by UV-Visible spectroscopy.
The substitution in position 5 of the SQ seems to have great importance in the capability of the molecule to release singlet oxygen. In fact, our squaraines activity is directly linked with the atomic number of the substituent
with the following activity order: -COOH < -SO2NH2 < -Br < -I.
This behaviour suggests that the intersystem crossing is due to the spin-orbit coupling and this trend indicates
that the limiting step is the triplet generation.[5]
The PS more interesting for a PDT application are the 5-bromo and 5-iodoindolenine squaraines that showed
an activity comparable with the methylene blue, generally higher than others squaraines previously reported.[6]
These compounds are now testing in vitro to study the uptake, the toxicity and the PDT efficiency.
Fig. 1. Library of prepared squaraines
References
1
M. C. DeRosa, R. J. Crutchley Coord. Chem. Rev. 233-234 (2002) 351.
[2]
R. R. Avirah, D. T. Jayaram, N. Adarsh, D. Ramaiah Org. Biomol. Chem. 10 (2012) 911.
[3]
C. Barolo, J-H Yum, E. Artuso, N. Barbero, D. Di Censo, M. G. Lobello, S. Fantacci, F. De Angelis, M. Grätzel, M. K.
Nazeeruddin, G. Viscardi ChemSusChem 6 (2013) 2170.
[4]
R. Borrelli, S. Ellena, C. Barolo Phys. Chem. Chem. Phys. 16 (2014) 2390.
[5]
S. Webster, D. Peceli, H. Hu, L. A. Padilha, O. V. Przhonska, A. E. Masunov, A. O. Gerasov, A. D. Kachkovski, Y. L.
Slominsky, A. I. Tolmachev, V. V. Kurdyukov, O. O. Viniychuk, E. Barrosso, R. Lepkowicz, D. J. Hagan, E. W. Van
Stryland Phys. Chem. Lett. 1 (2010) 2354.
P46
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2014
7thth JFIC -GIFC,
FTIR and Raman Spectroscopy of Porous Aromatic Frameworks (PAFs)
with Adsorbed Methane: an Experimental and Theoretical Study
M. Errahali1*, G. Gatti1, L. Tei1, M. Cossi1, L. Marchese1
1
Dipartimento di Scienze e Innovazione Tecnologica and Centro Nano-SiSTeMI, Università del Piemonte Orientale “A.
Avogadro”, Via T. Michel 11 - 15121 Alessandria, Italy
Keywords: Porous aromatic frameworks, PAFs, methane interactions, DFT calculations, FTIR
Porous materials have attracted enormous scientific attention due to their potential applications in several
fields such as separation, heterogeneous catalysis, and gas storage. 1 In 2009, Ben et al.2 have developed a method to
synthesise the first 3D porous aromatic framework, named PAF-302, which shows a very high surface area and an
exceptionally high thermal stability. This material is a microporous polyphenylic network obtained by the replacement of the C-C tetrahedral covalent bonds of diamond-like structure with phenyl rings. PAF-302 has shown very
interesting properties for methane storage suitable for automotive aplications4. For this reson, FT-IR and Raman
spectroscopies are employed in this contribution, along with ab initio calculations, to describe the vibrational features of PAF-302 material and investigate the interactions of methane with the porous framework.
A comparative investigation of the physico-chemical properties of the material was carried out by a multidisciplinary approach using FTIR, Raman, SS-NMR, TGA, N2 physisorption at 77K. Particular attention was devoted to a
detailed infrared spectroscopic study of CH4 and CD4 adsorbed into PAF-302. The experimental spectroscopic results were compared with those obtained with DFT ab initio calculations on simple methane/aromatic model systems.
FTIR and SS-NMR spectra of PAF-302 show that a complete polymerization occurred leading to a material with
the expected structural units. PAF-302 shows a high thermal stability (up to 450 °C) and high specific surface area
(BET up to 4500 m2/g) with a predominant microporosity.
We also collected the infrared spectra for the adsorption of
CH4 on PAF-302 at low temperature: the vibrational spectra of PAF-302 and its adduct with methane have been
recorded and resolved (Fig.1) to investigate the interactions with the adsorbed gas.
The analysis shows that the polymerization process is
essentially complete, and that the adsorbed CH4 molecules
interact with PAF surface either with one or two phenyl
rings in a monodentate (C3v local symmetry) or bidentate
(C2v local symmetry) fashion, though multiple interactions (i.e. guest-guest interaction) can be envisaged, especially at high pressures. 4
Fig.1. IR spectra of CH4 gas and difference spectrum of
PAF-302 at equilibrium pressure of 10 mbar CH4
Acknowledgement: The financial support provided by OMB-Saleri and SOL-Group is gratefully acknowledged.
References
[1] McKeown, N. B.; Budd, P. M. Chem. Soc. Rev. 2006, 35, 675–683
[2] Ben, T.; Ren, H.; Ma, S.; Cao, D., Lan, J.; Jing, X.; Wang, W.; Xu, J.; Deng, F.; Simmons, J.M.; Qiu, S and Zhu, G. Angewandte Chemie (International ed. in English), 48(50), 9457-60.
[3] M. Cossi, G. Gatti, L. Canti, L. Tei, M. Errahali and L. Marchese (2012) Langmuir 28(40),14405-14.
[4] M. Errahali, G. Gatti, L. Tei, M. Cossi, L. Marchese, J.Phys.Chem C. Submitted
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P47
Organically modified MCM-41 nanoparticles for Photodynamic
Therapy: synthesis and characterization
B. M. Estevão
1
1,2,*
, Enrica Gianotti1, F. Cucinotta1, N. Hioka2, L. Marchese1
Dipartimento di Scienze e Innovazione Tecnologica, Centro Nano-SiSTeMI, Università del Piemonte Orientale, Via T. Michel
11, 15100, Alessandria, Italy
2
Departamento de Química, Núcleo de Pesquisa em Sistemas Fotodinâmicos, Universidade Estadual de Maringá, Avenida
Colombo 5790, 87020-900, Maringá, Paraná, Brazil
Keywords: photodynamic therapy, MCM-41, Rose Bengal, singlet oxygen, amino-functionalized MSNs
The Photodynamic Therapy (PDT) is a therapeutic treatment that has been used to combat abnormal tissue
growth and localized infections. Its acting principle is based on the generation of highly cytotoxic species by thelight activation of a photosensitizer dye (PS) in the presence of molecular oxygen [1]. Halogen-xanthene dyes, such
as Rose Bengal (RB, Fig. 1A) are well-known molecules with high singlet oxygen quantum yield values (ɸ 1O2), an
important factor for its use in PDT. However, as a hydrophilic photosensitizer, RB suffers from poor intracellular
uptake ability and thus cannot be used to treat solid tumors. Recent literatures have demonstrated the use of nanoparticles as the vehicle to conjugate with RB in order to enhance the uptake efficiency by cancer cells [2]. This
approach can also enhance the selectivity of the delivery process, reduce the side effects and increases the active
ingredient efficiency. Among a variety of nanoparticles that can be used for therapy and diagnostics, there are some
polymeric micelles, inorganic nanoparticles, liposomes, solid lipid nanoparticles, carbon nanotubes, mesoporous
silica nanoparticles, dendrimers, quantum dots, etc [3]. The use of mesoporous silica nanoparticles (MSNs, Figure
1B), for example, is a relatively new and promising approach for applications ranging from catalysis to medical
issues. The MSNs show very interesting structural characteristics as high surface area, porous volume tuneable and
suitable to accommodate a large amount of drug, two functional porous surfaces (internal and external) and a stable
structure compatible with red blood cells and the immunological system. The high density of silanol groups on the
MSNs surfaces is one of the most important features of MSNs which allows their functionalization. The addition of
functional groups on the surface can play many important roles for drug delivery as adjustment the charge surface
in order to allow specific molecules to be inserted inside or outside de MSNs, avoiding an early PS delivery.
In this contribution, we report a simple surface modification process that conjugates a photosensitizer, Rose
Bengal (RB), a xanthene dye, with amino-functionalized MSNs through covalent bonding to yield RB-modified
MSNs for PDT study. The amine groups are necessary to conjugate the activated RB. Several hybrid systems with
different RB loading were prepared in order to optimize the photosensitizer concentration and to obtain a high efficiency of 1O2 release. A detailed structural and morphological characterization of the hybrids by using XRD,
HRTEM, volumetric and thermogravimetric analysis combined with spectroscopic characterization by using DR
UV-Vis, FTIR, SS-NMR and photoluminescence spectroscopies will be presented. The 1O2 generation will be evaluated by using uric acid, which reacts irreversibly with 1O2. These hybrid materials represent the first step in the
design of multifunctional nanoplatforms for cancer theranostics (imaging, targeting and therapy).
(A)
I
I
(B)
O
O
HO
I
I
Cl
COOH
Cl
Cl
Cl
Fig. 1. (A) Molecular structure of Rose Begal and (B) Scheme of organically modified MSNs.
References
1 R. R. Allison, G. H. Downie, R. Cuenca, X. H. Hu, C. Childs, e C. H. Sibata. Photodiagn.Photodyn.Ther.,1 (2004), 27.
[2] A. Uppal, B. Jain, P. K. Gupta, K. Das. Photochem. Photobiol., 87 (2011),1146.
[3] A.H. Faraji, P. Wipf. Bioorgan. Med. Chem., 17 (2009), 2950.
P48
77ththJFIC
JFIC-GIFC,
-GIFC,Turin,
Turin,Italy,
Italy,May
2014
Cerium based Metal-Organic framework for CO2 capture
J Ethiraj*1, J.G. Vitillo1, F. Bonino1, S. Bordiga1
1
University of Turin, Department of Chemistry, NIS--INSTM Reference CenterVia G. Quarello 15A, 10135, Torino, Italy
(*) Jayashree Ethiraj: [email protected]
Keywords: Metal organic framework, Cerium, PXRD, FT-IR, CO2
Metal organic frameworks (MOFs) are new group of porous materials, synthesized from metallic center/clusters
connected with organic linkers[1,2] with varying porosity and surface area. A real understanding of the molecular
processes that take place during the formation of these materials, nucleation and crystal growth, might lead to a
proper control of their properties, like morphology and composition including concentration of defects [3]. Literature survey reports Ce-BTC as micro-crystals [4] and as single crystals [5]. Designing of new Cerium based MOFs
could be promising materials for CO2 capture and storage. BTC as linker might provide environment for formation
of CeOx as inorganic units.
Preliminary results revealed highly crystalline material with high porosity which are shown by lower angle high
intensity peaks and the material is stable upon activation upon 200°C. The CO adsorption monitored by FT-IR
spectroscopy shows three bands at 2155, 2148 and 2137 cm-1. The band at 2137 cm-1 corresponds to CO condensed in pores in liquid phase and other two bands corresponding to cerium open metal sites. The CO2 storage
capacity wt% at 1bar for Ce-BTC is 12.3.
-1
CO2 amount (mol kg )
3
2
1
26°C
Ce-BTC
ZIF-8
0
0.0
Fig.1. PXRD of as synthesized Ce-BTC and after
thermal activation at 200°C for 2h
References
[1] K. Sumida, et al., Chem. Rev., 112 (2012), 724
[2] H. Furukawa. et al, Science, 341 (2013) 1230441
[3] G. Ferey, Chem. Soc. Rev., 191 (2008) 37
[4] Khan et al., Eur. J. Inorg. Chem., (2010) 4975
[5] Li et al., Acta Cryst., E67 (2011) m1020
Fig.2. FT-IR spectra of
CO adsorption (100K)
0.2
0.4
0.6
0.8
pressure (bar)
1.0
Fig.3. CO2 adsorption isotherm done at
299K
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P49
Amide bond formation on silica surfaces: an in situ FTIR study
M. Fabbiani*, C. Deiana, Y. Sakhno, P. Ugliengo, G. Martra
University of Torino, Department of Chemistry and Interdepartmental Centre “Nanostructured Interfaces and Surfaces- NIS”
Via P. Giuria 7, 10125 Torino, Italy
Keywords: Surface silanols, IR spectroscopy, amide bond formation
Silica is a widely studied and used material for industrial purposes, as stationary phase in chromatography, catalyst support and in many pharmaceutical applications [1]. Lately it has also been addressed as an effective catalyst
for the direct formation of amide bonds from unactivated carboxylic acids [2]. Moreover, silica also appeared to be
active towards the formation of long polypeptides from unactivated glycine [3], by using a method consistent with
the Bernal’s hypothesis of the formation of biopolymers in abiotic conditions [4]. Indeed, many efforts have been
made for better understand the role of silica surface in the adsorption and reaction amino acids [5] and possible
correlations between surface properties and reactivity were recently reviewed [6].
Basically, silanols are supposed to be the active sites, but experimental information on specific structural and/or
grouping requirements for an affective catalysis towards amidation is still lacking. Actually, isolated (Si-OH),
geminal [=Si(OH)₂], vicinal or H-bonded silanols can be present on the silica surface [6]. Here we report preliminary results of an in situ FTIR investigation aimed to shed some light on possible difference in silica surface reactivity in dependence on the silanol distribution. A commercially available fumed silica (Aerosil OX50) was thermally treated in order to selectively remove, by condensation, H-bonded and then vicinal silanols. Pentylamine and
formic acid were then dosed on the samples from the vapour phase, following the procedure already reported in the
case of titania [7], and their adsorption and reaction was monitored by in situ FTIR spectroscopy. The analysis of
the spectral pattern indicated that amidation, as well as salification, occurred at room temperature independently on
the presence of H-bonded silanols, whereas the presence of non-interacting silanols appeared to be required for the
occurrence of both reactions.
Fig. 1. Schematic representation of the amidation reaction occurring on silica surface.
References
1
J. Nawrocki, J. Chromatogr. A 29 (1997) 779
2
J. W. Comerford, J. H. Clark, D. J. Macquarrie, S. W. Breeden, Chem. Commun. (2009) 2562
[3]
G. Martra, C. Deiana, Y. Sakhno, I. Barberis, M. Fabbiani, M. Pazzi, M. Vincenti, Angew. Chem. 126 (2014)
[4]
J. D. Bernal, The Physical basis of life, Routledge and Kegan Paul, London (1951)
5
M. Meng, L. Stievano, J. F. Lambert, Langmuir 20 (2004) 914
6
A. Rimola, D. Costa, M. Sodupe, J. F. Lambert, P. Ugliengo, Chem. Rev. 113 (2013) 4216
7
C. Deiana, Y. Sakhno, M. Fabbiani, M. Pazzi, M. Vincenti, G. Martra, CHEMCATCHEM 5 (2013) 2832
P50
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
Rationalization of dye soaking parameters in relation with DSC efficiency by a
chemometric approach.
G. Favaro*1, S. Galliano2, C. Barolo2, M. Milanesio1, V. Gianotti1,
1
Dipartimento di Scienze e Innovazione Tecnologica, Università del Piemonte Orientale “A. Avogadro”, Viale T. Michel
11, I-15121 Alessandria, Italy
2
Dipartimento di Chimica and NIS Interdepartmental centre, Università di Torino, Via P. Giuria 7, 10125 Torino, Italy
Keywords: D5, Chenodeoxycholic Acid, DSC Efficiency, Chemometric Approach, UV-Vis Spectroscopy.
Dye-sensitized solar cells (DSCs) have attracted a lot of interest for their abilities to convert solar light into electricity at low cost. Recently, a chemometric Factorial Experimental Design approach was used for the determination
of the uptake of D5 dye (Figure 1) on TiO2 surface (represented by the sphere in Figure 1), to obtain information
about the correlations between the three variables governing the uptake itself, i.e. D5 concentration, dispersant (cheno-deoxycholic acid, CDCA) concentration and contact time [1]. The obtained Ordinary Least Squares
(OLS) regression model shows that large uptakes can be obtained, as expected, when CDCA is present if the contact time is high, but, surprisingly, in absence of CDCA if the contact time is small. This behaviour can be related
to the effects of the intermolecular interactions.
Exploiting the same chemometric approach, the preparation of the DSC device was studied and the correlation
of the above described chemical parameters to DSC efficiencies, in term of I/V curve, is under development. Starting from the results obtained in first part of the work [1], some experiments were carried out with different electrolytes. The efficiency and the stability of the cells were evaluated. D5 (1·10 -4 M) and CDCA (8 mM) were loaded
with a contact time of 16 h on nanocrystalline-TiO2 electrodes fabricated by screen printing technique. The resulting electrodes were characterized for their thickness both by profilometry and spectrophotometric analyses in order
to be able to correctly compare the dye uptakes and final cell efficiencies. It was possible obtaining highly transparent DSC test devices in a reproducible way obtaining a medium efficiency of about 3,089±0,012 %.
.
Fig. 1. (E) 3-(5-(4-Diphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid D5 molecule, bonded to a titanium oxide nanosphere.
References
[1] V. Gianotti et al., Rationalization of dye uptake on TiO2 slides for Dye-sensitized Solar Cells by a combined chemometric and structural approach, submitted for publication
P51
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Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
Synthesis and Structural Characterization of Regio Substituted
4-Hydroxy-1H-1,2,3-triazols as Possible Tool in Bioisosteric Applications
A Federico,1* S.Sainas,1 A. Ducime,1 K. Martina,1 F. Bosca,1 D. Boschi,1 M.L. Lolli.1
1
Keywords: 4-hydroxy-1H-1,2,3-triazole system, triazole alkylation, isoster.
Bio(iso)steric replacement is a widely used approach within Medicinal Chemistry for improving properties of a lead
compound such as bioavailability, selectivity, and potency. 1 Two functional groups should be called isoster if they
share similar physico-chemical properties.1 When isosters share a commune biological profile, they can also be
defined bioisosters. It could be say that while chemistry rules the isosteric similarity between groups, only the biological target will be able to answer positively to the second bioisosteric hypothesis. A number of clear bioisosteric
relationships have been established for many functional groups, in particular for the carboxyl group, which successfully has been substituted by heterocycles such as tetrazole, 3-hydroxyisoxazole, 3-hydroxyisothiazole, 3-hydroxy1,2,5-thiadiazole, and 3-cyclobutene-1,2-dione. These cyclic systems have been used extensively to design amino
acid mimetics active at subtypes of central nervous system (CNS) receptors. 2
Since 2006,3 our group focused its attention in the chemical study of hydroxylated pentatomic heterocyclic systems
as possible isoster of carboxylic group. Recently our studies was focalized to bioisosteric applications of the acidic
4-hydroxy-1H-1,2,3-triazole poorly described in literature. In this system, the presence of three nitrogen atoms will
offer occasions for regiodirect substituents in fixed and specific directions, in order to look for binding affinity depending from the target requirement. In this occasion, we described the chemical synthetic strategies developed to
obtain different N-substituted hydroxytriazole isomers. The structure of regioisomers obtained were univocally
attribuited by using 2D-NMR (HSQC and HMBC) techniques applied to carbon as heteronucleus. Currently, the
acidic 4-hydroxytriazol scaffold is under investigation, in collaboration with University of Copenhagen, as bioisoteric replacement of the distal glutamate carboxylic group. 4
Fig. 1 4-hydroxy-1,2,3-triazole system
References
1
N. A. Meanwell. Synopsis of some recent tactical application of bioisosteres in drug design. Journal of Medicinal
Chemistry 2011, 54, 2529-91.
[2]
C. Ballatore, D. Huryn, A. Smith. Carboxylic Acid (Bio)Isosteres in Drug Design. ChemMedChem 2013 8, 385-395
[3]
M.L Lolli ML, C. Giordano, D.S.Pickering, B.Rolando, K.B. Hansen, A. Foti, A. Contreras-Sanz, A. Amir, R. Fruttero, A.
Gasco, B. Nielsen, T.N. Johansen. 4-Hydroxy-1,2,5-oxadiazol-3-yl moiety as bioisoster of the carboxy function. Synthesis, ionization constants, and molecular pharmacological characterization at ionotropic glutamate receptors of compounds
related to glutamate and its homologues. Journal of Medicinal Chemistry 2010, 53(10), 4110-8.
[4]
S. Sainas, A. Federico, C. Bertolotti, B. Nielsen, D. Boschi, B. Frølund 2 and M. L. Lolli 4-Hydroxy-1H-1,2,3-Triazol-5-yl
moiety as bioisoster of carboxylic group. Synthesis and pharmacological ionotropic glutamate receptors characterization of
Glu analogues. 7th JFIC -GIFC, Turin, Italy, May 5th-6th, 2014
P52
JFIC -GIFC,
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC
Study of hydrogen storage in porous carbon / nickel nanoparticles nanocomposites
Déborah Fernand*,1, Philip Llewellyn1, F. Chaspoul2, Virginie Hornebecq1
2
1
MADIREL Laboratory UMR 7246, Aix-Marseille University, Marseille France
IMBE Laboratory UMR 6263, Faculty of Pharmacy, Aix-Marseille University, Marseille, France
Keywords: Nanocomposites, Porous, Nanoparticles, Hydrogen, Adsorption
Hydrogen is a promising energy vector. However, scientific and technological constraints must still
be thwarted in order to obtain an efficient storage of high surface area materials. The reversibility of
storage is one of those challenges. Indeed, the hydrogen and the material must provide specific
interactions for obtaining high amounts of adsorbed gas while avoiding spending too costly in terms of
energy during the desorption.
The idea developed in this study is to combine the same material a large surface area and specific
adsorption sites. Since the micro/mesoporous carbon are widely studied in the context of hydrogen
storage and the nickel is known to possess specific interactions with hydrogen, we chose to study
porous nanocomposites resulting from the incorporation of nanoparticles of Ni in porous carbons. The
latter were first synthesized via a soft chemistry route the so-called self-assembly route by using, as
structuring agent a triblock copolymer and resols as carbon precursors. Then, the incorporation of Ni
nanoparticles within the porosity was performed via impregnation with a precursor of nickel followed
by reduction of the latter in liquid phase. Conventional techniques such as nitrogen sorption at 77K,
transmission electron microscopy (TEM ) were used to characterize the porous matrices before and
after incorporation of the Ni nanoparticles . Finally, the Ni NPs@Carbon nanocomposites were studied
for the storage of hydrogen at low temperature (77K) and at low pressures (p < 1 bar) using a TianCalvet type microcalorimeter coupled to a conventional manometer. This apparatus allows the
construction of hydrogen adsorption isotherms (adsorbed amounts depending on the pressure), and
the determination of the adsorption enthalpies as a function of the surface coverage. In view of the
results obtained and those contained in the literature, a new hybrid material that combines a number
of requirements is proposed.
P53
P52
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
Arylpiperidines as a new class of oxidosqualene cyclase inhibitors
T. Ferrante3, M. Keller1, A. Wolfgardt1, C. Müller1, R. Wilcken2, F.M. Böckler2, G. Balliano3, F. Bracher*1, S. Oliaro-Bosso*3
1
Department of Pharmacy – Center for Drug Research, Ludwig-Maximilians University, Butenandtstr. 5-13, 81377 Munich,
Germany
2
Department of Pharmacy, Eberhard-Karls University, Auf der Morgenstelle 8, 72076 Tübingen, Germany
3
Dipartimento di Scienza e Tecnologia del Farmaco, Università di Torino, Via Pietro Giuria, 9, 10125 Torino, Italy
(*) corresponding authors: [email protected], [email protected]
Keywords: Oxidosqualene cyclase, enzyme inhibitor, high energy intermediate, arylpiperidine
Oxidosqualene cyclase (OSC) is one of the most important and studied enzyme involved in the biosynthesis of
sterols. It catalyzes the formation of the first cyclic intermediate of the pathway: lanosterol in animal and fungal
cells, cycloartenol in plant cells. The oxidosqualene cyclization to lanosterol goes through a number of carbocationic high energy intermediates (HEI). Mimicking these intermediates is a promising approach to the development of
inhibitors of this enzyme. 3-Arylpiperidines and tetrahydropyridines were designed with steroidomimetic rings,
A+E equivalents, containing two protonable amino groups to mimic both the pro-C4 HEI and the pro-C20 HEI of
OSC-mediated cyclization cascade [Figure 1].
These newly designed molecules were assayed in a whole-cell assay suitable for detection of target enzymes
in the post-squalene part of cholesterol biosynthesis [1] and for determination of their inhibition of total cholesterol
biosynthesis in a human cell line [1].
Compounds which turned out to be OSC inhibitors were tested on yeast OSC as well as on human and Trypanosoma cruzi OSCs expressed in yeast, by incubating cell homogenates with the radiolabeled substrate of the enzyme, squalene epoxide, in the presence and absence of inhibitors at different concentrations (10 M – 0,1M).
The inhibitory activities were expressed as IC50 value (half maximal inhibitory concentration). Data obtained
show a significant difference in the inhibitory properties of these three different OSCs and led us to draw some
structure-activity interaction hypotheses, based also on the comparison with the binding mode of Ro 48-8071, already studied by co-crystallization [2]. Inhibitory activity seems dependent on the nature of the lipophilic substituent mimicking the sterol side chain. All inhibitors showed to be more active on human OSC than on T. cruzi and S.
cereviseae enzymes, proving to be a good starting point to develop an interesting group of hypocholesterolemic
molecules.
Fig. 1.
References
[1]
M. Giera, F. Plössl, F. Bracher, Steroids 72 (2007) 633-642.
2
R. Thoma et al. Nature 432 (2004) 118-122.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P54
Synthetic and Electrochemical Investigation about novel Re(I) and Mo(0) Complexes as efficient Photo- and Electrocatalysts for CO2 reduction
Federico Franco1*, Claudio Cometto1, Cunfa Sun1, Luca Nencini1, Fabrizio Sordello1,
Claudio Garino1, Roberto Gobetto1, Carlo Nervi1, Claudio Minero1
1
Department of Chemistry and NIS, University of Turin, via P. Giuria 7, 10125 Torino, Italy
(*) federico.franco@E-mail address (font style: Times 9pt)
Keywords: Rhenium, CO2 reduction, Electrocatalysis, Photocatalysis, Polypyridyl ligands
In recent years, the photo- and electrochemical conversion of CO2 to higher-energy products has been improved by employing transition metal coordination compounds with polypyridyl ligands (e.g. Ru, Os, Re, Mn [1,2]), in
the form of molecular or supramolecular organometallic catalysts. In this perspective, our research has mainly focused on the synthesis of a series of novel Re(I)-carbonyl diimine complexes, to be efficiently used as catalysts in
either photo- and electrocatalysis for CO2 reduction. In more detail, this new class of compounds is characterized
by the presence of common polypyridyl ligands covalently attached to the highly fluorescent PNI cromophore (N(diimine)-4-(1- piperidinyl) naphthalene-1,8-dicarboximide), which revealed to be able to provide a huge excited
state lifetime enhancement in a Re(I) charge-transfer complex [3]. This feature may play a key role in the process
of catalytic CO2 reduction (especially in photocatalysis). The new organometallic compounds were spectroscopically characterized, whereas their electrochemical behaviour was studied either in inert atmosphere and in presence of
CO2 ; this was finally compared with that of Re(CO)3(bipy)Cl, taken as a reference compound. The results of the
electrocatalytic measurements are reported in the Fig. 1.
Fig. 1. Activities, in terms of Turnover Number (TON) over electrolysis time, for the compounds 1 (orange), 2 (black), 3 (yellow) and 4 (blue).
On the other hand, looking at a practical use of these systems, the usage of quite abundant first and second
row transition metals instead of rare ones is very attractive. For example, to our knowledge there are no reports
about the use of tetracarbonyl Mo(0) complexes for the same purpose. This reason lead us to synthesize also a series of [Mo(CO)4(L)] complexes (L = 2,2’-bipyridyl and derivatives), testing them for electrochemical reduction of
carbon dioxide. Our first results are quite promising, showing certain activity and selectivity in reducing CO 2 to
CO.
References
[1] Bourrez, M.; Molton, F.; Chardon-Noblat, S.; Deronzier, A.; Angew. Chem. 50 (2011) 9903-9906.
[2] Morris, A.J.; Meyer, G.J.; Fujita, E.; Acc. Chem. Res. 42 (2009) 1983.
[3] Yarnell, J. E.; Deaton, J. C.; McCusker, C. E.; Castellano, F. N.; Inorg. Chem. 50 (2011) 7820-7830.
P55
New Bio-Polymers from refuse derived products
1
S. Tabasso , F. Franzoso*,1, D. Causone1, A. Bianco Prevot1, E. Montoneri2, D. Antonioli3,
K. Sparnacci3, M. Laus3
1
2
Università degli Studi di Torino, Dipartimento di Chimica, Via P. Giuria 7, 10125 Torino (I)
STAR Integrated Research Unit, Università di Foggia, Via Gramsci 89-91, 71121 Foggia (I)
3
DISIT, Università del Piemonte Orientale, Viale T. Michel 11, 15121 Alessandria (I)
Keywords: Biopolymer, Biomass, Solvent casting, PEAA
Bioplastics [1,2] currently available in the market, or known as research products, are based on the content of biopolymers isolated from dedicated crops or obtained by fermentation. Most commercial products are blended materials containing synthetic polymers derived from fossil sources and polymers of natural origin. The result is a compostable new
polymer that maintains original mechanical properties.
Our aim is to replace substances, such as starch, derived form dedicated crops with soluble bio-organics substances
(SBO) derived from hydrolysis of municipal or agricultural bio-wastes.
These substances are produced in a pilot plant made available by “Studio Chiono e Associati” in Rivarolo Canavese,
Italy, with a production capacity of 10 kg/week. Bio-wastes are a rich source of bio-organic matter, providing a wide
variety of products with different chemical and technological properties, depending on the source nature and waste process working conditions. Chemical composition data also show that these SBO are humic-like substances containing
several functional groups and C types of different polarity [3]. SB are already used in the chemical’s market in different fields, such us detergent formulations, textile auxiliaries, fuel, fertilizers and nanostructured materials [4-6].
In order to achieve the goal, new types of bioplastics containing both a synthetic polymer and a biobased product
have been obtained and studied on a laboratory scale [7,8]. In particular, in this work, we focused on a bio-polymer
prepared mixing a polyacrylicacid-polyethylene copolymer (PEAA) and soluble bio-organic substances (SBO) isolated
from municipal bio-wastes.
Figure 1 shows a schematic image of the two main reactants used and the biopolymer obtained at the end of the
solvent casting process.
Fig. 1. Chemical structure and aspect of EAA (a), virtual structure and pellets’s photo of SB (b) and the PEAA-SBO biopolymer
obtained (c).
The products were obtained at varying PEAA-SBO ratios. In this contribution physico-chemical, thermal and mechanical properties are reported, to elucidate the interaction occurring between PEAA and SBO into bio-polymeric
films thus obtained. A substantial dependence of thermal and mechanical properties on the SBO content was observed.
References
1
2
3
4
5
6
7
8
. Cioica, C. CoŃa, M. agy, G. Fodorean, Agriculture 65 (2008) 23.
L. Pei, M. Schmidt, W. Wie, Biotechnology of Biopolymers Chapter 3 (2011) M. Elnashar, Ed., Published by InTech, Croatia.
E. Montoneri, V. Boffa, P. Savarino, D.G. Perrone, C. Montoneri, R. Mendichi, E.J. Acosta, S. Kiran, Biomacromolecules 11
(2010) 3036.
E. Montoneri, V. Boffa, P. Savarino, D.G. Perrone, M. Ghezzo, C. Montoneri, Waste Management 31 (2011) 10.
G. Magnacca, E. Laurenti, E. Vigna, F. Franzoso, L. Tomasso, E. Montoneri, V. Boffa, Process Biochemistry 47 (2012) 2025.
E. Montoneri, A. Bianco Prevot, P. Avetta, A. Arques, L. Carlos, G. Magnaccia, E. Laurenti, S. Tabasso, The Economic Utilisation of Food Co-Products Chapter 4 (2013) 64-109.
R. Chandra, R. Rustgi, Prog. Polym. Sci. 23 (1998) 1273-1335.
U. Siemann, Prog. Colloid Polym. Sci. 130 (2005) 1-14..
th th
th 5 -6 , 2014
7th JFIC
-GIFC,
Turin,
Italy,
7th JFIC -GIFC,
Turin,
Italy,
May
5th-6May
, 2014
P56
Study of the interaction between cytotoxic cationic Pt(II) complexes
and dextran sulfate
F. Fregonese1, E. Gabano1, M. Ravera1, D. Osella1*
1
Università del Piemonte Orientale “A. Avogadro”, Dipartimento di Scienze e Innovazione Tecnologica, Viale
T. Michel 11, I-15121 Alessandria, Italy
Keywords: Pt(II) complexes, drug targeting and delivery
In recent years, the interest in the field of cancer chemotherapy has been moved to new platinum
based drugs to improve the effect of classical complexes derived from cisplatin. More attention has
been paid to the “drug targeting and delivery” systems [1]. These systems can, for example, allow
greater accumulation of the drug inside the cell and, therefore, impart greater selectivity to the drug
itself. For these purposes platinum based drugs can be linked to a drug delivery vector like
nanoparticles, nanotubes or macromolecules. In this case platinum(II) complexes with one chloride
and three amino groups (two ammonia molecules and one aromatic ammine) with a positive charge
have been synthesized (Figure 1) according to the Lippard’s procedure [2].
1
2
3
Fig. 1
Complexes 1, 2 and 3 are known to have good anticancer proprieties. For these reason, in the
following step, they have been linked to a macromolecule such as dextran for a drug targeting
process. In this work dextran sulfate has been used to create an electrostatic interaction between
positive platinum(II) complexes and negative sulfate groups to bring drug into cancer cells. The
synthesis, characterisation and stability in aqueous solution of the studied complexes will be
reported together with the preliminary results on the loading of dextran with the complexes.
Reference:
[1] E. Gabano, M. Ravera and D. Osella, Current Medicinal Chemistry, 2009, 16, 4544-4580
[2] Park, G. Y.; Wilson, J. J.; Song, Y.; Lippard, S. J. Proc. Natl. Acad. Sci. U.S.A. 2012, 109, 11987
P57
JFIC -GIFC,
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,,2014
2014
77thth JFIC
Synthesis of fast water exchange GdIII complexes as MRI Contrast Agents
1
1
Luca Gaino, 1Lorenzo Tei, 1Giuseppe Gugliotta, 1Mauro Botta
Dipartimento di Scienze ed Innovazione Tecnologica, Università degli Studi del Piemonte Orientale ”Amedeo Avogadro”,
Viale T. Michel 11, 15121 Alessandria, Italy
([email protected])
Keywords: Magnetic Resonance Imaging, Gadolinium(III), macrocyclic ligands, relaxometry
Polyaminopolycarboxylic ligands based on the tetraazacrown cyclen have received particular interest for the complexation of Gd3+ ions to be used as MRI contrast agent (CA). One of the most well-known CA is GdDOTA (Dotarem®, DOTA = 1,4,7,10 - tetraazacyclododecane - 1,4,7,10 - tetraacetic acid), that has been used in the clinics for
more than 20 years. The tetramethyl analogue bearing methylacetic pendant arms is known as GdDOTMA and it
has received attention especially for the faster exchange rate (kex) of the coordinated water molecule with respect to
GdDOTA.[1] kex is one of the parameters that strongly influence the efficiency of a CA (called relaxivity, r1), especially when the CA is conjugated or interacts with a macromolecule or a nanoparticle. In order to explain this faster
kex, we must consider that the LnDOTA complexes may exist in the form of four stereoisomers, in particular two
pairs of enantiomers. The stereochemistry of each structure and defined by two elements: the conformation of the
macrocyclic ring (δδδδ or λλλλ) and the orientation of the arms acetic (both Δ or Λ ). When the helicity of these
two elements is the same the coordination geometry is defined by a monocapped twisted square antiprism (TSAP),
when they are opposed by a monocapped square antiprism (SAP). The LnDOTA complexes that are present mostly
as isomer SAP, the complexes are LnDOTMA mainly in the form TSAP. In this last conformation kex is much faster due to a slightly longer water-metal ion distance and thus to a weakening the metal-water interaction.[1]
Starting from this considerations, we have designed three functionalized derivatives of DO3MA ((1R,4R,7R)
,’,”-trimethyl-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) with one acetic (DO3MAAc), one Naminoethyl-acetamido (DO3MA-MA) or one 2- hydroxypropyl (HPDO3MA) arms (Figure 1). The GdIII complexes
of these three new ligands were prepared and characterized by 1H and 17O relaxometric techniques in order to evaluate the modulation of the parameters influencing the relaxivity by changing one of the coordination site. Furthermore, DO3MA-MA has the advantage to be a bifunctional probe containing a terminal amino group which can be
used for conjugation to vectors or biomolecules bearing a free carboxylic group.
O
O
O
OH
N
OH
N
N
OH
OH
O
N
OH
OH
N
O
OH
N
N
N
O
OH
N
N
O
HO
N
H
N
N
O
HO
HO
O
O
O
HPDO3MA
DO3MA-Ac
DO3MA-MA
Figure 1. Ligands synthesised and studied in this work.
References
1S. Aime, M. Botta, et al, Inorg. Chem. 50 (2011) 7955.
NH2
P58
7thth JFIC -GIFC,
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
The effect of the dipping temperature on the photovoltaic performances of
Dye-Sensitized Solar Cells
S. Galliano1,2,*, D. Cielo1, A. Smarra2, L. Bonandini2, N. Barbero1, R. Buscaino1,
C. Barolo1, G. Viscardi1
1
University of Torino, Department of Chemistry and NIS Interdepartmental Centre, Via Pietro Giuria 7, 10125 Torino, Italy
2
DYEPOWER, Viale Castro Pretorio 122, 00185 Roma, Italy
Keywords: Dye-sensitized Solar Cell, sensitizers, dye-loading.
Dye-sensitized Solar Cells (DSCs) represent a promising and emerging technology because of their advantages like simple fabrication process and low environmental impact. In recent years the research has focused on
the understanding of the photovoltaic processes and the improvement of the photoconversion efficiencies, currently
around 12-15% [1,2]. Despite these continuos advances, DSCs are not yet commercialized on large-scale, because
they are subjected to undesirable phenomena, i.e. photodegradation of the dye anchored on semiconductor, leakage
of the electrolyte, diffusion of pollutants from the outside and corrosion of some components. Another problem is
due to the difficulty in realizing devices able to guarantee high photovoltaic performances with reliable reproducibility. The reason is that the cells are assembled with different and heterogeneous layers
(FTO/TiO2/sensitizer/electrolyte/Pt-FTO), each one affected by intrinsic variability; moreover the layers influence
each other and this increases the number of variables involved at the same time in the photoconversion process. For
this reason, the present research is been conducted with a chemometric multivariate approach, that allows to simultaneously evaluate multiple variables at time. In this way, we investigated the effect on the photovoltaic performances of DSCs of different dipping conditions, varying some factors, i.e. concentration of sensitizer and coadsorbent, time and temperature of soaking. In particular, we observed a significant temperature dependence on
dye-loading [3], causing an improvement in efficiency, specially for organic and NIR sensitizer. We are firmly
convinced that this approach will make possible to find the optimal experimental conditions to achieve the best
performance with different dyes.
References
1
A. Yella, H. Lee, H. Tsao, C. Yi, A. Chandiran, M. Nazeeruddin, E. Diau, C. Yeh, S. Zakeeruddin, M. Grätzel, Science
343 (2011) 629-633.
2
J. Burschka, N. Pellet, S. Moon, R. Humphry-Baker, P. Gao, M. Nazeeruddin, M. Grätzel, Nature 499 (2013) 316-319.
3
F. Sauvage, J. Decoppet, M. Zhang, S. Zakeeruddin, P. Comte, M. Nazeeruddin, P. Wang, M. Grätzel, J. Am. Chem. Soc.
133 (2011) 9304-9310.
P59
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Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
Explorative study of novel ternary intermetallic compounds in
Yb-T-X systems (T = Pd, Pt; X = Bi, Pb, Sn)
F. Gastaldo*,1, M. Giovannini1, A. Saccone1
1
Dipartimento di Chimica e Chimica Industriale, Università di Genova, via Dodecaneso 31, 16146 Genova, Italy
(*) corresponding author: [email protected] (F. Gastaldo)
Keywords: Ternary alloys, Highly correleted electron systems, Heavy fermions
Rare-earth intermetallic compounds have attracted considerable interest for the past four-decades, because of their
use in various technological applications and from the viewpoint of their fundamental properties. In particular, a
field of great interest of rare-earth intermetallics is the study of magnetism and transport properties at low temperatures. Under these conditions we can freeze out the phonon contributions making it easier to detect the correlated
electron behavior and the ground state of matter. These materials often behave as highly correlated electron systems
in which the interaction more or less strong between conduction electrons and f-electrons of rare-earths is observed.
This gives rise to a variety of novel phenomena such as unconventional superconductivity, intermediate valence,
heavy fermion (HF) behavior, Kondo effect and quantum phase transitions [1].
An explorative study on the ternary intermetallics Yb-T-X (T = Pd, Pt and X = Bi, Pb, Sn) is presented. All the
samples were prepared by induction melting of the selected elements previously closed in tantalum crucibles. Afterwards they were characterized by optical and scanning electron microscopy (SEM) and X-ray powder diffraction
(XRPD), in order to detect the existence of new ternary phases and related phase equilibria. Preliminary results on
new ternary compounds and phase equilibria of these systems will be shown.
References
[1]
T. Muramatsu, T. Kanemasa, T. Kagayama, K. Shimizu, Y. Aoki, H. Sato, M. Giovannini, P. Bonville, V. Zlatic, I.
Aviani, R. Khasanov, C. Rusu, A. Amato, K. Mydeen, M. Nicklas, H. Michor, and E. Bauer, Phys. Rev. B 83 (2011)
180404.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P60
Inorganic Markers of Stress in Natural and Genetically Modified Plants
After Chemical and Physical Stress
A. Giacomino1*, M. Malandrino2, I. Zelano2, O. Abollino2
1
University of Torino; Department of Drug Science and Technology, Via Giuria, 9 10125 Torino
2
University of Torino, Department of Chemistry, Via Giuria 5,10125 Torino
Keywords: Modified plants, chemical stress,physical stress, cations, anions
The action of biotic and abiotic stresses on plants can induce within the plant the production of compounds able
to contrast the effects of the attack. The knowledge of the response of the plants to unfavourable conditions can
have useful effects in many fields (biological, environmental, agronomic), taking into account the climatic changes
which occur in these last years.[1,2].
The plant that we considered is Nicotiana langsdorffii in its wild type form and transgenic for the rat glucocorticoid receptor gene, for the rolC gene from Agrobacterium rhizogenes and for the rolD gene of Agrobacterium
rhizogenes.
The plants were grown in controlled and reproducible conditions (Fig. 1), with the aim of providing a well characterized reference sample and better detecting the variations induced by stresses. The investigated plant samples
were exposed to chemical (high concentration of cromium) and physical (dehydration and thermal) stresses, that
give rise to the alteration of the cellular concentrations of a series of inorganic species.
Fig. 1. Plant of Nicotiana langsdorffii grown in controlled conditions
We studied such effects, monitoring the modification of a series of ions, such as the concentration of sodium
and potassium cations, of nitrate and chloride anions, that are known to be markedly altered both by physical and
chemical stress.(3)
The total content of considered cations and of some other elements (Al, Ba, Ca, Fe, Mg, Mn, P and Si) were determined using an inductively coupled plasma-optical emission spectrometer (ICP-OES) after acid digestion in
microwave oven.
Three procedures were selected among the different ones available in literature regarding the extraction of anions from vegetables. These procedures were tested preliminary onto lettuce plants purchased from local market to
value the efficiency of the extraction obtained for all the considered markers. Water was chosen as the most suitable
extractant; then nitrates and chlorides were extracted into water and determined by ion cromatography. Also the
extractable amount of all the considered cations was determined.
The obtained results were treated with multivariate chemometric techniques (Principal Component Analysis and
Hierarchical Cluster Analysis) to identify correlations among the the different considered markers and similarities
or dissimilarities among samples.
The study of the behavior of the plants and the effect of genic modifications in different environmental conditions
can be very useful to predict the variation induced in the normal development of the plants caused by environmental
pollution and climatic variations, taking into account the increasing water scarcity and temperature warning that are
taking place on Earth. The availability of genetically modified forms of the investigated plant allowed us to evaluate the role played by the modifications for the improvement or the reduction of the resistance of such plants to the
different environmental stresses.
References
(1) C. Poschenrieder, R. Tolra, J. Barcelò, Trends in Plant Science 11 (2006).
(2) N. Candan, L. Tarhan. Plant Science 165 (2003).
(3) M. Patra, N. Bhowmikb, B. Bandopadhyay, A. Sharma. Environmental and Experimental Botany 52 (2004).
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P61
Non-conventional extractions and antioxidant properties evaluation of microalga
Spirulina maxima
D. Garella1, M. Giorgis1, C. Cena1, A. Di Stilo1, E. Marini*, 1
1
Dipartimento di Scienza e Tecnologia del Farmaco, University of Turin, Via P. Giuria 9, 10125 Turin, Italy.
Keywords: Spirulina maxima, antioxidant activity, extraction, ultrasound, microwave
Free radical reactions, especially those with participation of oxidative elements, have been shown to be associated with damage on lipids, proteins, cell membranes and nucleic acids, ultimately resulting in various chronic diseases. In the last decades there has been an explosive interest in the use of antioxidant nutritional supplements. Several studies demonstrated that intake of some vitamins, minerals, and other food constituents may help to protect
the body against many diseases, and that antioxidants exert their protective effect either preventing these diseases or
decreasing their severity. In the search for new and alternative sources of antioxidants, extraction from microalgae
has recently gained importance [1]. During the photosynthesis process microalgae generate molecular oxygen,
which can reach locally high concentration levels and can be easily activated by ultraviolet radiation or heat from
sunlight into toxic ROS. Microalgae, like plants, have developed protective mechanisms which consist in the production of antioxidant compounds able to minimize ROS concentration. The great biodiversity, the ease of cultivation and modulation of growth conditions are important factors that allow to count microalgae among the natural
resources with high antioxidant potential. The blue green microalgae Spirulina species have been widely used as an
excellent nutrient source for humans and animals due to their nutritional profile characterized by a high-protein
content (55–65%), with all the essential aminoacids in perfect balance. Spirulina contains as well a whole spectrum
of natural mixed carotene and xanthophyll phytopigments which, together with phycocyanin, seem to be related to
its antioxidant activity. For all these properties Spirulina extracts are increasingly studied and used in the supplements industry.
Since microalgae are a complex matrix, it is important to find optimum extraction conditions for selective isolation of specific groups of compounds. The traditional extraction methods (maceration, Soxhlet and hydrodistillation) are energy intensive, with low yields and moderate selectivity, and require as well a long extraction time. Several innovative extraction methods have been successfully used in food and pharmaceutical applications for the
extraction of bioactive compounds with beneficial results in terms of time, cost and yield [2]. The bioactive compounds intracellularly located, require the cell wall destruction for their extraction and this could be enhanced by
the use of the so called non-conventional techniques. Most cell disruption methods developed for nonphotosynthetic microorganisms can be applied to microalgae and cyanobacteria, e.g. microwave (MAE) and ultrasound assisted extraction (UAE). The shear forces created by the implosion of cavitation bubbles, which are in turn
created by ultrasonic waves, disrupt plant tissues and facilitate extraction at room temperature. The easy scaling up
of UAE, the safety aspects, the low energy consumption and the moderate investment required make this technique
very attractive for industrial application [3].
The aim of this work is to find optimum extraction conditions, comparing several extracts of Spirulina maxima,
in term of antioxidant activity. The extracts were obtained in different conditions of solvent polarity and with several techniques, either traditional or non-conventional (UAE and MAE). The antioxidant activity was determined with
two different assays: Trolox Equivalent Antioxidant Capacity (TEAC) assay and the Oxygen Radical Absorbance
Capacity (ORAC) assay, here reported for the first time for Spirulina extracts.
The authors acknowledge the Fondo Finanziamento Locale 2013 from University of Turin for finantial support
and FiToLife (Turin) for providing microalgae material.
References
[1]
M. Plaza, M. Herrero, A. Cifuentes, E. Ibañez, J. Agric. Food Chem. 57 (2009) 7159.
[2]
L.J. Wang, C.L. Weller, Trends Food Sci. Technol. 17 (2006) 300.
[3]
F. Chemat, M. Abert Vian, G. Cravotto, Int. J. Mol. Sci., 13 (2012) 8615.
P62
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Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
Aromatic profile and the metal content variation of strawberries due to different
treatments with bacterial strains and arbuscular mycorrhizal fungi
F. Gosetti*,1, E. Mazzucco1, E. Robotti1, V. Todeschini1, N. Ait-Lahmidi2, E. Marengo1
1
University of Piemonte Orientale, Department of Science and Technological Innovation,viale T. Michel 11, 15121 Alessandria,
Italy
2UMR Agroécologie/INRA 1347/Agrosup/Université de Bourgogne, Plant Microorganism Interactions Dpt – ERL 6300 CNRS,
17 rue Sully, 21000 Dijon, France
Keywords: strawberry characterization; aromatic profile; metal content; PCA; LDA
Among the wide variety of available fruits one of the most popular is strawberry, not only for the its high content in vitamins and minerals but also for its sensory characteristics as the flavor and aroma. Most land plants, including strawberry, interact with soil microorganisms like plant growth-promoting bacteria and arbuscular mycorrhizal fungi (AMF), which are able to improve plant growth and health.
In the month of February 2012, three species of AMF (Funneliformis mosseae, Glomus viscosum and Rhizophagus irregularis) and three Pseudomonas strains were inoculated in pairs (all possible combination of 1 fungus + 1
bacterium) on Fragaria x ananassa var. Eliana F1 plantlets, which were grown in a greenhouse under controlled
nutritional conditions (low phosphate supply). Fruits were collected from May to July, frozen in liquid nitrogen and
stored at -80 °C until analysis.
The aim of this work was to evaluate possible differences among these samples of strawberries as concerns both
their metal content and their aromatic profile. The determination of metals was carried out by using ICP MS and
ICP OES, preceded by acidic digestion, whose conditions were optimized as a function of the concentration of extracted analytes, whereas the characterization of the aromatic profile was carried out by using HS SPME GC-MS.
An overall dataset of 45 samples was analysed and 111 variables (50 metals and 61 GC-MS peaks) were used
to characterise each sample.
The obtained data were subjected to multivariate statistical methods both unsupervised, as Principal component
analysis (PCA), and supervised, as Linear Discriminant Analysis (LDA) or coupling PCA and discriminant analysis
(PCA-DA), to identify possible groupings between samples which underwent the same treatment.
All chemometric methods agreed that the quality of classification based on fungus was better than that on bacterium, probably due to the biological variability of the data.
The chemometric data highlighted the fact that the different treatments of the strawberry plants were able to significantly affect both the aromatic profile and the metal uptake.
Fig. 1. Classification based on fungus: scores plots of the first two PCs of the PCA-DA model after centering on the bacteria
dataset
JFIC -GIFC,
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,,2014
2014
77thth JFIC
P63
Trace metals dynamic in water column, particles and sediments from a river impacted by untreated wastewaters (The Sebou river, Morocco)
H. Hayzoun1,2, C. Garnier1, G. Durrieu1, V. Lenoble1, A.Ouammou2, S. Mounier1
1
2
Laboratoire PROTEE, Université du Sud Toulon Var, BP20132, 83957 La Garde, France
Laboratory of Materials and Molecular Organometallic engineering , Faculty of Sciences Dhar El Mehraz P.O. Box: 1796.
Atlas – Fez, Morocco
Keywords: Sebou river, anthropogenic activities, water pollution, trace elements, sediments
During recent years, massive economic growth and industrial development in the region of Fez (Morocco) has
led to significantly decrease aquatic systems quality. The uncontrolled release of industrial effluents results in the
introduction of nutrients, inorganic (metals, metalloids) and organic ( HA, CB, pesticides,…) compounds into the
Sebou river, one of the most important Moroccan rivers [1]. The main industrial sources of polluting substances
from Fez city include tanneries, textile factories, metal finishing facilities, and oils mills. All these industries produce various effluents that are discharged untreated into the Fez river, which, in turn, discharges into the Sebou
River.
Among the various contaminants, trace elements are of particular concern because of their toxicity, persistence and bioaccumulative nature. Leather tanning industry and brassware facilities generate a large volume of
wastewater with high concentrations of toxic metals (Cr, Cu, Ni) 2. Once discharged into the environment, the
behavior and fate of these metals will be determined by water column conditions, river hydrology, sediments properties and biological activity 3.
The objective of this work was to (1) quantify the contaminants brought to Sebou by Fez inputs, (2) study the
distribution of trace metals between dissolved and particulate fractions (3) understand the interaction between metals in particles and sediments. For that purpose, various sampling campaigns were performed during dry periods in
the Fez river (downstream Fez city) and the Sebou river (upstream and downstream the mixing with Fez river waters). Samples were analyzed for physico-chemical parameters, organic carbon and trace metals concentrations (dissolved/particulate). Additionally, three 30-cm sediment cores were sampled and then 2-cm sliced, frozen, freezedried and 2-mm sieved. Each sediment slice was studied for organic and inorganic content (TOCmeter), mercury
(CV-AAS), and major and trace metals (acid mineralization assisted by micro-wave followed by ICP-OES, FAAS
and GF-AAS analysis).
The obtained results showed that major and trace metals concentrations in the upstream sampling site are
mainly determined by geological catchment, while the elevated trace metals contents, particularly Cr, in Fez river
and Sebou downstream from the Fez city inputs, reflected the impact of direct wastewaters discharges. Especially,
suspended particles were intensively enriched with metals, even exceeding the levels recorded in sediments. These
particles represent a potential sink and source of metals and other elements, and could act as potential carriers of
pollution from Fez region to significant distances downstream section of Sebou basin. The study of sediments samples shows that the lowest metal contents were identified in the upstream sampling site of the Sebou river, whilst
the Fez' sediments were heavily polluted and exhibited bottom-up accumulation trends, which is a clear signature of
recent and continuous inputs from the untreated wastewaters of Fez city [1].
References
[1]
H. Hayzoun, C. Garnier, G. Durrieu, V. Lenoble, C. Bancon-Montigny, A. Ouammou, S. Mounier. Environ. Monit. Assess, DOI: 10.1007/s10661-013-3585-5 (2014)
2
PRIDE. Project in Development and the Environment (1996)
3
A.M. Shiller, Geochim. Cosmochim. Acta. 61, 4321-4330 (1997)
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P64
Innovative materials in cement field: from structural to multifunctional
applications
1
E. Boccaleri , S. Irico
1
*1,2
, F. Canonico2, D. Gastaldi2, L. Buzzi2
Università del Piemonte Orientale A. Amedeo Avogadro, DISIT, Viale T. Michel 11, 15121, Alessandria, Italy
2
Buzzi Unicem S.p.A. , Ricerca e Sviluppo, Via L. Buzzi 6, 15033, Casale (AL), Italy
Keywords:Multifunctional building materials, Photocatalytic cement, Self-healing building materials
Why talking about a traditional material like cement as an innovative and smart material?
In the last years the scientific research in the field of building materials is directing more resources to the development and the optimization of advanced and multifunctional cement-based materials. The main purpose is to increase the potentiality of application of these materials responding to specific use requirements, combining new
physico-chemical properties to the characteristic features of common building materials (e.g. structural properties,
performances, durability, etc..) in order to achieve innovative properties and performances.
The physico-chemical properties of cementitious materials can be tailored to obtain materials with multifunctional properties and characteristics that had never been achieved, nor regarded, in the past. These innovative materials are often called "smart materials or designed materials": in these materials one or more properties can be significantly changed in response to an external stimulus, in controlled environmental conditions.
In the field of cement-based material science, some very interesting examples from the scientific and commercial point of view are: (i) photocatalytic manufacts and buildings able to reduce air pollutants and purify the air of
our cities; (ii) self-cleaning cement-based materials that are not soiled to atmospheric smog; (iii) self-healing materials which have the intrinsic ability to repair themselves when damaged, extending the life time.
In the present work the photocatalytic activity of different cement-based materials (standard mortars, drying concrete, pervious concrete) containing TiO2 photocatalysts has been evaluated. The NOx (NO and NO2) gas abatement rate of the photocatalytic building materials has been evaluated both on the lab scale and on industrial prototypes and related to the production costs.
The research on self-healing building materials is aimed to provide an autonomous healing process when cracks in
a building structure occurred. The technological approach investigated is based on the encapsulation technique [1]:
when cracks break the capsules, the healing agent is released inside the cracks healing the damage. In this study a
prototype of a self-healing cement-based material has been developed, in which precast nuclei of liquid sodium
silicate/sodium alginate were encapsulated by a wax shell. The healing agent efficiency has been verified by a combined approach instrumental techniques, and the morphology of the capsules has been characterizated by optical
stereomicroscopy; moreover, a first overview of structural recovery has been obtained by means of three point
bending test.
Fig. 1. (i) NOx oxidation mechanism by a photocatalytic cement-based materials and (ii) Self-healing process in a concrete
containing an encapsulated healing agent in the cement matrix.
References
1
White SR, Sottos NR, Geubelle PH, Moore JS, Kessler MR, Sriram SR, et al. Autonomic healing of polymer composites.
Nature 2001; 409(6822):794.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P65
DRIFT or Transmission FT-IR?
A comparative study applied to high surface area carbons.
A. Lazzarini1,* E. Groppo1, C. Lamberti1, R. Pellegrini2, G. Leofanti3
1
2
Dept. of Chemistry, NIS and INSTM unità di Torino, University of Torino
Chimet SpA - Catalyst Division, Via di Pescaiola 74, I-52041 Viciomaggio (Arezzo), Italy
3
Consultant, Via Firenze 43, 20010 Canegrate (Milano) Italy
Keywords: DRIFT, Transmission FT-IR, Mie scattering, Active Carbons, Kramers-Kronig
High surface area carbons are materials exploited in several technological applications, ranging from filtration, to
gas trapping and catalysis(1, 2); for the latter application they are usually employed as supports for metal nanoparticles. Surface morphology and functionalization are fundamental to confer the desired properties (shape, size distribution, surface coverage) to the deposited nanoparticles.
IR radiation is a well-known probe to have information about surface groups and bonds in the bulk. The most
common instrumental configuration is the transmission setup (1), following Lambert-Beer law (A=µ∙x). However,
strong absorbing materials (large µ value) are difficult to be measured, unless you work with very diluted samples
(in KBr) or with thin depositions (i.e. suspending the material in a solvent and depositing it on a KBr window). An
easier way to collect data with IR radiation is the diffuse reflectance setup (DRIFT) (3, 4), which measures the radiation backscattered by the sample. Both techniques have been employed to collect FT-IR spectra of different activated carbons.
Fig. 1. FT-IR spectra of high surface area carbons measured in transmission(red) and DRIFT (blue): Full range (a) and detail (b)
Figure 1 shows the FT-IR spectra of the same carbons measured in transmission (spectra shown in absorbance
units) and in DRIFT (spectra shown in Kubelka-Munk values). It is evident that absorption bands belonging to the
same chemical species are shifted in the two cases. This is due to Mie scattering(5) occurring when there is a strong
change in refraction index between the sample and the medium (η air=1; ηcarbon≈2.4) and when the particles dimensions are comparable to the wavelength of the incident radiation. It is however possible to correct this kind of artifact applying Kramers-Kronig relationship(6, 7).
References
1.
2.
3.
4.
5.
6.
7.
D. B. Mawhinney, J. T. Yates Jr, Carbon 39, 1167 (2001).
J.-H. Zhou et al., Carbon 45, 785 (2007).
J. L. Figueiredo, M. F. R. Pereira, M. M. A. Freitas, J. J. M. Órfão, Carbon 37, 1379 (1999).
G. Mul, J. P. A. Neeft, F. Kapteijn, J. A. Moulijn, Carbon 36, 1269 (1998).
P. Bassan et al., Analyst 134, 1586 (2009).
M. H. A. Kramers, in Atti del Congresso Internazionale dei Fisici N. Zanichelli, Ed. (Como, 1927), vol. 2, pp. 545-557.
R. d. L. Kronig, Journal of the Optical Society of America 12, 547 (1926).
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P66
Quantitative Imaging Techniques for Monitoring the Conservation State of
Cultural Heritage
M. Manfredi*1, G. Bearman2, P. Shor3, E. Marengo1
1
Università del Piemonte Orientale, Dipartimento di Scienze ed Innovazione Tecnologica,
Viale T. Michel 11, 15121, Alessandria, Italy
2
ANE Image, Pasadena, CA (USA), Consultant to the IAA for the Imaging Technologies of the Dead Sea Scrolls
3
Director of the Dead Sea Scrolls Digitization Projects, Israel Antiquities Authority, Jerusalem, Israel
Keywords: Quantitative Imaging, Monitoring Conservation, Cultural Heritage, Multispectral Imaging, 3D Imaging
In recent years, the need to improve the quantitative imaging techniques for monitoring purposes has become
increasingly relevant.
The study of cultural heritage, archaeological, historical, artistic and archive, library or museum objects must
be dealt with on an interdisciplinary level, making use of different experiences and skills necessary in achieving a
common objective: preservation of the original object, both substrate and the media that contains the information on
the object. In the last years the targets of the research in this field has concerned the development of monitoring
methodologies that not only do not damage the object of art, leaving it unchanged for successive examinations, but
that were also respectful of the museum or the environment in which the appropriate equipment must operate.
Our studies are focused on the application of new imaging methods for monitoring the conservation of cultural
heritage. Quantitative imaging includes the development, standardization and optimization of imaging acquisition
protocols, data analysis and results interpretation in order to have a validated, reliable and precise methods.
We developed a quantitative multispectral imaging method for monitoring the conservation state of the Dead
Sea Scrolls for the Israel Antiquities Authority and of the Santa Maria di Castello frescoes[1, 2]. Moreover, a reliable “surface 3D” imaging method for the non-invasive detection of morphological changes in paintings and drawings was developed[3]. Both the imaging methods are coupled with statistical technique.
The method described follows a new approach in the context of cultural heritage aimed at the non-invasive automatic and fast detection of a developing deterioration process and its localization and identification.
The results showed that quantitative imaging techniques can be used for monitoring spectral and morphological changes of objects of art and in general of any surfaces.
References
1 E. Marengo, M. Manfredi, et all, Analytical Chemistry, 83 (2011) 6609–6618.
2 E. Marengo, M. Manfredi, et all, Analytica Chimica Acta 706 (2011) 229– 237.
3 M. Manfredi, M. G. Williamson, et all, Proceeding of Digital Heritage 2013 Conference, 2013.
P67
th
th
7th 7JFIC
-GIFC,
Turin,
Italy,
, 2014
5th-65thth,-62014
MayMay
Italy,
Turin,
GIFC,
Oxidative esterification of renewable furfural over highly dispersed gold catalysts
M. Manzoli1*, F. Menegazzo2, M. Signoretto2, F. Pinna2, G. Cerrato1, V. Aina1, F.
Boccuzzi1
1
2
Department of Chemistry and NIS Interdepartmental Centre, University of Torino, via P. Giuria 7, 10125 Turin (Italy)
Department of Molecular Sciences and Nanosystems, Ca’ Foscari University of Venice, Dorsoduro 2137, 30123 Venice (Italy)
Keywords: gold catalyst, furfural, oxidation, esterification, biomass
The upgrading of lignocellulosic biomass wastes into higher added-value chemicals is one the most researched
topics in the forthcoming concept of bio-refinery. The sustainability of biorefineries derives from their ability of
exploiting every product, as actually occurs in the oil refineries. In particular, additional transformations of furfural
are highly desired, and the synthesis of alkyl furoates could open very interesting perspectives for the use of xyloses
[1]. Currently, we are studying the oxidative esterification of furfural to either methyl or ethyl furoate on gold based
catalysts [2, 3]. The goal of the present work is to understand the role of the nature of the support on the reactivity
of highly dispersed Au samples; in particular, zirconia (Z), sulphated zirconia (SZ), titania (T) and ceria (Ce) oxides
have been investigated.
The oxidative esterification of furfural with methanol was tested without the addition of NaCH 3O, a base that
would make the process less green and more expensive [4]. Both molecular oxygen and air were charged in the 1-6
bar pressure range, while temperature was investigated in the 60 – 120 °C range.
Au supported catalyst
Fig. 1. Furfural oxidative esterification reaction.
The comparison among Au samples over different supports was performed under identical experimental conditions, showing that the catalytic performances follow the trend: AuSZ≥AuZ>AuCe> >AuT.
Fresh and used samples were characterized by metal content analysis, ionic chromatography (IC), N 2 adsorption, HRTEM, FTIR spectroscopy, pulse-flow CO chemisorption, TPO analyses. In order to obtain the best performing catalyst, both gold dispersion (for good conversion) and acid/base properties of the support (for good selectivity) must be taken into account: these were achieved only for the zirconia-supported catalysts. This feature can be
ascribed to the high gold dispersion combined with the presence of the proper uncoordinated basic sites (i.e., O 2-)
on zirconia. AuCe catalyst exhibited a lower performance than the zirconia-based ones, due to a very low amount of
free basic sites, as the surface is covered almost totally by anionic species. Moreover, ceria displayed an enhanced
redox behaviour, that seems to have no role in the reaction. The AuT sample exhibited a low conversion degree,
which can be due to the worst Au dispersion, even if it was extremely selective due to the proper amount of O 2sites. Catalysts stability and recycling were investigated too, and the opportunity of reusability by thermal oxidation
at a proper temperature was successfully proved.
Au-based catalysts were investigated in the oxidative esterification of furfural by an efficient and sustainable
process. The furoate ester can be obtained with optimal yields by a process greener than the actual one.
The chemical and morphological properties observed for zirconia samples seem to fulfil the best compromise
between high dispersion and the proper acid-base properties for good selectivity. AuSZ catalyst is therefore active,
selective, recyclable and proper for a chemistry based on renewable resources.
References
[1]
E. Taaring, I. S. Nielsen, K. Egeblad, R. Madsen, C.H. Christensen, ChemSusChem, 1 75.
[2]
F. Pinna, A. Olivo, V. Trevisan, F., Menegazzo, M. Signoretto, M. Manzoli, F. Boccuzzi, Catal. Today, 203 (2013) 196.
[3]
M. Signoretto, F. Menegazzo, L. Contessotto, F. Pinna, M. Manzoli, F. Boccuzzi, Appl. Catal. B., 129 (2013) 287.
[4]
O. Casanova, S. Iborra, A. Corma, J. Catal., 265 (2009) 109.
th
th
7th 7JFIC
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Turin,
Italy,
, 2014
GIFC,
Turin,
Italy,
MayMay
5th-65thth,-62014
P68
Highly active Au/Co3O4-CeO2 catalysts for low temperature CO
oxidation
M. Manzoli*1, T. Tabakova2, D. Dimitrov3, F. Vindigni1, P. Petrova2, L. Ilieva2, R. Zanella4, G. Munteanu5, K. Ivanov3
1
Department of Chemistry and NIS Centre of Excellence, University of Torino, via P. Giuria 7,10125 Torino, Italy
2
Institute of Catalysis, Bulgarian Academy of Sciences, Acad. G. Bonchev St.,Bl. 11, 1113 Sofia, Bulgaria
3
Department of Chemistry, Agricultural University, 4000 Plovdiv, Bulgaria
4
Centro de Ciencias Aplicadas y Desarrollo Tecnológico Universidad Nacional Autónoma de México. Circuito Exterior S/N,
Ciudad Universitaria.C. P. 04510 México D. F., Mexico
5
Institute of Physical Chemistry”Ilie Murgulescu”, Romanian Academy, Bucharest, Romania
(*) corresponding author: @E-mail address [email protected]
Keywords: CO oxidation, gold catalysts, ceria doped by Co3O4, HRTEM, FTIR, TPR
Gold nanoparticles supported on metal oxides have attracted significant attention in recent two decades due to
their high activity for catalyzing various oxidation reactions at low temperatures [1]. The catalytic oxidation of CO
is a subject of considerable interest due to its relevance in many industrial applications. The oxidation activity of
gold catalysts is closely related to the size of the gold nanoparticles and the ability of the support to provide active
oxygen species. For this reason, the selection of the support has been proposed to be a critical factor. Ceria is
known as a very attractive support material, because of its ability to maintain a high dispersion of the active
components and to change the oxidation state of the Ce cation, which results in rapid formation and elimination of
oxygen vacancy defects. The doping of ceria can increase the concentration of oxygen vacancies. The aim of the
present study was to optimize the amount of Co3O4 in CeO2-Co3O4 supports and to examine the effect of mixed
oxides composition on the CO oxidation activity of the gold catalysts. The addition of 5, 10 and 15 wt% Co 3O4
significantly affects the catalytic behaviour of Au/CeO2 (Figure 1A) and the best performance was observed over
the catalyst doped by 10 wt% Co3O4 (AuCe10Co) even below 0 oC, pointing out a positive effect of the modification with Co3O4. Moreover, the most active AuCe10Co catalyst demonstrated high stability. A 100 hours test was
conducted at 20 oC and 20000 h-1 and it was seen that the CO conversion dropped from 98 to about 90 % only in the
first 15 h and then remained constant. XRD analysis revealed the presence of the ceria phase and of a small amount
of Co3O4 phase, whilst no Au diffraction lines were detected. HAADF measurements indicated that on AuCe10Co
Au particles with the smallest average size (1.8 nm) are present, while as for AuCe5Co and AuCe15Co, Au average
size is 2.4 and 2.1 nm, respectively. The analysis of the fast Fourier transform (FFT) of the HRTEM images collected on AuCe10Co and undoped Au/CeO2 indicated that the co-presence of Co3O4 during the preparation affects
the defectivity of ceria exposed faces, influencing the reducibility and the catalytic activity. FTIR spectra of adsorbed CO show Au0 sites as well as positively charged Au adsorption sites, mainly on AuCe10Co. FTIR measurements of CO-18O2 interaction at low temperature have been performed to gain more insights on the oxygen mobility. H2-TPR analyses indicated that H2 consumption was the highest on AuCe10Co, whereas the reduction seems
hampered over AuCe5Co and AuCe15Co (Figure 1B).
100
C
AuCe15Co
CO conversion, %
80
90
60
129
40
AuCe10Co
93
 AuCe10Co
 AuCe15Co
0
-5
152
 AuCe5Co
20
-15
160
93
5
15
Temperature, oC
25
AuCe5Co
50
100
150
200
o
Temperature, C
Fig. 1. A)Temperature dependence of CO conversion over the catalysts; B) H2-TPR profiles of the gold catalysts.
The high defectivity of ceria exposed faces, the presence of both Au particles with the smallest size and a highly
reducible CoOx phase resulted in a larger enhancement of the mobility/reactivity of O atoms on the ceria surface.
These features render the AuCe10Co catalyst able to produce CO2 already at very low temperature, as confirmed by
FTIR. The results revealed the potential applicability of these catalysts for an efficient removal of CO.
References
1 G.C. Bond, C. Louis, D.T. Thompson, Catalysis by Gold, Imperial College Press, London, 2006.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P69
Directed studies towards the total synthesis of
CDEF rings of lactonamycine
Muhammad Idham Darussalam Mardjan*, Romain Blanc, Raphaël Rahmani,
Sébastien Dubois,Virginie Héran, Jean-Luc Parrain, Laurent Commeiras.
Aix-Marseille Université, Institut des Sciences Moléculaires de Marseille, ISM2 – UMR 6263, Centre Saint Jérôme, Service
532, 13397 Marseille Cedex 20, France.
Keywords: lactonamycin, Diels-Alder cycloaddition, Michael addition.
Lactonamycin is an antibiotic with unique structure unlike the other antibiotics. It was isolated from the
culture broth of Streptomyces rishiriensis in 19961. The potent biological activity of lactonamycin against various
MRSA and VRE as well as several tumor cell lines encouraged researchers to develop the different approaches for
the metabolites. Various synthetic strategies have been proposed and realized to afford the unique hexacyclic core
and the highly oxygenated structure of lactonamycin.
In the study of total synthesis of CDEF-ring of lactonamycin, the key steps of Diels-Alder and Michael addition reaction were employed. In the previous study, CDEF-ring has been accessed by successfully installing the
angular methoxy group which was difficult to introduce by other research groups2. However, the hydroxyl group on
C-5a has not been incorporated yet. In this study, we would like to prepare the CDEF-ring of lactonamycin including the incorporation of both angular methoxy group and the hydroxyl group on C-5a.
References
[1]
N. Matsumoto, T. Tsuchida, M. Maruyama, R. Sawa, N. Kinoshita, Y. Homma, Y. Takahashi, H. Iinuma, H. Naganawa,
T. Sawa, M. Hamada and T. Takeuchi, J. Antibiot., 49 (1996) 953-953.
[2]
S. Dubois, F. Rodier, R. Blanc, R. Rahmani, V. Héran, J. Thibonnet, L. Commeiras and J.-L. Parrain, Org. Biomol. Chem.,
10 (2012) 4712-4719.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P70
Characterisation study of tomato sauce preserved in different packaging materials
E. Mazzucco*, E. Robotti, F. Gosetti, M. Manfredi, G. Calabrese, E. Marengo
University of Piemonte Orientale, Department of Sciences and Technological Innovation, Viale Michel 11, 15121 Alessandria
Keywords: tomato sauce, characterisation study, chemometrics
In Mediterranean diet, tomato rapresents one of the most consumed food and provide an optimal mix of dietary antioxidants such as phenolic compounds, ascorbic acid, and carotenoids, mainly lycopene, whose individual,
additive, or synergistic actions may be responsible for the reported health benefits of its consumption [1-3]. A characterisation study of tomato sauce conserved in different packaging materials was performed.
Several commercial products, stored in cans, glass or multilayer, were collected and each sample was characterized evaluating the volatile profile, the content of anions (both organic and inorganic), carotenoids (lycopene, αand β-carotene), flavonoids (epicatechin and quercetin), metals, total polyphenols, and vitamins (B1, B2, B5, B6,
B9 and C). According to the target analytes, different sample pretreatments and analytical techniques were developed. Indeed, to study the volatile profile head space solid phase microextraction (HS SPME) technique followed
by gas chromatography and mass spectrometry detection (GC-MS) were used and about eighty molecules were
identified. High performance liquid chromatography (HPLC) with spectrophotometric detector was used to identify
and quantify the carotenoids contents after a liquid liquid extraction. A ultra high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method was developed to study simultaneously the content of
vitamins and flavonoids. The contents of anions was determined by ion chromatography while metals were determined by inductively coupled plasma with optical emission spectroscopy (ICP OES) and mass spectrometry (ICP
MS). Each analytical method was optimised and validated according to ISO 17025.
An overall dataset of 31 samples, purchased form local markets, was analysed and about 200 variables were
determined to characterise each sample. The results were subjected to multivariate statistical analysis by Partial
Least Squares Discriminant Analysis (PLS-DA) and Ranking PCA to asses differences in the tomato composition
by comparing glass with can or glass with multilayer.
References
1
F.J. García-Alonso, S. Bravo, J. Casas, D. Pérez-Conesa, K. Jacob, M.J. Periago, J. Agric. Food Chem. 57 (2009) 6815.
[2]
K. Jacob, M.J. Periago, V. Böhm, G.R. Berruezo, Br. J. Nutr. 99 (2008) 137.
[3]
J.W. Jr Erdman, N.A. Ford, B.L. Lindshield, Arch.Biochem. Biophys. 483 (2008) 229.
P71
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Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
Discovery and development of a new family of anti-melanoma compounds
A. Millet1, M. Cerezo2, S. Rocchi2, R. Balotti2 and R. Benhida1*
1
Institut de Chimie de Nice, ICN, UMR 7272 CNRS, Université Nice-Sophia Antipolis, 28 avenue de Valrose,
06108 Nice Cedex 2, France.
2
INSERM U895, team 1, Centre Méditerranéen de Médecine Moléculaire (C3M), équipe 1: Biologie et pathologies des cellules mélanocytaires, Bâtiment Archimed, 151 route Saint Antoine de Ginestière, BP 2 3194, 06204 Nice Cedex 3, France.
Keywords: Resistant melanoma, inhibitors, structure activity relationship
Melanocytes are melanin-producing cells originating from the neural crest. Those cells, primarily located
in the hair follicle, epidermis and eye, are responsible for skin hair and eye pigmentation. The malignant transformation of melanocytes leads to a particularly aggressive type of cancer, a malignant melanoma. Malignant melanoma is often considered as one of the most aggressive cancer, with a median survival that does not exceed 12
months, and is particularized by its capacity to rapidly evolve into metastatic cancer 1. Surgery is often used for the
treatment of melanoma but remains useless for the treatment of metastatic melanoma. In such case, chemotherapy
and immunotherapy are used to prolonged patient survival but those treatments are often palliative instead-of being
curative, despite encouraging progress in melanoma treatment 2.
Vemurafenib and Dabrafenib (figure 1) are active on the mutated B-Raf protein kinase called the V600E
mutation where valine residue is substituted with glutamic acid residue. But some patients develop resistance within
few months to those treatments. Therefore, there is an urgent need to find new anti-melanoma drugs with new
modes of action.
In this project, we focused on the design, synthesis and biological evaluation of new series of compounds
for the treatment of melanoma, in collaboration with Dr. S. Rocchi. We first developed a synthetic strategy based
on the optimization of thiazolidindiones (or glitazones) 3 compounds to access new series of lead compounds. This
series of compounds appears to be highly efficient on both sensitive and resistant melanoma cell line, while they
have very low effects on normal cells. This new class of molecules is a new alternative to the current chemotherapy
and open the way for treatment of metastatic melanoma resistant to B-Raf inhibitors.
1
Vemurafenib (FDA approved in 2011)
2
Dabrafenib (FDA approved in 2013)
Fig. 1. Developped structure of Vemurafenib (1) and Dabrafenib (2), currently used for chemotherapies
References
1
Goding, C. R. The International Journal of Biochemistry & Cell Biology 2007, 39, 275–279.
Hofmann, M.A. et al., Skin Cancer : Recognition and Management, Second Edition 2008, 2, 477-507.
3
Botton T. et al. Cell Death and Differentiation 2011, 18, 109–121.
2
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P72
Synthesis and Biological Evaluation of Colchifulvin, a Colchicine-Griseofulvin
Hybrid
Alberto Minassi,*Azucena Marset, Armando Genazzani and Giovanni Appendino
Dipartimento di Scienze del Farmaco, Università del Piemonte Orientale, Via Bovio 6, 28100, Novara, Italy
(*) Alberto Minassi: [email protected]
Keywords: natural compounds, antimitotic agent, antifungal antibiotic
The molecular biologist François Jacob once remarked that ature is “like a tinkerer who does not know exactly
what he is going to produce but uses whatever he finds around him to produce some kind of workable object. None
of the material at the tinkerer’s disposal has a precise and definite function. Each can be used in different ways.
Novelty comes from previously unseen association of old material. To create is to recombine”. [1] The biogenetic
origin of many classes of natural products, (meroterpenoids, flavonoids, indole alkaloids..) cogently testifies the
materialization of this strategy to create bioactivity, as does the structure of many secondary metabolites. These
principles have inspired the design of a hybrid construct between the antigout agent colchicine (1) and the orally
active antifungal antibiotic griseofulvin (2). Both compounds bind tubulin and kinetically suppress microtubule
dynamics, but interact with different sites of the target, namely the eponymous site for colchicine, and the paclitaxel
site for griseofulvine. Colchicine is too toxic to be used as an anticancer agent, and its current use in medicine is
limited to the management of acute gout crises and the prevention of Familial Mediterranan fever, a rare genetic
disease. On the other hand, griseofulvin, although capable to induce apoptosis in cancer cells sparing the healthy
ones, has higher affinity for fungal tubulin compared to mammalian tubulin, and its potency as an anticancer agent
seems too low, at least as a stand-alone chemotherapeutic agent.
With the aim of combining the profiles of colchicine and griseofulvin into a domesticated hybrid endowed with
potent anticancer activity and modest toxicity, we have designed colchifulvin (3), a spirodienone derivative where
the A-ring of colchicine is bound to a spirodienone B,C system reminiscent of the B,C ring system of griseofulvin,
and also reminiscent of a twisted version of the cis-stilbenoid system of combretastatin (4), another antimitotic
agent binding tubulin at the colchicine site. We report here the synthesis of colchifulvin and an evaluation of its
antimitotic and anti-tubulin profile.
References
1 F.Jacob, Science 196 (1977) 1161-1166
P73
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Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
Photocatalytic process on TiO2–Reduced Graphene Oxide hybrid materials: UVbased, dye sensitized or visible sensitized photocatalysis?
M. Minella1(*), V. Maurino1, C. Minero
1
Department of Chemistry and NIS Center of Excellence, University of Torino, Via P. Giuria 5,
Torino 10125, Italy http://www.environmentalchemistry.unito.it.
Keywords: Graphene Oxide, Dye Sensitized Photocatalysis, TiO2-rGO hybrid materials, Visible Sensitization
Graphene oxide (GO) suspensions were adsorbed on titanium dioxide and chemically reduced by hydrazine at
room temperature.[1] Hybrid materials with different loadings of reduced graphene oxide (rGO), from 0.5 to 5%,
were produced on nanosized TiO2 and silica and their photocatalytic behavior compared with pristine supports using phenol and methylene blue (MB) under two different irradiation conditions (near UV and Vis light) with the
aim of clarifying the role of rGO in the photocatalytic mechanism. MB is strongly adsorbed on the surface of the
hybrid materials, and the amount of dye adsorbed at the surface increases with the increment of the rGO loading.
Significant MB degradation rates were observed on pristine titania and hybrid TiO 2-rGO materials both under UV
and Vis irradiation. The presence of rGO has the largest effects on the degradation kinetics under Vis light. MB
degradation experiments performed on rGO-silica exclude that MB could inject electrons to rGO [2]. MB degrades
by injecting photoexcited LUMO electrons in TiO2 conduction band. For MB the degradation under Vis is due to
the dye sensitized photocatalytic mechanism, while under UV the semiconductor-based photocatalytic mechanism
is working. [3] The role of rGO seems to be limited to that of adsorption. Conversely, the presence of rGO reduces
the rate of photocatalytic transformation for the poorly adsorbed phenol under UV irradiation, while negligible rates
of degradation were observed under Vis irradiation both on pure titania, and on TiO 2-rGO materials. No visible
sensitized photocatalytic mechanism due to rGO is operating. The extensive analysis of UV-Vis absorption spectra
at different rGO loadings on TiO2 and different loadings of hybrid material shows that the rate reduction under UV
is due to the decrease of the band-gap absorption of TiO2. From this set of experimental data it emerges that the
beneficial effect of rGO at the surface of titanium dioxide is related only to the increase of adsorption. The inferences drawn by single substrate experiments, particularly with dyes (e.g. MB), or a single type of irradiation can be
misleading.
Fig. 1. Photocatalytic degradation of 4x10–5 M of Methylene Blue at pH 3 in the presence of TiO2-rGO hybrid materials with
different rGO loadings under UV irradiation. Catalyst concentration 0.5 g dm–3. Fraction of MB in solution at the time i with
respect to that at irradiation time zero. Inset: pseudo first order kinetic constants for the photocatalytic transformation of MB as a
function of the % rGO.
References
1
T. Szabó, O. Berkesi, P. Forgó, K. Josepovits, Y. Sanakis, D. Petridis, Imre Dékány, Chem. Mater. 18 (2006) 2740
[2]
V. Pagonis, C. Ankjærgaard, A.S. Murray, R. Chen, J. Lumin. 129 (2009) 1003
[3]
X. Lang, X. Chen, J. Zhao, Chem. Soc. Rev. 43 (2014) 473
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P74
Flux synthesis of intermetallic compounds in the R-Mg-Sn systems
(R = rare earth metal)
R. Minetti*, P. Solokha, S. De Negri, A. Saccone
Università di Genova, Dipartimento di Chimica e Chimica Industriale, Via Dodecaneso 31, 16146 Genova, Italy
Keywords: intermetallic compounds, flux synthesis
Ternary rare earth metal germanides have been extensively studied, whereas much less data are present for the
related stannides [1]. In the specimens obtained with standard methods three or more ternary intermetallic phases
with unknown structure are often present, making difficult the structure determination. Moreover several of these
phases present an unexpectedly high sensitivity to air even for R-poor compositions, that further hamper the study
of new compounds. In this study we investigate the use of the flux synthesis applied to the R-Mg-Sn systems (R =
La, Nd, Gd, Er). The flux, a low melting element, added in large excess, acting as solvent for the other elements,
could lead to the stabilization of specific phases [2].
We have carried out tests with two kind of flux: a reactive (Sn) and a non-reactive flux (such as In, Ga, Bi). In
our synthesis i twas used a ten times excess of the reactive (non-reactive) flux. The constituents were enclosed in
sealed Ta crucibles and subjected to a thermal treatment in a resistance furnace. Ingots obtained in such way were
cut along the vertical axis and observed by scanning electron microscopy (SEM). Different methods to separate the
obtained crustals from the flux were explored to perform further X-ray single crystal diffraction measurements.
References
1
P. Villars, K. Cenzual, Pearson’s Crystal Data, Release 2013/14
2
M. G. Kanatzidis et al., Angew. Chem. Int. Ed. 44 (2005) 6996-7023
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P75
Pure and mixed Pt-K/Al2O3 and Ce1-xZrxO2 systems for the simultaneous
abatement of NOx and soot from lean-burn engines.
S. Morandi1*, R. Matarrese2, L. Castoldi2, L. Lietti2, K. Gallucci3, P.L. Villa3
1
Dipartimento di Chimica and NIS Inter-departmental Center, Università di Torino, Via Giuria 7, 10125 Torino, Italy.
Dipartimento di Energia, Laboratory of Catalysis and Catalytic Processes and NEMAS, Centre of Excellence, Politecnico di
Milano, P.zza L. da Vinci 32, Milano, Italy.
3
Dipartimento di Chimica, Ingegneria Chimica e Materiali, Università degli Studi dell’Aquila, Via Gronchi 18, Zona industriale di Pile, 67100, L’Aquila, Italy.
2
Keywords: de-NOx catalysts, de-soot catalysts, in situ FT-IR.
The severe limits for emissions from mobile sources imposed by EURO 6 regulations are stimulating heavy
investments in the development on one hand of engines with high efficiency, on the other hand of catalytic systems
for the treatment of exhaust gases. Actually, the catalytic converters used in the conventional stoichiometric engines
are not able to eliminate efficiently NOx in diesel working conditions, due to excess oxygen. One of the main promising technology is based on Lean NOx Traps (LNT) proposed by Toyota [1]. The LNT approach employs a noble
metal (Pt) and an alkaline or alkaline-earth element (typically Ba or K) dispersed on a suitable support like alumina.
Besides, the control of particulate (soot) emissions is currently accomplished by the use of the so-called diesel particulate filters [2]. These devices, made by a cordierite or SiC filter, provide excellent filtration efficiency, but must
be periodically regenerated. Integrated de-NOx and de-soot after-treatment technologies have been proposed. One
example, recently developed by Toyota [3], is the diesel particulate-NOx reduction (DPNR) system that consists of
a porous ceramic filter coated with a LNT catalytic layer. Beside DPNR systems, good performances for soot combustion are shown by Ce1-xZrxO2 mixed oxides [4], in which the mobility of lattice oxygen has a key role. However,
the soot oxidation rate of these systems is maximum at temperature higher than 500 °C.
In this work, the efficiency in soot removal of a Ce 1-xZrxO2 system prepared by a citrate modified method with
the addition of K and Ru was checked. In situ FT-IR spectroscopy was coupled with gas phase analysis to investigate the fundamentals of the catalyst activity. In particular, the aim of the work consists in combining the de-soot
activity of the Ce-Zr system with the de-NOx properties of a Pt-K/Al2O3 LNT catalyst.
Fig. 1. Soot oxidation tests at increasing temperature performed without
catalyst (black line) or catalyzed by CeZrRuKO2 and Pt-K/Al2O3 systems.
Absorbance
CeZrRuKO2 system shows the maximum in the soot oxidation rate at temperature lower than 400 °C (Fig.1), therefore in the
temperature range of diesel engine exhaust gases. In addition, it
shows high NOx storage capacity but low NOx reduction activity.
In particular, FT-IR measurements show that CeZrRuKO2 stores
NOx as bulk nitrates with the initial formation of nitrites (Fig. 2).
High performances in NOx abatement of CeZrRuKO2 and PtK/Al2O3 mixture were found. It is worth of note that nitrates
formed on CeZrRuKO2 system are completely reduced when it is
1.5
mixed with Pt-K/Al2O3 catalyst, differently from the case with
30 sec
1 min
nitrates
pure CeZrRuKO2. Moreover, for the CeZrRuKO2 and Pt-K/Al2O3
3 min
mixture a synergic effect towards soot combustion is apparent
10 min
1.0
and the presence of soot does not appreciably affects the features
of the reduction of stored NOx. This makes mixed LNT/CeZr
catalytic system a good DPNR candidate (with reduced Pt connitrites
0.5
Ru-nitrosyls
tent) for the simultaneous removal of NOx and soot from Diesel
exhausts.
References
[1] Toyota Patent, European Patent Application No. 0 573 672 A1
(1992).
[2] B.van Setten et al., Catal. Rev. 43 (4) (2001) 489.
[3] Toyota Patent, European Patent Application No. 01107629.6 (2001).
[4] I. Atribak et al., Appl. Catal. B: Env. 92 (2009) 126.
[5] Villa, P.L., U.S. Patent 7,166,267, B2 (23 January 2007).
0.0
2000
1800
1600
1400
1200
-1
Wavenumbers (cm )
Fig. 2. FT-IR spectra of CeZrRuKO2 system
upon NO/O2 interaction at 300 °C and at increasing contact time.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P76
Preparation and Utilisation of new Lewis Acids derivatives of p-toluenesulfonic
acid and methanesulfonic acid as Catalyst in Friedel-Crafts Acylation Reaction
V. Morizur1, S. Olivero1, J. R. Desmurs2, E. Duñach*,1
1
2
Institut de Chimie de Nice, Université de Nice-Sophia Antipolis, CNRS, UMR 7272, Faculté des Sciences, Parc
Valrose, 06108 Nice cedex 2, France e-mail : [email protected]
CDP Innovation, 38 route de Ternay, 69360 Communay 63 Rue André Bollier, e-mail : [email protected]
Metallic triflates and triflimides are useful catalysts in organic chemistry. [1] However, these catalysts can be
expensive. In this context, the set-up of new catalysts easy to use and of lower cost is a challenge. We were
interested in metallic salts of methanesulfonic acid and p-toluenesulfonic acid. We thus prepared a series of new
Lewis acids derived from these two protic acids by using an ultrasound methodology [2], [3] (Figure 1). We
prepared salts of bismuth (III), indium (III), zinc (II) and copper (II) salts.
Figure 1: Preparation of new metal salts by sonochemistry
These salts were used as catalysts in the Friedel-Crafts acylation reaction (Figure 2) in order to study the influence
of the nature of the metal and of the anion on this process.
Figure 2: Influence of catalysts in Friedel-Crafts acylation reaction
The reaction has been extended to several aromatic substrates and the results are compared to the use of metal
triflates as the catalysts.
[1] Antoniotti, S. ; Poulain-Martini, S. ; Duñach, E. ; Synlett., 2010, 2973-2988.
[2] Legrave, N. ; Couhert, A. ; Olivero, S. ; Desmurs, J. R. ; Duñach, E. ; Eur. J. Org. Chem., 2012, 901-904.
[3] Desmurs, J. R. ; Duñach, E. ; Olivero, S. ; Antoniotti, S. ; Patent, WO 2012010752, 2012.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
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2014
7thth JFIC -GIFC,
P77
Design, synthesis and characterization of pH responsive luminescent hybrid mesoporous materials
G. Musso*,1, I. Miletto1, G. Caputo1, S. Coluccia1, Gloria Berlier1
1
Università degli Studi di Torino, NIS Centre of Excellence, Dipartimento di Chimica Via P. Giuria, 7, 10125 Torino, Italy
Keywords: pH sensing probe, mesoporous silica nanoparticles, stiryl cyanine dyes
This work is focused on the preparation of versatile mesoporous materials functionalized with fluorescent dyes to
monitor and track pH changes associated with inappropriate cell functions, cellular pathways and drug delivery
processes [1,2]. To this aim a new series of stiryl cyanine dyes have been developed. These molecules exibit pH
responsive fluorescent properties and a versatile structure that permits the introduction of different functional
groups in order to explore and compare different routes for the preparation, with the final goal to obtain different
working-range pH sensig luminescent hybrid systems. The use of a mesoporous silica as matrix for pH sensing
fluorophores provides brighter and more stable systems with respect to dyes alone [3]. This contribution includes
the textural, morphological and structural properties of the fluorescent nanosized silica materials and the
preliminary results on the photophysical performances and pH response of the selected fluorofores before and after
anchoring on the silica substrate.
Fig. 1. General structure of the stiryl cyanine dyes
References
[1]
[2]
[3]
H. Junyan and K. Burgess, Chem. Rev., 110 (2010), 2709.
Li Fan, Y.J. Fu, Q.L. Liu, D.T. Lu, C. Dong and S.M. Shuang, Chem. Commun., 48 (2012), 11202.
L. Mortati, I. Miletto, G. Alberto, G. Caputo and M.P. Sassi, J. Fluoresc, 21 (2011) 929.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
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2014
7thth JFIC -GIFC,
P78
RAFT-synthesized electroactive polymers based on ferrocenyl methacrylates
R. Nguema Edzang*,1, C. Bressy1, M. Lejars1, J-M. Raimundo2, H. Brisset1.
1
MAPIEM EA 4323, University of Toulon, France.
2
CiNaM, Aix-Marseille University, France.
(*) corresponding author: Ronald Nguema Edzang (E-mail: [email protected])
Keywords: Ferrocene, methacrylate, radical addition fragmentation chain transfer, electroactive polymers, cyclic voltammetry.
Abstract: Because of the reversible redox properties of ferrocene and its anti-bacterial activity [1], ferrocenylbased polymers are interesting to synthesize as new anti-adhesive binders for marine antifouling coatings [2]. This
study reports the reversible-deactivation radical homopolymerization (RDRP) of 1-ferrocenylmethyl methacrylate
(F-MMA) as well as of two new ferrocene bearing monomers, namely 2-ferrocenylmethoxyethyl methacrylate
(FMOEMA) and 3-ferrocenylmethoxypropyl methacrylate (FMOPMA), by the RAFT process (Figure 1).
Ferrocenyl methacrylates were first synthesized. The kinetics of homopolymerizations were studied by in situ
NMR spectrometry. The polymerizations were very well controlled using 2,2-azobis(isobutyronitrile) (AIBN) as
the initiator and 2-Cyanoprop-2-yl dithiobenzoate (CPDB) as the transfer agent at 70°C in toluene. The numberaverage molar masses of polymer chains were determined by 1H NMR comparing the signals of the CTA moieties
and the signals of the monomer units. In addition, molar masses and dispersity values of purified homopolymers
were determined by TD-SEC. Monomer conversion was evaluated by 1H NMR comparing the signals of the reactive double bond (6.4 to 6 ppm) from monomer with the methylene -CH2-O-C(O)- protons from monomer and polymer (from 5.2 to 4.6 ppm).
The monomer conversion follows the first order kinetic (up to 80 %) together with a linearly increase of the Mn
value with monomer conversion.The ferrocene containing monomers were found to be highly reactive in RAFT
polymerization, leading to monomer conversion values up to 96 %. Low dispersities (< 1.2) were obtained for all
homopolymers. Using the known FMMA as reference monomer, the distance between the polymerizable and the
ferrocene moieties is increased in FMOEMA and FMOPMA to enable the mobility of the side groups of the polymer chain. Electrochemical properties of both monomers and homopolymers were characterized.
S
S
n
NC
S
O
O
S
O
Fe
O
AIBN, Toluene-d8, 70°C
Fe
Figure 1. Synthesis of ferrocenyl methacrylic homopolymers by the RAFT process in the presence of 2-cyanoprop2-yl dithiobenzoate (CPDB) as chain transfer agent, azobisisobutyronitrile (AIBN) as initiator, at 70°C, in toluene.
References
1
M. Okochi, T. Matsunaga, Electrochimica Acta 42 (1997) 3247.
2 M. Lejars, A. Margaillan, C. Bressy, Chemical Review 112 (2012) 4347.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P79
Fabrication of self-assembled nanoporous organic coatings for membranes
technology
L. Iannarelli1,2, R. Nisticò1,2, P. Avetta1, G. Magnacca1,2, P. Calza1,2, D. Fabbri1, D.
Scalarone*,1,2
1
University of Torino, Department of Chemistry, Via P. Giuria 7, 10125 Torino, Italy
2
NIS Research Centre, Via P. Giuria 7, 10125 Torino, Italy
Keywords: Block copolymers; Nanoporous membranes; Self-assembly; Spin-coating
Aim of the present work is the preparation of organic membranes with narrow pore size distribution and high
porosity to be applied in the field of microfluidic analyses and as selective gates in microchip-based technologies
for separation, detection and dosing of molecular or ionic species, charged nanoparticles or biomolecules.
Highly selective membranes with controlled porosity can be obtained by coating appropriate supports with
nanoporous thin films. The capability of block copolymers to spontaneously arrange into well-defined ordered
structures with nanoscopic size has proven to be particularly advantageous for templating nanoporous membranes
and recently block copolymer-derived membranes have been proposed as highly selective layers in composite
membranes [1,2].
The main advantages of block copolymer-templated membranes over other types of polymer membranes are
their narrow pore size distribution, high void fraction and smooth surfaces, resulting in superior selectivity, high
fluxes and fouling resistance. Pore size can be easily varied to optimize size selectivity, and additional separation
mechanisms can be introduced by tuning the membrane surface properties through functionalization of the pore
walls.
In this contribution, we describe the fabrication procedure of nanoporous membranes with uniform pore size
and high pore density obtained by spin-coating polystyrene-block-poly(ethylene-oxide) (PS-b-PEO) solutions on
commercial silicon nitride microsieves (5μm of pores diameters). To better control the formation of well-defined
nanostructures, a supramolecular approach was applied, based on the complexation by hydrogen-bonding of the
PEO block with small molecules bearing hydroxyl groups, i.e. resorcinol. The addition of resorcinol in different
PEO/resorcinol ratios was investigated and the effect on the alignment of PEO domains (and consequently on the
final porosity) was confirmed [3]. From PS-b-PEO/resorcinol mixtures, ordered films with normally oriented
PEO/resorcinol cylindrical domains were obtained. These nanostructured films were subjected to a previous UV
treatment, to improve their mechanical properties by crosslinking the PS matrix, and then to a selective wet
treatement with iso-propanol, to remove resorcinol and create an hydrophilic porous system in the PEO domains.
Composite membranes consisting of large-pore silicon nitride support and a continuous polymeric nanoporous
layer were fabricated and tested as gates for controlled transport of chemicals (Fig.1).
Fig. 1. AFM topography showing the continuous nanoporous polymer layer covering the Si3N4 microsieve (side a: image of a
pore covered by polymeric membrane in a section 5μm × 5μm of the microsieve; side b: 1μm × 1μm section of the block
copolymer-derived membrane).
References
1
S.Y. Yang, J.A. Yang, E.S. Kim, G. Jeon, E.J. Oh, K.Y. Choi, S.K. Hahn, J.K. Kim, ACS Nano 4 (2010) 3817.
[2]
E.E. Nuxoll, M.A. Hillmyer, R. Wang, C. Leighton, and R.A. Siegel, ACS Applied Materials & Interfaces 1 (2009) 888.
3
J. Tata, D. Scalarone, M. Lazzari, O. Chiantore, Eur. Polym. J. 45 (2009) 2520.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P80
Metal triflate-catalysed cycloisomerisation of allenic enol-ethers
I. Diaf, P. Ondet, A. Joffrin, G. Lemière*, E. Duñach*
Institut de Chimie de Nice, Université de Nice Sophia Antipolis, CNRS, UMR 7272, Faculté des Sciences, Parc Valrose, 06108
Nice Cedex 2, France
(*) Elisabet Duñach: [email protected]
(*) Gilles Lemière: [email protected]
Cycloisomerisation, allene, enol ether, metal triflates, bismuth
Over the last twenty years, metal triflates catalysts have emerged as important contributors to modern organic
synthesis and for the development of sustainable chemistry. In particular, the non-toxic Lewis acid bismuth(III)
triflate has proven to be a useful catalyst in a wide range of different transformations under mild conditions.[1]
In this context, allenes constitute extremely valuable synthetic building blocks. In the presence of a Lewis acid, this functional group can exhibit nucleophilic or electrophilic behavior depending on the reaction conditions.[2]
The cycloisomerisation of enol-ether allenes catalysed by metal triflates are being developped as new catalytic and
‘atom economic’ tools for the formation of various cyclic compounds (eq 1). For instance, oxaspiro compounds can
be efficiently obtained from readily available starting allenic substrates upon with bismuth(III) triflate catalysis (eq
2) with an excellent diastereoselectivity.
The new compounds present a potential application in the field of flavours and fragrances. [3]
•
Bi(OTf)3 (0.1 mol %)
OMe
•
TIPSO
CH2Cl2
RT, 30 min
75%
same conditions
O
70%
(eq 1)
OMe
O
(eq 2)
OTIPS
one diastereoisomer
Fig. 1. Bismuth triflate catalysed allenic enol-ether cyclisation
References
1
a) J. M. Bothwell, S. W. Krabbe and R. S. Mohan Chem. Soc. Rev. 40 (2011) 4649-4707. b) H. Gaspard-Iloughmane and
C. Le Roux, Eur. J. Org. Chem. (2004) 2517-2532. c) T. Ollevier, Org. Biomol. Chem. 11 (2013) 2740-2755.
[2]
a) G. Lemière, B. Cacciuttolo, E. Belhassen and E. Duñach, Org. Lett. 14 (2012) 2750-2753. b) I. Diaf, G. Lemière, E.
Duñach, Angew. Chem. Int. Ed. (2014) DOI: 10.1002/anie.201310724.
[3]
G. Lemière, E. Duñach, Chem.Eur. J. 19 (2013) 3270-3280.
JFIC -GIFC,
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,,2014
2014
77thth JFIC
P81
X-ray structures of single crystal high-Tc superconductors (HTSC) modulated by
chemical substitutions.
L. Pascale1,2, U. Costa3, A. Pagliero3, A. Agostino*,1,2, M. Truccato3, L. Operti1,2
2
1
Chemistry Department, University of Turin, Via P. Giuria 7 10125 Turin (Italy)
CRISDI Interdipartimental Center for Crystallography, University of Turin, Via P. Giuria 7 10125 Turin (Italy)
3
Physics Department, University of Turin, Via P. Giuria 1 10125 Turin (Italy)
Keywords: High-Tc Superconductors, YBCO, Single-Crystal X-Ray Diffraction, chemical doping, Intrinsic Josephson Junctions
Josephson Junctions (JJ) can be considered as two superconducting materials separated by a thin layer of
insulator. By applying an electrical voltage at the heads of a series of JJ, an alternating current is generated, whose
oscillation frequency is proportional to the applied voltage and is in the range of Terahertz (THz).
Stacks of Intrinsic Josephson Junctions (IJJ) with atomic size are naturally present in layered high-Tc
superconductors (HTSC) such as Y1Ba2Cu3O7- δ (Y-123) and Bi2Sr2CaCu2O8+δ (Bi-2212) (Figure 1) [1, 2]. Among
the possible IJJ applications, high frequency devices can take advantage from the large Josephson plasma frequency
found in some HTSC IJJs. In particular, Y-123 has the highest Josephson plasma frequency and its properties can
be modulated, for instance, by cationic substitutions, as already noticed for Pb-doped Bi-2212 [3].
In view of a future exploitation of IJJ, HTSC whiskers, that are multilayered single crystals characterized by an
highly crystalline nature, low defects concentration and excellent superconducting features, like the ones belonging
to the Y-123 system, are ideal structures for the study and the design of THz devices based on IJJ.
Within this context, we investigated the effect of chemical cationic subtitutions as Al, Sb, Te, Ca and Pb [4],
of anionic doping (O2) [5] and of X-ray nanobeam irradiation [6] on both the electrical and the structural properties
of Y-123, Bi-2212 and Bi2Sr2Ca2Cu3O10+x (Bi-2223).
Fig. 1. Scheme of a JJ inside Y-123 structure.
In this work, we present some structural and superconducting modulations induced on Y-123 by chemical
doping with Ca, Al, Te and Sb to improve: chemical properties as aspect ratio (length/width), morphology, yield,
number of nucleation center; phisical properties as Tc and Jc; modulation of IJJ's stacks along the structure. The
effects of the elemental incorporation in the structure have been investigated using single crystal X-ray diffraction
technique and SEM/EDS measurements to obtain information on cationic distribution. In particular, single crystal
X-ray diffraction successfully correlate the cationic insertion with the substitution sites, highlighting sometimes a
modification of coordination frameworks of copper. The electrical characterization R-T indicates corresponding
changes in the conducting properties of the materials.
References
[1]
R. Kleiner, F. Steinmeyer, G. Kunkel, P. Muller, Phys Rev Lett. 68 (1992) 2394.
[2]
T. Kawae, M. Nagao, Y. Takano, H. B. Wang, T. Hatano, T. Yamashita, Physica C. 426 (2005) 1479.
[3]
H. Kambara, I. Kakeya, M. Suzuki, Physica C. 471 (2011) 754.
[4]
F. Bertolotti, L. Calore, G. Gervasio, A. Agostino, M. Truccato, L. Operti, Acta Cryst. (2014) B70.
[5]
M.M. Rahman Khan, S. Cagliero, A. Agostino, M. Beagum, C. Plapcianu, M. Truccato, Supercond Sci Technol. 22 (2009)
085011.
[6]
A. Pagliero, L. Mino, E. Borfecchia, M. Truccato, A. Agostino, L. Pascale, E. Enrico, N. De Leo, C. Lamberti, G.
Martínez-Criado, Nano Lett. 14 (2014) 1583.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
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2014
7thth JFIC -GIFC,
P82
Alternative ionomers for redox - flow batteries
L.Pasquini*1,2, R. Narducci1,2, K.Pelzer1, P.Knauth1, M.L. Di Vona2,
2
1
Aix Marseille Université, CNRS, MADIREL UMR 7246, 13397 Marseille, France
Università di Roma Tor Vergata, Dip. Scienze e Tecnologie Chimiche, 00133 Roma, Italy
Keywords: proton conductors, sulfonated, anion conductors, sulfaminated, PEEK
The need to improve the distribution of resources on the earth, including clean and renewable energy, the necessity to reduce the pollution and the continuous increase of petrol cost, have reinforced the interest of the scientific
community in systems for energy conversion and storage for medium to large scale application. In this scenario,
electrochemical systems appear a good choice, given their flexibility, high efficiency and noise-less operation [1].
This has projected our attention to the study of polymeric membranes able to increase the efficiency of operation
and decrease the costs of electrochemical energy storage devices like redox - flow batteries (RFB).
RFB can operate both with protonic and anionic membranes so that we study differents ionomers (fig.1) to obtain both types of ionic conduction. We mainly focused our attention on the functionalization of aromatic polymers,
especiallly polyetheretherketone (PEEK), because of its relatively low price and high chemical, thermal and mechanical stability.
To realize protonic conducting membranes, we synthesized sulfonated PEEK (SPEEK) by the introduction of
sulfonic acid groups on the main chain and we stabilized them via cross-linking sulfone bridges using a reticulation
agent (DMSO)[2]. We were able to maximize the ionic conductivity by controlling the degree of sulfonation (DS) of
the membranes and, by crosslinking, to lower the water uptake and consequently the swelling and deformation of
the membranes.
Furthermore, we synthesized and studied anion exchange membranes based on sulfaminated aromatic polymers
made in a first step by chlorosulfonation of the polymer, which reacts in a second step with secondary amines (dimethylamine or diethylamine). The cast membranes were then functionalized by reaction with various inorganic
acids (HCl, HBr, H2SO4, HNO3, H3PO4) to obtain anion-conducting ionomers. The main objective was to obtain
membranes with high ionic conductivity, and excellent chemical, mechanical and thermal stability controlling the
degree of sulfamination (DA).
Thermogravimetric analysis showed that the anionic membranes are thermally stable above 200°C, while mechanical tests gave a high elastic modulus and relatively low ductility; water uptake and ionic conductivity can be
tuned by the degree of functionalization thus to obtain values of conductivity up to ≃ 3 mS/cm.
Fig. 1. Example of synthesized membranes with exchange groups and formula of the corresponding repeat units:
right proton conductor, left anionic conductor.
References
1
2
P.Alotto, M. Guarnieri, F. Moro, Redox flow batteries for the storage of renewable energy: A review, Renewable and
Sustainable Energy Reviews, vol. 29, 2014, p. 325-335
M.L. Di Vona, L. Pasquini, R. Narducci, K. Pelzer, A. Donadio, M. Casciola, P.Knauth, Cross – linked sulfonated aromatic polymers via SO2 bridges: conductivity properties, Journal of Power Sources, vol. 243, 2013, p. 488-493
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P83
Anion exchange membranes for fuel cells
L. Pasquini
2
*1,2
, R. Narducci1,2, K.Pelzer1, P. Knauth1, M.L. Di Vona2
1
Aix Marseille Université, CNRS, MADIREL UMR 7246, 13397 Marseille, France
Università di Roma Tor Vergata, Dip. Scienze e Tecnologie Chimiche, 00133 Roma, Italy
Keywords: Hydroxide conductivity, polysulfone, amines, impedance spectroscopy, cross-linking
The need for reduction of pollution and the continuous increase of petrol cost have reinforced the scientific interest for Fuel Cells (FCs) as efficient and clean systems to convert chemical energy into electrical energy. We
incentrate our work on polymer electrolyte fuel cells, because they exibit excellent characteristics of weight, volume and current density for automotive application and co-generation systems [1].
Taking advantage of our previous studies and knowledge about proton exchange membranes [2,3], we focused
our recent studies on anion exchange membranes (AEM) for alkaline polymer electrolyte fuel cells that are promising devices given their fast fuel cell kinetics and inexpensive metal electrodes, even if AEM generally present low
ionic conductivity, low stability and risk of carbonation [4].
In our work, we chose aromatic polymers, above all polysulfone (PSU), to be functionalized with anionic
groups to obtain AEM. In particular we synthesized chloromethylated precursors with different degrees of substitution and we quaternized them by reaction with various amines, such as trimethylamine and cyclic amines (1,5diazabicyclo-[4,3,0]-non-5-ene (DBN) and 1,4-diazabicyclo[2.2.2]octane (DABCO)), to explore the stability in
alkaline media. We realized membranes from the synthesized polymers (figure 1) by casting from DMSO solutions.
We studied various chemical and physical properties of the membranes using technique like 1H NMR, impedance spectroscopy, thermogravimetric analysis, mechanical tests and water uptake measurements. The stability test
(treatment during 7 days in KOH at 60°C), water uptake and conductivity measurements evidenced that the utilized
amines, the degrees of chloromethylation and amination (DAM) and a cross-linking treatment of the polymers
strongly influence the properties. The hydroxide conductivity increases with DAM, but the stability decreases. The
use of DBN, probably by delocalization of the positive charge on a second cycle, as well as the cross - linking improves the stability of membranes.
Fig. 1. PSU-trimethylammonium hydroxide membrane after casting from DMSO and repeat unit.
References
1
G.Alberti, R.Narducci, M.L. Di Vona, Perfluorinated sulfonic acids as proton conductor membranes, in Solid State Proton Conductors, P.
Knauth and M. L. Di Vona ed., Wiley, 2012, p. 295-330.
[2] M.L. Di Vona, L. Pasquini, R. Narducci, K. Pelzer, A. Donadio, M. Casciola, P.Knauth, Cross – linked sulfonated aromatic polymers via
SO2 bridges: conductivity properties, Journal of Power Sources, vol. 243, 2013, p. 488-493
[3] P. Knauth, L. Pasquini, B. Maranesi, K. Pelzer, R. Polini, M.L. Di Vona, Proton Mobility in Sulfonated PolyEtherEtherKetone (SPEEK):
Influence of Thermal Crosslinking and Annealing, Fuel Cells, vol. 13, 2013, p.79-85.
[4] Y.-J. Wang. J. Quiao, R. Baker, J. Zhang, Alkaline polymer electrolyte membranes for fuel cells applications, Chem. Rev. Soc. Vol. 42,
2013, p. 5768-5787
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P84
Potential use of entropy functions as a measure of complexity
Emilio Marco Pellegrino*,1, Elena Ghibaudi1
1
Università di Torino, Dipartimento di Chimica, Via P. Giuria 7 10125 Torino
Keywords: complexity, transformation, information, protein, modelling relation
The speculation over the methodological aspects of the current chemical research implies the use of a logical architecture wherein the concept of complex system [1] is essential not only from a theoretical viewpoint. In fact,
reasoning in a complex perspective may provide useful insights for data interpretation and experimental design
within a variety of experimental research fields, ranging from nanomaterials to protein chemistry. Moreover, the
complexity debate opens up new possibilities for classifying the borderline phenomenology that falls at the edge of
different disciplines and may be described under different and irreducible perspectives in distinct disciplinary domains. This is the case of many phenomena that lie at the border between chemistry, physics and biology.
The investigation on complex systems leads inevitably to questioning about the possibility of defining the
complexity degree of a system or to recognize, inside a complex system, distinct levels of complexity. From a qualitative perspective, this multiplicity may often appear intuitive, based on classification hierachies such as the “complexity pyramid of life” proposed by Oltvai e Barabási [2]; but the consistency of these classifications becomes
critical as soon as a quantitative evaluation is attempted. Is it really possible to quantify the complexity degree of a
system? Some authors propose to use entropy as an index of complexity [3]. This instance made us drill down the
concept of entropy and highlight a plethora of entropy definitions (more than 40), not always consistent between
them, that can be found in the scientific literature. In order to perform a critical investigation of the existing relationships among these different definitions and of their implications, we classified the entropy definitions in five
main groups, each one based on a distinct theoretical reference system: i) physical entropy, an experimentally
measurable entity, includes the original definition by Clausius (dS=δq/T) and represents a measure of the transformation content (Verwandlungsinhalt) of a thermodynamic system [4]; ii) mathematical entropy, a formal instance,
includes all definitions referring to the faff’s theory on differential equations and the assiomatic approach to the
Second Law of thermodynamics, e.g. the entropies by Caratheodory [5], Lieb-Yngvason [6] and Tsaliss [7]; iii)
quantum entropy, outlined for the first time by von Neumann [8] with reference to the Density Matrix formalism,
can be seen as a measure of the “purity” of an arbitrary quantum state. iv) cybernetic entropy, related with the Information Theory, includes the functions by Kolmogorov and Shannon [9]; v) statistical-mechanics entropy includes definitions developed inside Statistical Thermodynamics, e.g. the Gibbs’s [10] and Boltzmann’s [11] entropies.
Our work leads towards two main conclusions: i) being aware of the variety of entropy definitions suggests
the need for carefully contextualizing the concept of entropy before using it; ii) the plurality of entropy definitions
can be exploited as a tool for defining the complexity degree of a system, according to the definition of complex
system proposed by Rosen [12]. In fact, the availability of a variety of functions, referred to distinctly different
theoretical models, that are irreducible to each other, is a peculiarity of the complex nature of a system.
The application of this theoretical approach to the case of a protein system will be discussed.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
G. Nicolis, I. Prigogine, Exploring Complexity, Freeman, New York 1989.
N. Z. Oltvai, A. Barabási, Science.298 (763) 2002.
N. Lehman 1, C. Díaz Arenas , W. A. White, F. J. Schmidt, Entropy 13 (17-37) 2011
R. Clausius, Phil. Mag. 2 (102) 1851.
C. Caratheodory, Math. Annalen. 67 (355) 1909.
E.H. Lieb, J. Yngvason, Physics Reports. 310 (1) 1999; Phys.Today 53 (32) 2000.
C. Tsallis, J. Stat. Phys. 52 (479) 1988.
J. von Neumann, Z. Phys. 57 (30) 1929.
C.E. Shannon, Bell System Tech. J. 27 (379) 1948
J.W. Gibbs, The Scientific Papers of J. Willard Gibbs, Vol. 1 Thermodynamics, Longmans, London, 1906.
L. Boltzmann, Wiener Ber. 66 (275) 1872.
R. Rosen, Theoretical biology and complexity: three essays into the natural philosophy of complex systems (165–203)
Orlando Academic 1985.
77ththJFIC
JFIC-GIFC,
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Turin,Italy,
Italy,May
May55thth-6
-6thth,,2014
2014
P85
Strategies for the synthesis of shape controlled TiO2 nanoparticles.
L. Pellutiè *,1, C. Deiana 1, G. Martra 1, V. Maurino 1
1
University of Turin, Department of Chemistry, Via Pietro Giuria 5, 10125 Turin, Italy
Keywords: TiO2, anatase, nanoparticles, synthesis, shape-controlled
Important challenges are related to the establishment of validated method and instrumentation for characterization and analysis of TiO2 nanoparticles, due to the promising possible multisectorial applications of TiO2 nanocrystals. For example, in photocatalysis on anatase nanocrystals some results suggest that (001) surfaces can be
considered essentially as oxidation sites with a key role in the photoxidation, while (101) surfaces provide reductive
sites [1,2]. Furthermore, integrated studies of CO molecular probe on truncated bipyramidal TiO 2 anatase nanoparticles mainly exposing smooth (101) surfaces provide the missing link between TiO 2 single crystals and commercial
TiO2 nanopowders with complex morphology [3]. The availability of different sets of shape and dimension controlled TiO2 NPs can allow a proper definition of the correlation between the morphological and functional properties of TiO2. In the tentative to achieve these goals our work focused on the synthesis of TiO2 NPs and allowed us
to obtain dimension and shape-controlled nanoparticles. Shape-controlled titania nanoparticles were prepared by
forced hydrolysis of TiIV(triethanolamine)2 complexes [3,4].
In fact we obtained truncated bipyramidal TiO2 anatase nanoparticles mainly enclosed by (101) and (001) type
facets. The crystallographic phase was investigated by X-Ray Diffraction (XRD), while the shape parameters and
the exposed facets by the analysis of the HR-TEM and FE-SEM images. Figure 1 shows the FE-SEM and HR-TEM
images and the XRD patterns of some of the synthetized materials.
Fig. 1. (left) HR-TEM images of one of the obtained materials, original magnifications (A) 100k × and (A’) 600k ×; (B) XRD
patterns of TiO2 NPs prepared using different synthesis temperatures; (right) FE-SEM images of one of the obtained materials.
Nanoparticles dimensions were determined by Dynamic Light Scattering (DLS) obtaining the medium hydrodynamic radius (rH) and polidispersity index, and by the analysis of the X-Ray Diffraction patterns. All the synthetized materials had shown a low polidispersity index (ca. 0.1). The modulation of the size, between 12 - 41 nm of
the hydrodynamic radius, was obtained varying the temperature of the forced hydrolysis (120-210 °C). Increasing
the TiIV(triethanolamine)2 complex concentration the shape of the NPs changes from bypiramidal to elongated
along c-axis, probably due to the coalescence of pristinely formed bypiramids (Figure 1C). This important data is
presented in Table 1.
Table 1. Nanoparticles dimension distribution (polidispersity index) and dimensions (r H and crystal size from XRD patterns).
Synthesis temperature Polidispersity index
rn
120 °C
150 °C
180 °C
210 °C
12
15
22
29
0.118
0.082
0,129
0.135
(nm)
rw
14
17
29
41
(nm) Crystal size from XRD (nm)
14
18
21
---
References
[1]
[2]
[3]
[4]
M. D’Arienzo, J. Carbajo, A. Bahamonde, M. Crippa, S. olizzi, R. Scotti, L. Wahba and F. Morazzoni, J. Am. Chem. Soc.
133 (2011) 17652-17661.
T. Ohno, K. Sarukawa and M. Matsumura, New J. Chem. 26 (2002) 1167-1170.
C. Deiana, M. Minella, G. Tabacchi, V. Maurino, E. Fois and G. Martra, Phys. Chem. Chem. Phys. 15 (2013) 307-315.
T. Sugimoto, X. P. Zhou and A. Muramatsu, Journal of Colloid and Interface Science. 259, (1), (2003) 53-61.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P86
Relationship between cellular accumulation, DNA platination and antiproliferative
activity for a series of Pt(IV) complexes: the effect of the length of the axial ligand
E. Perin,1 M. Alessio,1 I. Zanellato,1 I. Bonarrigo,1 E. Gabano,1 M. Ravera,1 D. Osella*,1
1
Keywords: Pt(IV) complexes, lipophilicity, cellular accumulation, DNA platination, spheroids
The antitumoral activity of Pt(II) drugs, after their cell entrance, is related to their ability in making adducts with
nucleic acids, which in turn correlates with their cytotoxicity. Octahedral Pt(IV) complexes are considered as Pt(II)
pro-drugs, since they remain intact until their arrival in the cells and, only intracellularly, they can be activated by
reducing biological agents. Their greater inertness, compared to Pt(II) complexes, is a very interesting feature because it may allow them for oral administration. According to the “activation by reduction” theory [1], Pt(II) and
Pt(IV) compounds having the same carrier group can generate the same final DNA damaging agent and this is supported by the observed cross-resistance between Pt(IV) and the parental Pt(II) complex. The nature of the ligands
influences the propensity to undergo reduction and the activity of the Pt(IV) compounds, as well as their cellular
uptake, and/or selectivity. The cytotoxicity of Pt(IV) complexes is related to both their reduction potential (Ep) and
lipophilicity [2, 3]: the easier the reduction and the higher the lipophilicity, the higher the cytotoxicity. These two
chemico-physical properties, in turn related to cellular uptake and activation by reduction in cytosol, can be tuned
through an accurate choice of the ligands. The increase of the lipophilicity is expected to enhance cellular uptake by
passive diffusion. Up to now, however, the Pt(IV) complexes relationship between lipophilicity, cell accumulation,
DNA platination and antiproliferative activity is quite unesplored. So, in order to thoroughly investigate these issues, our purpose is to synthesize a series of homologous dicarboxylatoplatinum(IV) complexes, based on the
square-planar cisplatin and containing carboxylato ligands of different length in axial position (Figure 1), and to
compare them with cisplatin itself. The study regarding the Pt cellular accumulation, the DNA platination and the
antiproliferative activity of these complexes is carried out on the very Pt-sensitive ovaric A2780 cell line.
Fig. 1. Scheme of the Pt-complexes under investigation
Moreover, the antiproliferative activity of the investigated compounds is tested on 3D multicellular tumour spheroids (MCTSs). MCTSs are in vitro compact aggregates of cells that are more similar to in vivo solid tumours with
respect to 2D cellular monolayers, as regards their cytoarchitecture and physiological features. Therefore, as compared to the two-dimesional cell models, MCTSs are more predictive of the efficacy of an antitumor drug candidate
in vivo. We report on the antiproliferative activity of the studied dicarboxylatoplatinum(IV) prodrug candidates in
terms of their effect on MCTSs growth.
References
1
N. Graf, S. J. Lippard, Advanced Drug Delivery Reviews 64 (2012) 993.
2
P. Gramatica, E. Papa, M. Luini, E. Monti, M. B. Gariboldi, M. Ravera, E. Gabano, L. Gaviglio, D. Osella, J. Biol. Inorg.
Chem. 7 (2010) 1157.
3
J. A. Platts, G. Ermondi, G. Caron, M. Ravera, E. Gabano, L. Gaviglio, G. Pelosi, D. Osella, J. Biol. Inorg. Chem. 16
(2011) 361.
th
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7th JFIC -GIFC,
P87
New alicyclic phosphorylated nitrones with antioxidant potential and their use
as free radical detectors in a model of acute joint inflammation
C. Petrocchi*, M. Robin, V. Pique, H. Rahmouni,
S. Thétiot-Laurent, S. Pietri, M. Culcasi
Aix-Marseille Université, CNRS, ICR UMR 7273, Equipe “Sondes Moléculaires en Biologie et Stress Oxydant”
13397 Marseille Cedex 20, France.
Keywords: nitrones, antioxidant, spin trapping, ESR, human cartilage cells
Although the possible occurrence of free radicals in the course of pathological events is well-documented it is
still questioned whether scavenging these transient species may be an efficient therapeutic strategy against oxidative stress. To address this issue we are developing new hybrid probes with both antioxidant function and electron
spin resonance (ESR)-based free radical detection properties. Twenty new phenyl-substituted, -phosphorylated
nitrones (1) derived from -phenyl-N-tert-butylnitrone (PBN) have been synthesized on the basis of: (1) the improved ESR characteristics (increased reaction rates and stability of nitroxide adducts, especially from carboncentered radicals) of P-containing spin traps [1−3]; (2) the introduction of natural antioxidant moieties, and (3) the
possibility to modulate lipophilicity to target subcellular sites. The general synthetic pathway of 1 is given in Fig. 1,
in which the nature, number and position of R substituents of the aromatic ring may ensure either direct scavenging
of biologically-relevant oxyradicals and/or specific multinuclei NMR detection of metabolites.
O
H
P
Acetone
O
H2N
NH3
O
P
O
KMnO4
O
O
O2N
P
O
Zn
O
O
O
HO
N
H
P
O
O
O
+
R
H
R
N
P
O
O
O
O
1
R= Antioxidant moiety, X
Fig. 1. General synthesis of hybrid antioxidant spin traps 1.
Data on ESR parameters of characteristic spin adducts formed in vitro, lipophilicity and cytotoxicity indices,
and antioxidant properties in standard assays will be presented. The nitrones that best meet the above criteria will
be tested in a human model of acute joint inflammation (ie, cartilage cells) [4] taken as an in vitro model of the
normal response to tissue injury consecutive to free radical formation.
References
1
C. Fréjaville, H. Karoui, B. Tuccio, F. Le Moigne, M. Culcasi, S. Pietri, R. Lauricella, P. Tordo. J. Med. Chem. 38 (1995)
258.
2
C. Rizzi, S. Marque, F. Belin, J. C. Bouteiller, R. Lauricella, B. Tuccio, P. Tordo. J. Chem. Soc., Perkin Trans 2 (1997)
2513.
3
G. Gosset, J. L. Clément, M. Culcasi, A. Rockenbauer, S. Pietri. Bioorg. Med. Chem. 19 (2011) 2218.
4
L. Li, B. Fox, J. Keeble, J. M. Salto-Tellez, P. G. Winyard, M. E. Wood, P. K. Moore, M. Whiteman, J. Cell. Mol. Med.
17 (2013) 365.
P88
th
7th JFIC
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Turin,
Italy,
MayMay
5th-65thth,-62014
7th JFIC
-GIFC,
Turin,
Italy,
, 2014
Development of new hydroxypyrazole-based inhibitors of Plasmodium
falciparum dihydroorotate dehydrogenase (PfDHODH)
A.C. Pippione1*, A. Giraudo1, I. Galleano1, U.J. Nilsson2, I. Fritzson3, A.P. Sundin2, S.
Al-Karadaghi4, D. Boschi1 and M.L. Lolli1.
1
2
Centre for Analysis and Synthesis, Department of Chemistry, Lund University, PO Box 124, 221 00 Lund, Sweden.
3
Active Biotech AB, PO Box 724, 220 07 Lund, Sweden.
4
Center for Molecular Protein Science, Department of Chemistry, Lund University, PO Box 124, 221 00 Lund, Sweden.
Keywords: malaria, PfDHODH inhibitors, hydroxypyrazoles.
Malaria is still a major global health challenge as current drug therapies are compromised by resistance. Plasmodium falciparum dihydroorotate dehydrogenase (PfDHODH) was validated as a new drug target after triazolopyrimidine-based inhibitors showed anti-malarial activity in vivo[1,2]. Here, we firstly present the synthesis and the biological evaluation of a new series of PfDHODH inhibitors bearing 3-hydroxypyrazole moiety (compounds 1 - 4). Compound 1 showed a micromolar activity on PfDHODH while it is inactive against the human DHODH isoform. This
preliminary result suggests that 1 could represent an interesting lead compound to design new selective PfDHODH
inhibitors. When docked inside the PfDHODH binding pocket, the carboxylic function present in 1, essential for
activity, seems to play a fondamental role. We hypothize that it interacts with protonated Arg 265, a key aminoacid
present in the area where inhibitors explain their activity. Close to the Arg 265 residue, the additional lipophilic
pocket could be easily occupied by the phenoxy moiety of 1 (figure 1). These assumptions allowed us to design
new derivatives based on the 1H-4-carboxypyrazole scaffold that could present additional interactions with the
protein. The biological assay of this second series would confirm whether our ligand-protein interaction assumptions are correct and will allow us to explore the binding site of PfDHODH, searching for more potent and selective
inhibitors based on this scaffold. In the second group of compounds the presence of substituents on the hydroxyl
and phenoxyl moieties of 1 (see structures C, figure 1) was investigated. Synthesis and pharmacological profiling of
this second modulation are presented and fully discussed.
Fig. 1. a) series of designed hydroxypyrazoles, proposed for the lead compound generation; b) hypothesized binding mode for
compound 1 (Ligand Scout™); c) series of 1H-4-carboxypyrazoles, designed from compound 1 and investigated in this study.
References
1
R. Gujjar, A. Marwaha, F. El Mazouni et al., J. Med. Chem. 52 (2009) 1864.
[2]
H. Munier-Lehmann, P.O.Vidalain, F. Tangyet al., J Med Chem. 56 (2013) 3148.
P89
Cannabinoid-like prenylresorcinols from Helichrysum umbraculigerum Less.:
Isolation and profile of activity against thermo-TRPs
G. Appendino1*, F. Pollastro1, O. Taglialatela-Scafati2, L. De Petrocellis3, V. Di Marzo3,
Heino Heyman4
1
Dipartimento di Scienze del Farmaco, Largo Donegani 2, 28100 Novara (Italy)
2
Dipartimento di Farmacia, via D. Montesano, 39, 80131 Napoli (Italy)
3
Istituto di Chimica Biomolecolare, CNR, via Campi Flegrei 34, Comprensorio Olivetti, 80078 Pozzuoli, NA, (Italy)
4
Department of Plant Science, University of Pretoria, Pretoria, 0002 Gauteng (South Africa)
(*) Giovanni Appendino: [email protected]
Keywords: cannabinoids, Helichrysum, cannabigerol, Heli-cannabigerol, TRP, CBs
South Africa hosts a large diversity of plants from the genus Helichrysum species, 245 of which are endemic. Unlike their Mediterranean relatives, some South-African species of Helichrysum are used not only in medicine, but
also as inhebriating incenses in ritual ceremonies [1]. One South African species of Helichrysum (H. umbraculigerum Less.) is, indeed, the only non-hemp source of cannabinoids discovered so far, containing large amounts of
cannabigerol (CBG, 1a) and its acidic precursor (pre-CBG, 1b). South African Helicrysum species also contain
stiryl analogues of cannabinoid (Heli-cannabinoids), a class of compounds characterized by the replacement of the
n-alkyl (pentyl or propyl) group of hemp-cannabinoids with a stiryl or a dihydrostiryl residue, as exemplified by
Heli-CBG (2). The biological profile of these compounds is, surprisingly, still completely unknown.
To fill this gap, we have investigated a collection of H. umbraculigerum from the Walter Sisulu Botanical Garden
in Johannesburg, South Africa, isolating several Heli-cannabinoids, including 2, as well as other related prenylated
phloroglucynols, that were investigated for their activity on the metabotropic (CB1 and CB2) and the ionotropic
(thremo-TRPs) targets of hemp-cannabinoids, discovering significant activity against some specific therm-TRPs.
The structure elucidation of the novel compounds and the bioactivity profile of these compounds will be presented.
References
1
A.C.U. Lourensa, A.M. Viljoenb, F.R. van Heerdena: South African Helichrysum species: A review of the traditional
uses, biological activity and phytochemistry, J. Ethnopharmacol., 119 (2008) 630–652
[2]
F. Bohlmann, E-. Hoffmann: Cannabigerol-aehnliche Verbindungen aus Helichrysum umbraculigerum, Phytochemistry,
18 (1979) 1371-1374.
P90
th
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7th JFIC -GIFC,
[Ag(PPh3)4][(PPh3)CdCl3], the first monomeric triclorocadmate ion bonded to a phosporous ligand: a structural and spectroscopic study.
Eliano Diana, Emanuele Priola*
Università degli studi di Torino, Dipartimento di chimica, Via Pietro Giuria 7
Keywords: cadmium, luminescence, phosphine,complex
Chloro complexes of cadmium have an important role in the study of the chemistry of this element, and recently
their structural versatility as potential building blocks for the construction of coordination polymers has been exploited. Apart the [CdCl4]2- species, the tetrahedral geometry is not common in chloro complexes, and few monomeric species have been studied [1], in particular the trichlorocadmate anion has been reported only in seven solid
structure [2] . We reported the first synthesis and analysis of a trichlorocadmate anion bonded to a phosphorous
ligand, [(PPh3)CdCl3]-. In this research, we have investigated the behaviour of this anionic complex in crystalline
state and solution, by using crystallographic, spectroscopic and computational tools. We report the crystal structure
of the first salt obtained with this anion, the heterobimetallic complex [Ag(PPh3)4][(PPh3)CdCl3] : this compound
has a monoclinic structure, based on non-classical hydrogen bonds that link aromatic C-H groups and chlorides and
on Van der Waals interactions between the phenyl rings. This compound shows photoluminescence, both in the
solid state and in solution. The electronic spectra have been analysed and correlated to the electronic structure. This
study has the aim of understanding the behaviour of the cadmium trichloro complexes with phosphorous ligands
for possible development in the synthesis of other analogues.
Figure 1:Cristal structure of [Ag(PPh3)4][(PPh3)CdCl3]
References
[1] A. F.Cameron et al, J. Chem. Soc. (A), (1971)1286-1289; J. M. Kessler et al ,Magn. Reson. Chem.., 29 (1991), 94-105
[2] C.-L. Chen et al. , Inorg. Chim. Acta ,358 (2005), 4527–4533
77ththJFIC
JFIC-GIFC,
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Turin,Italy,
Italy,May
2014
P91
Synthesis of Thiophene-Pyridine Ligands by C-C cross-Coupling Reaction
in Micellar Medium
S. Prosperini*, G. Viscardi, C. Barolo, R. Buscaino, P. Carfora and P. Quagliotto
Department of Chemistry, University of Turin, Turin, Italy
(*) e-mail: [email protected]
Keywords: Suzuki reaction, palladium catalyst, thiophene, pyridine, micellar catalysis.
Actually, the most exciting goals of molecular organic synthesis are related to architectures in which highlyefficient photoinduced energy- or electron-transfer processes can take place, in particular over long distances,
through polymeric condensation of small molecules. [1]. Thiophene-pyridines are small molecules that possess a
variety of potential applications such as in artificial photosynthesis [2a], photocatalysis, [2b], molecular photovoltaic cells [2c] and optoelectronic devices [2d]. Requirements of Green Chemistry for simpler and cleaner methodologies, pushed us to apply Cerichelli et al. [3] method by adapting and extending the micellar catalysis to both electron-rich and electron-poor heterocycle coupling partners. We report thiopheneboronic acids and bromopyridines
couplings as model system, also extended to oligopyridines, by using CTAB as the surfactant, and both homogeneous Pd(PPh3)4 and heterogeneous Pd/C or PdCl2 catalysts, in both thermal or MW conditions (Scheme 1a).
Scheme 1. a) general micellar conditions of reaction. b) synthesis in micellar medium of the ligand L1.
Fig. 1. Comparison of the yield for a reaction performed in thermal and microwaves conditions.
Reactions with 2-thiopheneboronic acid were performed at RT, while 3-thiopheneboronic acid required temperatures in the range 80-100°C as in micellar or ionic liquid medium systems [4]. Pd(PPh3)4 gave the best yields (7580%) with respect to Pd/C (40%) or PdCl2 (60%). The homogeneous conditions were optimized for both thermal
and MW activated reactions in the case of the 2-bromopyridines (Figure 1). Finally, we tested the synthesis in micellar medium of a ligand named L1, 4-(thiophen-3-yl)-2,2’-bipiridine, (85% of yield), applying the best conditions
identified for the reaction of 3-thiopheneboronic acid with 3-bromopyridine as a model (see Scheme 1b).
References
1 a) J.W. Verhoeven, J. Kroon, M.N. Paddon-Row, J.M. Warman, in Supramolecular Chemistry; V. Balzani, , L. De Cola, Eds.; NATO ASI Ser. C, Vol. 371, (1992); p 181. b) V. Balzani, F. Scandola, in Supramolecular Photochemistry; Harwood:
Chichester, 1991.
[2] a) D. Gust, T.A. Moore,. Science 244, (1989), 35. b) R. Ziessel, in Photosensitization and Photocatalysis Using
Inoganic and Organometallic Compounds; K. Kalyanasundaram, M. Grätzel, Eds.; Kluwer Academic Publishers: Dordrecht,
1993; p 217. c) B. ’Regan, M. Grätzel, Nature 353, (1991), 737. d). A. Mishra, C. Ma, P. Bauerle, Chem. Rev. 109, (2009),
1141.
[3] A. Arcadi, G. Cerichelli, M. Chiarini, M. Correa, D. Zorzan, Eur. J. Org. Chem. (2003), 4080.
[4] M. Massaro, S. Riela, G. Lazzara, M. Gruttadauria, S. Milioto, R. Noto Appl. Organometal. Chem. 28, (2014), 234.
P92
Deposition of Sb2Se3 nanofilm on Au by Electrochemical Atomic Layer Epitaxy
Y. Chen 1,2, A. Pradel2, A. Merlen1, M. Ribes2, M.-C. Record*,1
1
Université Aix-Marseille, CNRS, IM2NP, Case 142, Av. Escadrille Normandie-Niemen, F-13397 Marseille Cedex 20, France
2
Université Montpellier II, CNRS, Institut Charles Gerhardt, CC1503, F-34095 Montpellier Cedex 5, France
Keywords: Electrodeposition, Atomic Layer Deposition, monolayer, chalcogenides
Electrochemical Atomic Layer Epitaxy, abbreviated as EC-ALE, was put forward by Gregory and Stickney in 1991
[1]. EC-ALE is a method for preparing thin-film compounds at room temperature, which is based on the alternate
underpotential deposition (UPD) of atomic layers of elements to make up a compound.
UPD is a surface-limited electrochemical phenomenon that makes the deposition generally limited to a single atomic layer. In every cycle one monolayer of the compound is obtained, and the thickness of the deposit is only depending on the number of cycles. Each cycle consists in a series of individual steps, and each step can be optimized
independently, resulting in well-controlled deposits.
In the present work, the EC-ALE technique is employed to prepare a Sb2Se3 nano-film. The UPD behavior of selenium and antimony on polycrystalline gold substrates has been investigated by means of cyclic voltammetry, anodic potentiodynamic scanning and coulometry.
After the optimization of the depositing parameters of Se and Sb in each layer, three atomic layers of Sb-Se compound were obtained. The stoichiometry ratio for Se to Sb was calculated from coulometry and it was found to be
2.92 : 2. The deposits were then characterized by Scanning Electron Microscopy and Raman spectral analyses.
They were found to be compact and the observed Raman modes correspond to the heteropolar Sb-Se bond vibration
in the SbSe3/2 pyramides already reported in various Sb 2Se3 nanostructures [2-4].
This work shows the feasibility of electrodepositing Sb 2Se3 nanofilm controlled at atomic level by ECALE.
Fig. 1. Anodic potentiodynamic scanning curves (scanning rate 20 mV/s) and the corresponding schematic drawings of the
Se/Sb/Se deposition structure on Au substrate.
The authors would like to thank Dr. C. Pardanaud (PIIM Laboratory, Aix-Marseille university) for the Raman scattering measurements and the China Scholarship Council (CSC) for the financial support of uan Chen‘s hD thesis
References
1
2
3
4
5
B. W. Gregory, J. L. Stickney, J. Electroanal. Chem. 300 (1991) 543.
J. Lu, Q. Han, X. Yang, L. Lu, X. Wang, Mater. Lett., 62 (2008) 2415.
X. Ma, Z. Zhang, X. Wang, S. Wang, F. Xu, Y. Qian, J.Crystal Growth, 263 (2004) 491.
J. Wang, Z. Deng, Y. Li, Mater. Res. Bull., 37 (2002) 495.
Y. Zhang, G. Li, B. Zhang, L. Zhang, Mater. Lett., 58 (2004) 2279.
P93
77ththJFIC
JFIC-GIFC,
-GIFC,Turin,
Turin,Italy,
Italy,May
2014
Natural sources and total synthesis of quadrane sesquiterpenes
Yajun Ren, Marc Presset, Jeremy Godemert, Jean Rodriguez*, Yoann Coquerel*
Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France
presenting author: [email protected]; corresponding author: [email protected]
Keywords: Natural products / Sesquiterpenes / Quadrane / Total synthesis / Structure–activity relationships
Quadranes are a restricted family of naturally occurring sesquiterpenes belonging to the larger group of
polyquinanes, featuring a diquinane core fused with a bicyclo[3.2.1]octane system. [1] They were discovered in 1978
with the isolation of (–)-quadrone, which because of its challenging structure and highly potent biological activity
has attracted considerable attention. Since 2000, new members of this family of natural products with enhanced
biological activities have been isolated and have triggered renewed interest in these natural sesquiterpenes.
This communication will provide a rapid overview of the currently available data for quadranoids (including structural, biosynthetic, and biological considerations) together with a summary of the work directed towards
the total synthesis of quadranoids. Then our own synthetic approach based on a multicatalytic domino reaction for
the enantioselective construction of the key functionalized bicycle [3.2.1] octane ring system will be presented. [2]
Naturally occurring quadranes
O
O
O
HO2C
O
from fungal sources:
(–)-quadrone
O
from marine sources:
(+)-suberosenone
(+)-terrecyclic acid A
CO2H
CO2H
(–)-isishippuric acid B
References
1
[2]
Review: M. Presset, Y. Coquerel, J. Rodriguez, Eur. J. Org. Chem. 2010, 2247-2260.
Reviews: (a) M. Presset, Y. Coquerel, J. Rodriguez, ChemCatChem 2012, 4, 172–174; (b) M. Presset, Y. Coquerel, J.
Rodriguez, Chem. Rev. 2013, 113, 525−595.
JFIC -GIFC,
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
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2014
7thth JFIC
P94
Mass Spectrometry tools to study the molecular dialog in a cnidariandinoflagellate symbiosis
J. Revel1,2, L. Massi3, M. Mehiri3, L. Capron3, F. Priouzeau1,2, M. Wisztorski4, D. Moujjah4, C. Sabourault1,2*
1
2
UMR7138, IBPS, University of Nice, 06108 Nice Cedex 2
UMR7138, IBPS, CNRS-University Paris 6, 75252 Paris Cedex 05
3
UMR7272, ICN, University of Nice, 06108 Nice Cedex 2
4
PRISM, University of Lille 1, 59655 Villeneuve d’Ascq
Keywords: Mass Spectrometry, cnidarian-dinoflagellate association, metabolites, lipids
Coral reef ecosystems are renowned for their diversity and beauty. Their immense ecological success is due to
a symbiotic association between a cnidarian host, such as scleractinian corals and sea anemones, and dinoflagellates
of the genus Symbiodinium. Symbionts are hosted within the cnidarian gastrodermal cells [1], as presented in Figure
1A. The main benefit of this interaction is the translocation of photosynthetically fixed carbon (photosynthates) by
endosymbiotic dinoflagellate to their cnadiarian host, in the form of various metabolic compounds [2,3,4], schematized in Figure 1B. However, the identity of these metabolites and the mechanisms that control their exchange
across the host-symbiont interface remains underdevelopped.
To understand the molecular communication between the host and symbionts, we proposed to analyse the molecular diversity of a symbiotic sea anemone, Anemonia viridis. We therefore applied mass spectrometry tools to
determine molecules potentially exchanged between partners, and define specific patterns of the different cellular
compartments. GC-MS and LC-MS were used to characterize metabolite diversity and distribution. A focus on lipid
composition was made to investigate the lipid trafficking between host and symbiont, motivated by previous investigations highlighting the potential importance of lipid metabolism in such a molecular crosstalk [3,4,5,6]. Secondary metabolites are also under investigation, in order to identify the key signaling molecules in such interactions.
The further step will be to localize the identified compounds inside the sea anemone tissues. Mass spectrometry imaging (MSI) techniques such as Matrix-Assisted Laser Desorption Ionization Mass Spectrometry Imaging
(MALDI-MSI) or TOF-SIMS are under scrutinity to achieve in this aim. The perspective is to obtain a precise molecular imaging tool that can provide insights on both the origin and localization of key molecules in the symbiotic
interaction.
A
B
A
B
E
Sunlight
Epidermis
Epidermis
Membrane
du du
Membrane
symbiosome
symbiosome
Cnidarian gastrodermal cell
Amino acids
Mesoglea
Gastrodermis
and
Symbiodinium
Mesoglea
CO2
Glucids
M
symbiosome
Symbiosome
Symbiosome
Gastrodermis
O2
Lipids
G
S
10 10
µmµm
Secondary
metabolites
Symbiodinium
Fig. 1. Schematic representation of symbiotic cnidarian organization. A, schematic representation of a cnidarian polyp and its
tissue organization; B, schematic representation of molecular exchanges compounds between the symbiotic partners.
References
1
T. Wakefield, M. Farmer, S. Kempf, The Biological Bulletin 199 (1):76-84 (2000).
2
L. Whitehead, A. Douglas, Journal of Experimental Biology 206 (18):3149-3157N (2003)
3
M. Papina, T. Meziane, R. van Woesik, Comparative Biochemistry and Physiology, Part B 135 (3):533-537N (2003)
4
N.V. Zhukova, E.A. Titlyanov, Phytochemistry 62 (2):191-195 (2003)
5
M.A. Teece, B. Estes, E. Gelsleichter, D. Lirman, Limnology and Oceanography 56 (4):1285O (2011)
6
A.B. Imbs, I.M. Yakovleva, T.N. Dautova, L.H. Bui, P. Jones, Phytochemistry (In Press)
JFIC -GIFC,
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
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2014
7thth JFIC
P95
Innovative Polymer Gels for Cultural Heritage Applications
Chiara Riedo*, Oscar Chiantore
Department of Chemistry & NIS Nanostructured Interfaces and Surfaces Centre, Università degli Studi di Torino,
via Pietro Giuria 7- 10125 Torino, Italia
Keywords: polymer gels, cleaning, art conservation,rheology
In the field of cultural heritage hydrogels and high viscosity polymeric dispersion are used for cleaning and removal of superficial layers in artistic handiworks and for diagnostic purposes. Gels allow limitation of unwanted
effects due to direct application of solvents, as swelling and extraction of original materials. Required features are
the possibility of incorporating solvents and suitable viscoelastic properties to obtain mouldable material and complete removal after application.
A polymer chosen as gellant must be able to form a gel by itself or with addition of a crosslinker. One or more
additives can be added to obtain desired viscoelastic properties or to improve retention of cleaning solvents in the
gels. The ratio between different formulation components can be varied to modulate gel properties.
Polyvinylacohol (PVAl) in the presence of borax as crosslinker is known to form hydrogels capable of incorporating organic solvents [1,2]. To improve mechanical properties and compatibility between gel and the cosolvent,
formulations with different amounts of polyethyleneoxide (PEO) added to PVAl were investigated in this work.
Transparent gels with interesting viscoelastic properties have been obtained and it was found that the addition of
PEO increases the retention of water and organic solvents. The structure of the composite gels was investigated
with rheological test, differential scanning calorimetry and release of liquid phase evaluation, in order to find correlations with stability behaviour and the physical properties.
Cleaning test on lab specimens were also performed, showing the ability of these formulation to remove acrylic
protective from limestones.
References
1 Lin, H.-L.; Liu, W.-H.; Shen, K.-S.; T.LeonYu; Cheng, C.-H., Weak Gel Behaviour of Poly(vinyl alcohol)-Borax Aqueous Solutions. Journal of Polymer Research 10 (200) 171-179
[2] Carretti, E.; Grassi, S.; Cossalter, M.; Natali, I.; Caminati, G.; Weiss, R. G.; Baglioni, P.; Dei, L., Poly(vinyl alcohol)Borate Hydro/Cosolvent Gels: Viscoelastic Properties, Solubilizing Power, and Application to Art Conservation, Langmuir15
(2009) 8656-8662.
JFIC -GIFC,
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
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2014
7thth JFIC
P96
TiO2 nanotubes made by electrochemical anodization as negative electrode for
Li-ion 3D microbatteries
M. Riesenmey*, N. Plylahan, T. Djenizian, P. Knauth
Aix-Marseille University, CNRS, Madirel (UMR 7246), Centre St Jérôme, 13397 Marseille cedex 20, France
Keywords:Titania nanotubes; All-solid-state microbatteries; Nano-architectured electrodes; Electropolymerization.
The development of microbatteries is an important objective for powering autonomous microdevices for remote or nomadic use, including microelectromechanical systems (MEMS), microsensors and microactuators, implantable medical devices, RFIDs and many others. Two-dimensional (2D) microbatteries are generally fabricated
by a sequential deposition of thin-films, especially by sputtering. They currently show low areal capacity and energy density; increasing layer thicknesses might increase the areal capacity, but reduces the power density, due to
increased diffusion lengths. However, a three-dimensional (3D) design can significantly improve the power density,
by increasing the interfacial area between active components of the battery, while keeping the diffusion distances
short.
In this contribution, we will present the current status on the development of 3D microbatteries, based on TiO2
nanotubes made by electrochemical anodization of titanium metal films deposited on silicon substrates [1,2]. The
length, diameter and wall thickness of the nanotubes can be designed by changing the electrochemical parameters
(potential, time, electrolyte composition); the electrical properties and point defects were also analyzed [3]. The
remaining back side metal allows direct integration on microelectronic circuitry, because Ti is well known to form
TiSi2 with silicon, allowing Ohmic contacts to be formed. Various strategies for further improvement of the areal
capacity and cyclability of the nanotube electrodes were explored, such as the preparation of composite materials
with tin [4] or iron oxides [5], or the doping of the nanotubes with Fe [6] or Sn [7]. Li-ion conducting polymer electrolyte (PEO-PMMA) can be electro-deposited inside the nanotubes, forming a continuous lining [8]. Electrophoretic deposition of the positive electrode material on the polymer lining is currently explored to give a fully electrochemically fabricated 3D microbattery.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
G. Ortiz, I. Hanzu, T. Djenizian, P. Lavela, J.-L. Tirado, P. Knauth, Chem. Mater. 21 (2009) 63.
T. Djenizian, I. Hanzu, P. Knauth, J. Mater. Chem. 21 (2011) 9925.
I. Hanzu, T. Djenizian, P. Knauth, J. Phys. Chem. C, 115 (2011) 5989.
G. F. Ortiz, I. Hanzu, P. Lavela, P. Knauth, J. L. Tirado, T. Djenizian, Chem. Mater. 22 (2010) 1926.
G. F. Ortiz, I. Hanzu I, P. Lavela, J. L. Tirado, P. Knauth, T. Djenizian, J. Mater. Chem. 20 (2010) 4041.
N. A. Kyeremateng, V. Hornebecq, H. Martinez, P. Knauth, T. Djenizian, ChemPhysChem. 13 (2012) 3707.
N. A. Kyeremateng, F. Vacandio, M.-T. Sougrati, H. Martinez, J. C. Jumas, P et al., J. Power Sources. 224 (2013) 269.
N. Plylahan, N. A. Kyeremateng, M. Eyraud, F. Dumur, H. Martinez, et al., Nanoscale Research Letters. 7 (2012) 1.
JFIC -GIFC,
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
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2014
7thth JFIC
P97
Modeling of nanotubular TiO2 for 3D microbatteries
M. Riesenmey*1,2, Marielle Eyraud 1, Philippe Knauth1, Thierry Djenizian 1,
Alan Chadwick2, Maria Alfredsson2
1
Aix-Marseille University, CNRS, Madirel (UMR 7246), Centre St Jérôme, 13397 Marseille cedex 20, France
2
School of Physical Sciences, University of Kent, Canterbury, Kent CT2 7NH, United Kingdom
Keywords: Ab Initio calculations; Electronic properties; Titania nanotubes; Li-ion microbatteries.
The miniaturization of portable devices requires the development of power sources at the micrometer scale,
which is a huge potential market. Due to their high energy density, Li-ion microbatteries are very promising devices
to power small electronic equipments, such as microsensors, smartcards or medical implants. However, the low
energy per unit area and the lifetime of actual microbatteries, based on the two dimensional (2D) thin film technology, are holding back the development of the latter applications. One approach to increase the capacity of microbatteries is to change the configuration from 2D to three dimensional (3D) nano-architectured electrodes. Titania can
self-organize into nanotubes (nt-TiO2) by a template-free, simple anodization process [1] leading to an increase of
the microbatteries capacities by 65% [2].
However, the fundamental processes involved in nt-TiO2 as anode are still poorly understood; further improvements require a deeper understanding of both the chemical and structural changes occurring in this electrode.
Although the lithium intercalation mechanisms in the different titanates have been widely studied using different
modeling methods [3], no study concerning nt-TiO2 has been reported to our knowledge. Ab initio calculations on
nt-TiO2 were carried out using Crystal09 [4] by wrapping a 2D slab of a given thickness and crystalline structure.
The three monolayer (3 ML) thick [001] anatase nt-TiO2 model is the only structure showing a negative strain energy in the whole diameter range [5], indicating a higher stability of the nanotube compared to a 3 ML surface. As a
result, this model, providing information on the electronic structure of the atoms, is very promising to acquire a
better understanding of nt-TiO2 as negative electrode for 3D Li-ion microbatteries and hence to optimize their performances.
References
[1] G.F. Ortiz, I. Hanzu, T. Djenizian, P. Lavela, J.L. Tirado, P. Knauth, Chem. Mater. 21 (2009) 63.
[2]
I. Hanzu, T. Djenizian, P. Knauth, J. Mater. Chem. 21 (2011) 9925.
[3]
M.V. Koudriachova, J. Solid State Electrochem. 14 (2010) 549.
[4] R. Dovesi, V. R. Saunders, C. Roetti, R. Orlando et al., CRYSTAL09, (2009) CRYSTAL09 User's Manual, University of
….. Torino, Torino.
[5]
A. M. Ferrari, D. Szieberth, C.M Zicovich-Wilson, R. Demichelis, J. Phys. Chem. Lett. 1 (2010) 2854.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
P98
Enabling technologies for cyclodextrins complexation, funtionalization and material grafting.
L. Rinaldi1, M. Caporaso2, M. Calcio Gaudino2, G. Cravotto*,2
1
Dipartimento di Biotecnologie Molecolari e Scienze per la Salute, University of Turin, Via Nizza 52, 10126, Torino, Italy
2
Dipartimento di Scienza e Tecnologia del Farmaco, University of Turin, via P. Giuria 9, 10125, Torino, Italy
E-mail: [email protected]
Keywords: Microwaves, Ultrasound, Ball-Mill, Cyclodextrins.
Synthetic chemists are increasingly paying attention to combinations of enabling technologies with an eye to
achieving the double goal of obtaining high efficiency and meeting the green criteria of energy savings and the
absence of dangerous or harsh reagents. Microwave (MW) [1,2], power ultrasound (US) [3], hydrodynamic cavitation [4] ball milling [5] and hybrid flow-reactors [6] are a valid and versatile alternative for process intensification
in organic synthesis [7]. We exploited MW and US for the synthesis of cyclodextrin (CDs) derivatives which can
be applied in many different fields due to their unique features [8]. The use of new MW reactor with high power
(up to 1.5 kW) pressure resistant (up to 200 bar) equipped with separate multiple gas inlets, allowed us the use of a
wider range of low-boiling reagents such as allylamine, butylamine and allylamine and butylamine [9]. We also
experimented MWs as powerful energy source to graft nanomaterials [10] and fabrics [11] with suitable CD derivatives. Simultaneous MW/US irradiation was used for the mono-functionalization of the 6-monoazido--CDs catalyzed by metallic copper [12]. Thank to this procedure new cyanine--CD derivatives have been synthesized to be
used like “turn on” or “turn off” fluorescent chemical sensors, in which fluorescence intensity is enhanced or decreased by complexation with guest molecules. Ball-milling technique was employed for the formation of CD inclusion complexes to improve the solubility and bioavailability of poorly water-soluble molecules of synthetic and
pharmaceutical interest. Figure 1 shows the main reactors used for all these applications.
Fig. 1. From left: MW reactor SynthWave (Milestone S.r.l., MLS GmbH); US/MW system professional MW oven (Milestone
MicroSYNTH) with the Pyrex horn; Planetary ball mill PM100 (Retsch GmbH).
References
1
Microwaves in Organic Synthesis, 3rd Edition (2012), Springer Science, New York, USA.
[2]
Microwave-assisted extraction for bioactive compounds: Theory and practice. (2013), Springer Science, New York, USA.
[3]
G. Cravotto, P. Cintas, Chem. Soc. Rev. 35 (2006) 180.
[4]
D. Bremner, S. Di Carlo, A.G. Chakinala, G. Cravotto, Ultrason. Sonochem. 15 (2008) 416.
[5]
G. Cravotto, D. Garella, D. Carnaroglio, E. Calcio Gaudino, O. Rosati, Chem. Commun. 48 (2012) 11632.
[6]
G. Cravotto, W. Bonrath, S. Tagliapietra, C. Speranza, E. Calcio Gaudino, A. Barge, Chem. Eng. Process. 49 (2010) 930.
[7]
P. Cintas, D. Carnaroglio, L. Rinaldi, G. Cravotto, Chem. Today 30 (2012) 58.
[8]
F. Trotta, K. Martina, B. Robaldo, A. Barge, G. Cravotto, J. Incl. Phenom. Macrocycl. Chem. 57 (2007) 3.
[9]
K. Martina, G. Cravotto, M. Caporaso, L. Rinaldi, C. Villalonga-Barber, G. Ermondi, Org. Biomol. Chem. 11 (2013) 5521.
[10] S. Tagliapietra, G. Cravotto, E. Calcio Gaudino, S. Visentin, V. Mussi, Synlett 23 (2012) 1459.
[11] L. Beltramo,S. Sapino, A. Binello, E. Carlotti, G. Cravotto, J. Mat. Sci. 22 (2011) 2387.
[12] P. Cintas, A. Barge, T. Tagliapietra, L. Boffa, G. Cravotto, Nature Protocol, 5 (2010) 607.
P99
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Turin, Italy,
Italy, May
May 55thth-6
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2014
7thth JFIC -GIFC,
Is the term “heat” clear and precise for everybody?
J.Rouquerol*, F.Rouquerol
1
Aix Marseille Université-CNRS, MADIREL Laboratory, Centre de St Jérôme, 13397 Marseille Cedex 20
Keywords: heat, heat storage, heat transfer, thermal radiation
This presentation deals with one of the basic quantities measured in thermodynamics – namely heat - in view
of determining the state functions (energy, enthalpy, entropy, Gibbs energy) which are so useful to predict, control
and improve any chemical reaction. The meaning of the term « heat » looks clear to most scientists. In reality, we
use to be satisfied with the definition we learned as students and which we have no reason to object. The trouble is
that several, inconsistent, definitions are used among physicists, chemists, thermodynamicists, leading to an unsuspected source of confusion and misunderstanding. It is this inconsistency which we wish to illustrate and adress
here.
On the one hand, many physicists are considering to-day (in-line, it looks, with Prigogine and Defay1), that the
energy transfer by radiation is not a heat transfer : they only include in the term « heat » the propagation of disordered vibrational energy by direct contact between the atoms or molecules, i.e. the thermal transfer by conduction
and convection.
On the other hand, many thermodynamicists and thermal engineers use the term « heat » with a broader meaning which includes the thermal transfer by radiation.
Finally, a number of calorimetrists, especially those using adiabatic or quasi-adiabatic calorimeters, like to
consider that heat cannot only be transferred but that it can also be stored and measured in their calorimeters.
We can stress that the main reason for the above uncertainty in the definition of « heat » is not any more an insufficient knowledge of the thermal phenomena, since they are now well understood both at the macroscopic and
microscopîc levels. The origin of the problem is simply that the question « What physical quantity do we exactly
wish to embrace in the term « heat » ? », which is a simple matter of convention, does not seem to have received,
yet, a generally agreed answer. This ambiguity explains that the term « heat » was completely expelled from a few
teaching programs in France, in spite of its broad use in the language. Is it the only possible answer ? In agreement
with a IUPAC recommendation2 (which was not addressing this issue proper, but which is helpful in this instance)
we end with a practical proposal.
References
1 I.Prigogine, R.Defay in “Thermodynamique Chimique”, Gauthier-Villars, Paris (1944) 26
2 M.Terazima, N. Hirota, S.E. Braslavsky, A. Mandelis, S.E. Bialkowski, G.J. Diebolds, R.J.D. Miller, D. Fournier, R.A.
Palmer, A. Tam, Pure Appl. Chem., Vol 76, N°6 (2004) 1083
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
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2014
7thth JFIC -GIFC,
P100
Ecofriendly microwave-mediated synthesis of organogelators from renewable
sources for cosmetic and pharmaceutical applications
Villa Carla*, Rum Silvia, Lacapra Chiara
Dipartimento di Farmacia - Sezione di Chimica del Farmaco e del Prodotto Cosmetico
Viale Benedetto XV, 3 - 16132 Genova
Keywords: Microwaves, Solvent-free synthesis, Organogelators, Renewable sources, Green Chemistry
Organogel are semi-solid systems in which an organic liquid phase is immobilised by a three dimensional
network composed of self-assembled, intertwined, organgelator fibers.
There are many applications for organogels in the food, pharmaceutical and cosmetic industries and as a result, there is an increasing interest for these soft materials.
Taking into account that organogelators are often prepared by multistep procedures, using environmentalunfriendly reagents and solvents, the aim of our research, following the Green Chemistry principles. is the development of an alternative solvent-free procedure, under microwave irradiation (MW) as an alternative energetic
source, to obtain organogelators from renewable sources.
The coupling of microwave technology with solvent-free conditions represents a new and particularly efficient, powerful and attractive synthetic pathway. Significant improvements in yields and reaction conditions can be
achieved, together with considerable simplification of work-up and low environmental impact.
In particular in this work we have studied the synthesis of sorbitol derivatives, such as 1,3:2,4-Dibenzylidene
sorbitol (DBS), which are able to lead to the formation of a gelling networks in the presence of a lipophilic solvent,
at very low concentrations. Their conventional synthesis suffer from long reaction times, use of hazardous solvents,
complex procedures and low yields [1-3]. In this work, we propose a rapid microwave assisted synthetic procedure
in dry media, using a simple mixture of reagents in the presence of an acidic catalyst[4]. The target compounds
were obtained in good yield (up to 90%) in less than ten minutes. Several experiments were carried out to study
advantages and limits of the selected methodology; in order to highlight the advantages of microwave activation,
the reactions were performed at the same conditions but in a thermostated oil bath and results compared.
Microwave irradiation was carried out using a scientific monomode reactor. Methods and results will be reported.
References
1 Hunping Xie, Jiang Li, Jusong Xia US patent 2006/0079720,
2 Joseph M. Salley, Walter A. Scrivens US patent 5,731,474.
3 Hiroshi Uchiyama US patent 4,267,110.
[4] M.T Genta.C., Villa et al. International Journal of Pharmaceutics , 231/1, (2002) 11.
Italy, May
May 55thth-6
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2014
7 th JFIC -GIFC, Turin, Italy,
P101
On the adsorption of hydrocarbons on Micro and Mesoporous high Silica
Materials: a combined experimental and computational study
C. Bisio1, V. Sacchetto1*, M. Cossi1, G. Gatti1, G. Paul1, L. Marchese1, I. Braschi1,2,
G. Berlier3
1
Dipartimento di Scienze e Innovazione Tecnologica and Centro Nano-SiSTeMI, Università del Piemonte Orientale,
Alessandria, Italy; 2Dipartimento di Scienze Agrarie, Università di Bologna, Bologna, Italy; 3Dipartimento di Chimica and
NIS Centre of Excellence, Università di Torino, Italy
Keywords: adsorption, pollutant, zeolite, mesoporous silica, DFT calculations
Fuel-based compounds are organic pollutants generally coming from industrial waste and are usually present in
water and soil from areas where oil refineries and gas stations are situated. Among all contaminants that can pollute
waters, methyl tertiary butyl ether (MtBE), toluene and n-hexane were selected as model molecules representative
of the most common classes of pollutants. The use of sorbent materials as micro and mesoporous silicas to adsorb
these contaminants from polluted areas is receiving increasing attention [1]. The sorption capacity of silicas, with
different nature and number of surface OH sites and pore size architecture, were studied. High silica ZSM-5
(SiO2/Al2O3= 280), mordenite (MOR) and Y zeolites (both with a SiO 2/Al2O3 ratio of 200) [2, 3] were indeed chosen for their different physico-chemical properties. Their sorption properties were compared with those of mesoporous MCM-41 and MSA silicas. The interactions of MTBE, toluene, and n-hexane on the three dealuminated zeolites and MCM-41 and MSA silicas were studied by means of both experimental and computational approaches.
FTIR and SS-NMR spectroscopy were used to elucidate the host/guest interactions between surface of sorbents and
model molecules. H-bonding and van der Waals interactions occurring between the surface of solids and molecules
were modeled by DFT calculations (Fig.1). Gravimetric analysis allowed to quantify the different sorption capacities of the micro and mesoporous silicas. In addition, binary mixtures of the model pollutants were adsorbed to
study the relative affinity and interactions of each molecule with the sorbent phase. The adsorption of contaminants
- as single pollutants or in a binary mixtures - on the three zeolites was not appreciably reduced when it was conducted in the presence of water sorbed onto zeolites, thus suggesting reasonable performances under wet working
conditions. On the contrary, water affects the structure and surface adsorption sites of MCM-41 by lowering the
retention capacity of the three fuel-based pollutants. The sorbent was hence modified by grafting with hexamethyldisilazane to enhance the hydrophobicity of the silica surface and to increase both the hydrothermal stability and the
adsorption of hydrocarbons.
Figure 1. FTIR spectroscopy of MTBE adsorbed on MOR and a DFT model of MTBE in the zeolite channel
References
[1]
R.S. Bowman, Micropor. Mesopor. Mater., 61, (2003) 43.
[2]
I. Braschi, G. Gatti, C. Bisio, G. Berlier, V. Sacchetto, M. Cossi, L. Marchese J. Phys. Chem. C., 116, (2012) 6943.
[3]
V. Sacchetto, G. Gatti, G. Paul, I. Braschi, G. Berlier, M. Cossi, L. Marchese, R. Bagatin, C. Bisio, Phys.Chem. Chem.
Phys., 15, (2013) 13275.
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
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2014
7thth JFIC -GIFC,
P102
Improvement of Aza-Heterocycles Synthesis by Microwave Irradiation
D. Saccone, G. Volpi, S. Ellena, R. Buscaino
Department of Chemistry, University of Torino, NIS Centre of Excellence
via P. Giuria 7, Torino 10125, Italy
(*) Davide Saccone: [email protected]
Keywords: microwave, aza-heterocycles, arylimidazo[1,5-a]pyridine, indolenine, terpyridine.
DSSC, OLED and artificial photosynthesis have grown interest in last years. Development of organic compounds for these applications have to be fastest as possible. One way to reduce times in organic synthesis is microwave irradiation. Microwaves heat reactants much more quickly than conventional means, so syntheses that usually
take hours can be done in just a few minutes. Microwave-enhanced chemistry is based on the efficient heating of
materials by “microwave dielectric heating” effects. This phenomenon is dependent on the ability of a specific material (solvent or reagent) to absorb microwave energy and convert it into heat1. The very efficient internal heat
transfer results in minimized wall effects (no hot vessel surface) which may lead to the observation of so-called
specific microwave effects.
A comparison of conventional heating and microwave irradiation in the synthesis of different aza-heterocycles
is discussed. As previously demonstrate by Hill et al. for the synthesis of pyrimidine, benzopyrimidine and
thieno[3,2-b]pyridine, microwave irradiation was found to increase the yields of the desired products and shorten
the reaction times.2 Same results were also achieved for the synthesis of arylimidazo[1,5-a]pyridine, indolenine and
terpyridine simply applying the microwave use to same procedure of the literature3-5 as described in figure 1. Arylimidazo[1,5-a]pyridine and terpyridine can be used for the formation of complexes that emit or absorb light, while
indolenine is widely used in the synthesis of squaraines, dyes able to absorb the spectrum in the near infrared. So
getting these products faster allows rapid development of products designed to search fields in continuous and constant evolution as DSSC, OLED and artificial photosynthesis.
O
Ar
O
AcOH
AcONH4
Ar
Ar'
N
Br
AcOH glacial
N
H
N
NH
NH2
Ar'
1
Cl
OO
N
Cl
AcONH4
N
OH
Cl
H
N
N
Cl
Cl
N
N
EtOH
O
N
O
2
Cl
N
Br
N
O
3
Fig. 1. Synthesis by microwave irradiation of (1) arylimidazo[1,5-a]pyridine, (2) indolenine and (3) terpyridine.
References
[1] C. O. Kappe, Angewandte Chemie-International Edition. 43 (2004) 6250-6284.
[2] M. D. Hill, M. Movassaghi, Tetrahedron Letters 49 (2008) 4286–4288.
[3] G. Volpi, C. Garino, L. Salassa, J. Fiedler, K. I. Hardcastle, R. Gobetto, C. Nervi, Chemistry a European Journal 15, 2009,
6415.
[4] M.V.Reddington, Bioconjugate Chem., 18, No. 6,(2007), 2178–2190.
[5] T. Wieprecht et al., Journal of Molecular Catalysis A: Chemical. 203 (2003) 113–128.
P103
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
4-Hydroxy-1H-1,2,3-Triazol-5-yl moiety as bioisoster of carboxylic group.
Synthesis and pharmacological ionotropic glutamate receptors characterization of
Glu analogues
S. Sainas,*1, A. Federico,1 C. Bertolotti,1 B. Nielsen,2 D. Boschi,1 B. Frølund 2 and M. L.
Lolli 1
1
2
PHARMA - Department of Drug Design and Pharmacology, The Faculty of Health and Medical Sciences, University of
Copenhagen, Universitetsparken 2, DK-2100 Copenhagen, Denmark.
Keywords: Glutamate, AMPA, 4(5)-Hydroxy-1,2,3-Triazole, Glu analogues
(S)-Glutamate ((S)-Glu) plays a major role in the transmission of excitatory signals in the central nervous system
(CNS) and is implicated in epilepsy, pain, memory, excitotoxicity, and brain development. 1 Bioisosteric
replacement is a widely used strategy in Medicinal Chemistry for the rational design of new drugs.2 Previous
structure-activity relationships studies of the ionotropic glutamate receptors (iGluRs), using the 3hydroxyisoxazolyl moiety as a bioisostere to the carboxyl group of (S)-Glu, have shown the presence of a
hydrophobic pockets near the (S)-Glu binding site.3 At MEDSynth the acidic 4-hydroxytriazol scaffold is currently
under investigation in order to find bioisosteric applications for the carboxylic group4. In this work, the bioisoteric
replacement of the distal glutamate carboxylic group using this moiety is firstly presented. The hydroxytriazole
system, because the easily introduction of lipophilic substituent on the ring, should represent a valuable tool for the
investigation of the Glu receptor hydrophobic pockets. The synthesis and pharmacological properties of
enantiomerically pure triazole Glu analogues 3-Me-TRPA and 2-Me-TRPA are reported and discussed in terms of
the structural knowledge available for the Glu receptor.
Glu
AMPA
3-Me-TRPA
1-Me-TRPA
2-Me-TRPA
Fig. 1. Glu analogues
References
1
L. Juknaitė; . Sugamata; K. Tokiwa; . Ishikawa; S. Takamizawa; A. Eng; R. Sakai; D. S. Pickering; K. Frydenvang; G.
T. Swanson; J. S. Kastrup; M. Oikawa. Studies on an (S)‑2-Amino-3-(3-hydroxy-5-methyl-4-isoxazolyl)propionic Acid
(AMPA) Receptor Antagonist IKM-159:Asymmetric Synthesis, Neuroactivity, and Structural Characterization. Journal of
Medicinal Chemistry 2013, 56, 2283–2293.
2
N. A. Meanwell. Synopsis of some recent tactical application of bioisosteres in drug design. Journal of medicinal
chemistry 2011, 54, 2529-91.
3 S. B. Vogensen; K. Frydenvang; J. R. Greenwood; G. Postorino; B. Nielsen; D. S. Pickering; B. Ebert; U. Bølcho; J.
Egebjerg; M. Gajhede; J. S. Kastrup; T. N. Johansen; R. P. Clausen; and P. Krogsgaard-Larsen. Journal of Medicinal
Chemistry 2007, 50, 2408–2414.
4
A. Federico; S.Sainas; A. Ducime; K. Martina; F. Bosca; D.Boschi; M.L.Lolli. Synthesis and Structural Characterization
of Regio Substituted Hydroxytriazols as Possible Tool in Bioisosteric Applications. 7th JFIC -GIFC, Turin, 2014, Poster.
P104
JFIC -GIFC,
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC
Reactivity of oxide catalysts in the heterogeneous synthesis of amides
Y. Sakhno1*, P. Ivanchenko1, C. Deiana1, A.F. Lombardo2, G. Trunfio2, F. Arena2,
G. Martra1
1
University of Torino, Department of Chemistry and Interdepartmental Centre “Nanostructured Interfaces and Surfaces – NIS”
via P. Giuria 7, 10125 Torino,Italy
2
University of Messina, Department of Electronic Engineering, Viale F. Stagno D’Alcontres 31,98166 Messina, Italy
Keywords: Oxide catalysts; amides synthesis; reaction kinetics; surface functionality;IR spectroscopy of adsorbed reactants
The formation of amide bonds is among the most important reactions in organic chemistry [1], but usual synthetic pathways are affected by an overconsumtion of chemicals for the activation of carboxylic groups. Catalyzed
reactions are quite attractive as alternative methods, and compelling studies of amidation reactions promoted by
heterogeneous catalysts started to appear [2]. In this respect, insights on the amidation recation mechanism on TiO2
P25 in solvent free conditions have been recently elcucidated by some of us [2]. Herein we extended the study to
other oxide catalysts, TiO2 Merck, -Al2O3 ZrO2, CeO2, pairing catalytic and kinetic studies (propionic acid and
anyline in toluene) with in situ IR spectroscopy of adsorbed formic acid and 1-pentanamine as model reactants.
Catalytic tests and related kinetic data analysis allowed to establish that i) the reaction exhibits 0th-order
kinetic dependence, indicating the occurrence of a L-H reaction path involving strong adsorption phenomena on
neighboring acid-base Lewis pairs (i.e., active sites), and ii) the apparent specific 0th-order constants (i.e. constant
per weight and specific surface area units of catalysts, kw,SSA) can be ordered in the following series (Fig. 1.A):
kw,SSA TiO2 P25 > kw,SSA ZrO2, TiO2 Merck, CeO2 >> kw,SSA Al2O3
This trend appered related to the relative amount of different carboxylate species formed on the surface of
catalysts, as resulted from the solvent-free IR study of model reactants adsorbed from the vapor phase (Fig. 1. B).
The interaction of HCOOH with catalysts resulted in the formation of formates giving rise to asymCOO- and
symCOO- bands in the 1600-1500 and 1400-1300 cm-1 ranges, respectively (blue curves). The subsequent admission of 1-pentanamine resulted in a strong decrease of the components due to formate species and the appearance of
signals in the 1700-1600 cm-1 range due to the C=O mode of amide species (grey curves). The extent of such
transformation decreased passing from TiO2 P25 to ZrO2, TiO2 Merck and CeO2, while amidation essentially did
not occur in the case of Al2O3. Thus, the behavior pattern coming from IR measurements, matched the trend in
catalytic activity.
The calculation of the splitting between asymCOO- and symCOO- bands, which is sensitive to the structure
of carboxylates [3], revealed that the higher reactivity exhibited by TiO 2 P25 likely resulted from the formation of
larger amount of bidentate carboxylates with respect to bridging and unidentate ones, which, conversely, are the
more abundant species on ZrO2, TiO2 Merck and CeO2, and essentially the only ones present on Al2O3.
The elucidation of this structure-reactivity relationship can be useful for a knowledge-based selection/design
oxide catalysts with optimized performances in catalytic amidation.
Fig. 1. B: IR spectra (after
Fig. 1. A: Trend of the specific surface kinetic constant
of amide production (kSA) for the various catalysts (propionic acid, anyline; toluene; T = 383K).
subtraction of the materials
background) in the range of
1750-1250 cm-1 of TiO2 P25,
ZrO2, TiO2 Merck, CeO2, and
-Al2O3 catalysts contacted
with HCOOH and subsequently outgassed at r.t. (blue lines:
a-e, in the order); and after
subsequent admission of 1pentanamine (grey lines: a’-e’,
in the order).
References
1 V. Pattabiraman, J. Bode Nature, 2011, 480, p. 471–479.
2 C. Deiana, Y. Sakhno, M. Fabbiani, M. Pazzi, M. Vincenti G. Martra, ChemCatChem., 2013, 5, 2832 and reference therein
[3] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, Wiley, New York, 4th edition 1986,
p. 232 –233.
P105
Italy, May
May 55thth-6
-6thth,, 2014
2014
7th JFIC -GIFC, Turin, Italy,
Synthesis and photocatalytic activity of sulfur doped TiO2
E. Sanguineti1*, V. Caratto1,2, M. Provasi1,2, M. Ferretti1
1
2
Department of Chemistry and Industrial Chemistry, University of Genova, Genoa, Italy
Department of Earth, Environmental and Life Science, University of Genova, Genoa, Italy
[email protected]
Keywords: S-doped titanium dioxide, solgel synthesis, photocatalysis, methylene blue
The electrons and holes photogenerated in the TiO2 photocatalyst have strong reduction and oxidation power,
leading to the production of strong oxidizing agents applicable for many purposes, such as chemical and microbial
air and water treatments [1]. However, photocatalytic efficiency of TiO2 is often low, due to band gap value and
charge recombination. Thus development of new materials based on TiO 2 that show increased photoresponse and
photocatalytic performance remain research targets [2].
In this work, synthesis of sulfur doped TiO 2 prepared by solgel synthesis via hydrolysis of tetraisopropoxide
(TTIP), and photocatalytic activity of the obtained powders for degradation of methylene blue (MB) under UVA
light (40W) were investigated.
Synthesized S-doped TiO2 nanopowders were characterized by SEM, XRD, UV–vis and Raman spectroscopy
analysis. The S-doping caused the decrease of the energy gap in comparison of pure synthetized anatase TiO2 (3.24
eV) [3]; the Eg of the 3% and 10% H2SO4-doped TiO2 was reduced to 3.19 eV and 3.15 eV, respectively.
Undoped synthetized TiO2 crystalized in anatase structure after calcination at 350°C for 1 h, while S-doped
samples resulted amorphous; anatase phase was detected in XRD pattern for these powders when calcinated at
350°C for 2 h. SEM analysis showed that the presence of sulfur changes the morphology of the powders: undoped
anatase had grains or grains-aggregate of spherical shape, while the doped ones were more squared.
Among the different S-TiO2 concentrations tested in 10 mg L-1 MB solution, the 2 g L-1 exhibited the highest
photocatalytic activity; after 30 min irradiation, the degradation rate of MB reached approximately the 48% and
72% for 3% and 10% S-doping, respectively. In the case of 0.25 g L-1 catalyst loading similar results were achieved
after 120 min irradiation (Fig.1).
0.25 g L¯¹ S-TiO₂ (10%)
0.25 g L¯¹ S-TiO₂ (3%)
0.5 g L¯¹ S-TiO₂ (10%)
0.5 g L¯¹ S-TiO₂ (3%)
1 g L¯¹ S-TiO₂ (10%)
1 g L¯¹ S-TiO₂ (3%)
2 g L¯¹ S-TiO₂ (10%)
2 g L¯¹ S-TiO₂ (3%)
MB degradation (%)
100
80
60
40
20
0
0
30
60
90
120
150
180
210
240
270
Irradiation time (min)
Fig. 1. MB degradation rate versus time for different catalyst loadings and doping percentage at 10 ppm dye concentration.
References
[1]
[2]
3
A. Fujishima, T. N. Rao, D. A. Tryk, J. Photochem. Photobiol. C/Photochem Rev 1 (2000) 1–21.
K. Nakata, T. Ochiai, T. Murakami, A. Fujishima, Electrochim Acta 84 (2012) 103-111.
V. Caratto, L. Setti, S. Campodonico, M.M. Carnasciali, R. Botter, M. Ferretti, J Sol-Gel Sci Technol 63 (2012) 16-22.
Acknowledge
This work was funded by Regione Liguria under PO CRO FSE 2007/13.
Italy, May
May 55thth-6
-6thth,, 2014
2014
P106
Use of a gold nanostructured electrode for the electrochemical
determination of Hg. Optimisation, characterization and evaluation of its
applicability for fish products-analysis
A.Giacomino1*, G.F. Schirinzi2, M.Malandrino2, O. Abollino2,
1
University of Torino, Department of Drug Science and Technology, Via Giuria 9, 10125 Torino, Italy
2
University of TorinoDepartment of Chemistry, Via Giuria 5, 10125 Torino, Italy
Keywords: Mercury, gold nanoparticles, gold salts, electrode surface, fish-products.
Mercury is a metal with interesting properties and it is widely used in various sectors as industry, medicine and
science. However, it has been extensively studied for its high toxicity. Each species of this metal (elemental, organic and inorganic mercury) is responsible for significant human health problems and environmental pollution, even
at low concentration. Therefore, it is important to develop sensitive analytical methods for its determination.
Good results are obtained with electrochemical methods, primarily using anodic stripping voltammetry (ASV),
with various working electrodes. Gold is an excellent material for Hg determination since it exhibits a high affinity
for Hg, thereby improving the effects of pre-concentration before stripping.
Metal nanoparticles can be exploited in electroanalysis for their ability to catalyze the redox processes, since
they facilitate the electron transfer; moreover, the large surface area of the deposited nanoparticles could permit an
improvement of the analytical performance.
This study focuses on the determination of Hg by ASV using a home-made gold nanoparticle-modified glassy
carbon electrode (AuNPs-GCE). The performance of this electrode and of the technique have been show in previous works [1]. The aim of this work is to continue the evaluation of the possible fields of applicability of the optimized technique: in this case “fish-based products” (fish, fish oil, dietary supplements containing fish oil,..)
Modification with gold nanoparticles was performed by dipping the electrode into a 50 mg/l or 100 mg/l
HAuCl4 3H2O solution and applying a potential of 0.80 V for 6 min. In this study the use of two different gold salts
for the deposition was compared: the salts present different level of purity declared by the producer: ≥49,0% (used
in the previous studies) and ≥99,9%.
Repeatability, linearity and detection limit were evaluated for the different AuNPs-GCEs obtained by changing
gold salt and the concentration of the gold solution adopted for the deposition. Better results are obtained using
50mg/l gold solution for both salts. Using HAuCl4 ∙3H2O with purity ≥99,9 % we observed a greater sensitivity of
the determination in comparison with that obtained using the other salt.
However, conflicting results obtained during mercury determination drove us to characterize the gold salts and
the quality of the final gold layer. Gold salts were characterized by pH measures, ICP-MS and ICP-OES quantitative-qualitative analysis. No relevant differences between both salts were observed, even if their appearance at the
solid state was different..
Cyclic voltammetry (CV) has been applied to monitor gold surface [2]. This study is used to value both the
presence of gold nanoparticles (strictly related to an anodic peak in the graph) and the amount of deposited gold
(related to a cathodic peak) on electrode surface. We observed a partial dissolution of the active layer and modifications of its physical structure over time.
Then, the gold surfaces were characterized by scanning electron microscopy (SEM). SEM images show many
surface irregularities of the carbon electrode surface and the presence of a gold film instead of gold nanoparticles.
The use of a glassy carbon working electrode with a more homogeneous surface (verified by SEM) permitted us to
obtain a gold nanoparticle layer showing the influence of the carbon surface morphology on the formation of gold
nanoparticles.
We valued the performance of the previously optimized technique for the determination of Hg in synthetic solutions, then in the sample ISPRA T220 “tuna fish”[3]. Finally, we valued the possibility to apply the method for
the analysis of real sample.
1] O. Abollino, A. Giacomino, M. Malandrino, G. Piscionieri, E. Mentasti, Electroanalysis 20, (2008).
[2] E. Bernaltea, C. Marín-Sánchez, E. Pinilla-Gil, C.M.A. Brett Journal of Electroanalytical Chemistry 709 (2013).
[3] A. Detcheva 1, K.H. Grobecker Spectrochimica Acta Part B 61 (2006).
Italy, May
May 55thth-6
-6thth,, 2014
2014
P107
In situ and in operando characterization of zeolite-based catalysts by means of
Raman spectroscopy
Matteo Signorile1*, Francesca Bonino1, Alessandro Damin1, Karl Petter Lillerud2, Silvia Bordiga1
1
2
Department of Chemistry, NIS - INSTM Reference Center, University of Turin, Via G. Quarello 15 I-10135 Torino, Italy
inGAP Center of Research Based Innovation, Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, 0315
Oslo, Norway
Raman,UV-Raman, Zeolites, In situ, In operando
Zeolites are three-dimensional microporous alumino-silicates, crystalline, with a well defined shape and size of
cavities. Due to the presence of Al3+ ions (with lower positive charge comparing with Si4+), some positive charged
counterions (H+, alkali / transition metal ions,...) are present in extraframework positions. Each type of counterion
gives different chemical properties to the framework, such as acidity with H + or redox properties with transition
metal ions. According to their structure and chemical properties, zeolites find application in several technological
fields, such as catalysis (e.g. MTH [1, 2], selective oxidation [3, 4],…). Raman spectroscopy is considered as a
powerful tool in order to understand the vibrational and
structural properties of zeolites. Comparing with FTIR
spectroscopy, Raman is much more sensitive to the low
frequency framework vibrational modes, has very low
sensitivity to atmospheric molecules (N2, O2, CO2) and
to water, can exploit the resonance effect and, working
in backscattering, allows to analyze also highly absorbing materials. Nevertheless, if the sample contains fluorophore species they will emit a strong fluorescence radiation when excited by the laser, “burying” the Raman
signal; moreover light sensitive samples can be damaged
by the laser, especially when a short excitation wavelength is used. Dealing with zeolites, the problem of fluoFig. 1. Raman spectra (λ=442nm) of a-Y, after different
rescence is extremely relevant, as these materials have a
treatments.
large surface area with exposed active sites, so that they
can contain a moiety of adsorbed fluorescent species. In order to avoid the fluorescence, we have characterized a
series of zeolitic samples using an excitation line falling out of the visible region where typically the fluorescence
phenomenon occurs [5]: a dedicated instrument equipped with a frequency doubled Ar + laser (emitting at λ=244nm)
was used. The choice of a UV excitation laser introduces a new problem: as the UV photons carry a considerable
amount of energy, the photo-induced damaging of the sample is highly probable with organic and photosensitive
materials. In some previous experiments [2], the capability to preserve the sample under UV irradiation by moving
it has been demonstrated. Our aim was to realize a new instrumental setup devoted to keep the samples under
movement during the measurement and to apply it to the fundamental study of zeolites. A systematic study on a
series of commercial and newly synthesized samples has been performed. Measurements have been carried out
under controlled conditions (e.g. in situ), involving the adsorption of probe molecules or the characterization of
trapped products of a reaction, wanting to elucidate the molecule-zeolite interaction. Moreover the same samples
have been characterized under reaction conditions, i.e.in operando. Because of this, we have optimized our measurement setup to allow fast measurements (i.e. short collections with high laser power) and in flow treatments.
References
[1]
[2]
[3]
[4]
[5]
U. Olsbye, S. Svelle, M. Bjørgen, P. Beato, T.V.W. Janssens, F. Joensen, S. Bordiga, K.P. Lillerud, Angew. Chem. Int.
Ed. 51 (24) 2012.
P. Beato, E. Schachtl, K. Barbera, F. Bonino, S. Bordiga, Catal. Today. 205 2013.
S. Bordiga, A. Damin, F. Bonino, G. Ricchiardi, C. Lamberti, A. Zecchina, Angew. Chem. Int. Ed. 41 (24) 2002.
F. Bonino, A. Damin, A. Piovano, C. Lamberti, S. Bordiga, A. Zecchina, ChemCatChem. 3 (1) 2011.
F. Fan, Z. Feng, C. Li, Accounts Chem. Res. 43 (3) 2010.
P108
Italy, May
May 55thth-6
-6thth,, 2014
2014
Gas-phase Lithium Cation Basicity: revisiting the high basicity range
by experiment and theory
C. Mayeux1, L. Sikk1,2, J-F. Gal*,2, P. Burk1,I. Kaljurand1, I. Koppel1, I. Leito1
2
1
University of Tartu, Institute of Chemistry, Ravila 14a, 50311, Tartu, Estonia
Institut de Chimie de Nice (UMR CNRS 7272), Université Nice Sophia Antipolis, 06108, Nice, France
Keywords: FTICR, lithium, basicity
The fundamental aspects of Li+ binding to organic molecules are relevant to many technological applications
ranging from lithium batteries to organic synthesis. Like proton, Li cation has an empty s-orbital for bonding with
Lewis bases, but the bonding of Li+ to organic ligands is much weaker, mainly attributed to the repulsion of ligand
electrons with the 1s2 electrons of Li cation. Therefore the Li+-ligand bond is less covalent than the H+-ligand bond
[1].
A thermodynamic measure of the interaction between a molecule L and the Li cation in the gas phase is the
lithium cation basicity (LiCB), which corresponds to the negative Gibbs energy change of the reaction
Li+(g) + L(g)  [LLi]+(g)
The upper part of the previous lithium cation basicity scale,[2] established by Fourier transform ion cyclotron
resonance mass spectrometry (FTICR-MS) equilibria at 373K, appeared to be biased by a systematic shift. Our
intention was to understand the source of this discrepancy between theoretical and previously published experimental LiCB values. To this aim, new experimental LiCB values at 373K have been measured by FTICR-MS. The
revised LiCB ranges from tetrahydrofuran (137.2 kJ mol-1) to 1,2-dimethoxyethane (202.7 kJ mol-1). The relative
basicities (ΔLiCB) were included in a single self-consistent ladder anchored to the absolute LiCB value of pyridine
(146.7 kJ mol-1). These new LiCB values exhibit a good agreement with theoretical values calculated at G2(MP2)
level.
Figure 1 shows a correlation between the computational and experimental LiCB obtained in this work.
220
LiCB, G2MP2
200
180
160
140
LiCB, this work
120
120
140
160
180
200
220
Fig. 1. Plot of computational vs. experimental LiCB scale (in kJ mol-1; R2=0,989).
The significance of these results as regard to the former LiCB scale [2] and to relationship to other scales [3]
will be illustrated.
References
[1]
R. S. Drago, D. C. Ferris, N. A. Wong, J. Am. Chem. Soc. 112 (1990) 8953.
[2]
P. Burk, I. A. Koppel, I. Koppel, R. Kurg, J.-F. Gal, P.-C. Maria, M. Herreros, R. Notario, J.L.M. Abboud, F. Anvia, R.W.
Taft. J. Phys. Chem. A 104, (2000) 2824.
[3]
C. Laurence, J.-F. Gal, Lewis Basicity and Affinity Scales: Data and Measurement, Wiley, Chichester, UK, 2010, Chap. 6.
Italy, May
May 5thth-6
-6thth,, 2014
2014
P109
Complexity of the photocatalytic hydrogen production on Pt-loaded TiO2
Sordello F.* and Minero C.
Università degli Studi di Torino, Dipartimento di Chimica, Via P. Giuria, 5, 10125 Torino
Keywords: Hydrogen Production, Photocatalysis, Complexity, Kinetic Model, TiO 2
Since the seminal paper of Fujishima and Honda [1], hydrogen production at irradiated semiconductors has attracted a lot of research efforts to understand the reaction mechanisms and to improve the overall efficiency. Nonetheless research is still very active, as witnessed by the high number of papers published on the topic in the last year
[2], and many complexities of the photocatalytic hydrogen production on semiconductors still have to be unravelled.
In the present communication we present the effect of O 2 and H2O2 on the photocatalytic H2 production over Pt–
loaded TiO2. While H2O2 suppressed H2 evolution, surprisingly O2 concentration up to 4% v/v enhanced the photocatalytic production of H2 in the experimental conditions we tested. Competition alone between O2 and water for
the photogenerated electrons cannot account for the observed increase in H2 production rate, because the system is
behaving like a complex one, in which interactions and feedback loops play a key role, as confirmed by kinetic
models. The observed trends can be understood if we consider that TiO2 surface sites can effectively trap photoelectrons and act as recombination sites. At low O2 concentration the scavenging of the electrons trapped on TiO2 surface prevails over the competition for photoelectrons at Pt islands, significantly reducing trapped electron-hole
recombination and increasing the overall efficiency. Electron trapping on TiO 2 surfaces is indeed one of the major
loss in the photocatalytic H2 production on Pt–TiO2, and any effort made to reduce it will improve the efficiency of
the process.
References
1
A. Fujishima and K. Honda, Nature, vol. 238, pp. 37-38, 1972
[2]
D. V. Esposito, I. Levin, T. P. Moffat, and A. A. Talin, Nature Materials, vol. 12, pp. 562-568, 2013
Italy, May
May 55thth-6
-6thth,, 2014
2014
P110
Enabling technologies for biomass conversion
S. Tabasso1, D. Carnaroglio2, A. Binello2, G. Cravotto*2
2
1
University of Turin, Dipartimento di Chimica, Via P. Giuria 7, I-10125 Turin, Italy
University of Turin, Dipartimento di Scienza e Tecnologia del Farmaco, Via P. Giuria 9, I-10125 Turin, Italy.
Keywords: biomass, microwave, chemicals, biopolymers
Although fossil fuels and their derivatives are still the main feedstock for the chemical industry, the demand
for renewable sources has steadily increased over the last two decades. Biomass has been recognized as a major
worldwide renewable source of fixed carbon and one which can be used for the production of biofuels and chemicals. Cellulose, hemicellulose and lignin are the main components of several types of lignocellulose waste and nonfood feedstock. Owing to ethical motivations, the origin of the transformable bio-source should not compete with
food and waste should be subsequently privileged. Recently, the use of conventional methods has been increasingly
replaced by environmental friendly procedures based on dielectric heating. Microwave-driven green chemical procedures enable energy saving and process intensification. The peculiar properties of microwaves as a volumetric
and selective dielectric heating have been efficiently exploited for the extraction of natural matrices, the hydrolysis
of biopolymers and the further conversion to highly valuable chemicals.1,2 Last generation of professional microwave reactors especially designed for extreme reaction conditions, guarantee a maximum of user safety when working at high temperatures and high pressure. Building-block chemicals, as considered in this work, are molecules
with multiple functional groups that reveal the potential to be transformed into new families of useful molecules.
All building block chemicals can further be converted to a wide spectrum of derivatives through chemical processes, such as direct polymerization. Monosaccharides, organic acids (levulinic, glycolic, lactic acids) and furans (e.g.
5-hydroxymethylfurfural—HMF and furfural) are among the key biomass-derived platform molecules that can be
obtained from different feedstocks and processed under microwave irradiation to yield high added value products
such as biofuels and biopolymers.
Fig. 1. Conversion of biomass into chemicals under microwave irradiation
References
1
A. Hernoux-Villière, U. Lassi, T. Hu, A. Paquet, L. Rinaldi, G. Cravotto, S. Molina-Boisseau, M.F. Marais, J.-M. Lévêque, ACS - Sustainable Chem. & Eng. 1 (2013), 995.
2 S. Tabasso, E. Montoneri, D. Carnaroglio, M. Caporaso, G. Cravotto, Green Chem. 16 (2014), 73.
P111
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May 55thth-6
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2014
Comparison of digestion methods for the determination of elements in woody
biomass using ICP-OES
J. Tafur Marinos*, M. Ginepro, V. Zelano
University of Turin, department of Chemistry, Via Pietro Giuria 7, 10125 Turin, Italy
Keywords: digestion methods; woody biomass; inorganic elements; chemical analyses
mg/kg
Biomass is increasingly being used as an alternative energy source to fossil fuels. Extensive investigations
have been carried out worldwide recently to enhance woody biomass use for energy conversion via thermochemical
processes such as pyrolysis, gasification or combustion [1]. Biomass is characterised by a variable composition;
among the inorganics elements contained in biomass some deserve special attention. For example, alkali compounds are responsible of fouling and corrosion in combustion and gasification systems.
The aim of this study is to quantify the contents of major (Al, Ca, Fe, K, Mg, Na, P, Si, S) and minor (As, Cd,
Co, Cr, Cu, Hg, Mn, Ni, Pb, Zn) elements present in woody biomass. Four digestion methods, wet digestion, dry
digestion, microwave digestion and ash fusion, were applied to two types of woody samples, pellets and wood
chips. The elements were determined by inductively coupled plasma optical emission spectrometry (ICP-OES)
except for Hg e As which were determined by cold vapour AAS and hydride-generation ASS respectively. The
reference material, BCR-62, olive leaves, was used in order to verify the accuracy of the digestion methods. The
contents of Al, Cd, Cu, Mn, Hg, Pb and Zn are certified on the basis of dry weight. The contents of Co, Cr, Fe, Na,
Ni, K, Ca, Mg, P and S are given for information only. The whole data were subjected to a statistical analysis.
In Figure 1 is reported the comparison of results obtained with the four digestion methods related to certified
values. The certified element contents generally were in good agreement (at the 95 % confidence level) with the
certified values, indicating that the dissolution of these elements was complete with the four methods. Except for Al
content that was lower than certified value for wet and dry methods. This was caused by incomplete dissolution of
the siliceous material.
It is well known that the ashing procedure may generally lead to erroneous results for the determination of elements, such as Zn, Cd, and Pb, which can form rather volatile compounds. However, comparing the analytical
methods, it can be noted that the dry digestion method at 550 °C did not lead to a significant loss of these elements,
while the ash fusion method at 900 °C led to a loss by volatilization of Cd and Pb. Zn is considered relatively volatile but it may form during incineration at 550 °C a stable oxide also at high temperatures. So no systematic errors
found in the dry and ash fusion methods for this element.
The contents of some indicative elements were in reasonable agreement with the values reported. Instead regarding elements that were not in agreement with not certified values, the statistical analysis showed that the values
obtained with the four methods were in good agreement between them. However, some elements, such as K and S,
were lost by volatilization. In any case the use of another CRM is recommended in order to corroborate the accuracy of these four methods for the indicative elements.
Finally, for the determination of Al is mandatory the use of HF or flux treatments in order to dissolve the siliceous matrix totally. Ash fusion method is not suitable for the determination of some volatile elements (Pb and Cd).
600
Certified value
500
dry digestion
400
wet digestion
300
ash fusion
200
MW digestion
100
0
Al
Cu
Mn
Pb
Zn
Fig. 1. Comparison between the results of the digestion methods and certified values.
References
1
Y.A. Lenis, A.F. Agudelo, J.F. Pérez, Appl. Therm. Eng. 51 (2013) 1006–1016.
Italy, May
May 55thth-6
-6thth,, 2014
2014
P112
Pd-Catalyzed Oxidative C-H Alkenylation: an Effective Method for Synthesizing
Arylvinyltriazole Nucleosides
J. Tang1, M. Cong1, Y. Xia1,3, G. Quéléver1, Y. Fan1,2, F. Qu2, L. Peng*,1
1
Aix Marseille Université, CNRS, CINaM UMR 7325, 13288, Marseille, France
College of Chemistry and Molecular Sciences, Wuhan University, 430072, Wuhan, P. R. China
3
The Vancouver Prostate Centre and Department of Urologic Sciences, University of British Columbia, Vancouver, British
Columbia, Canada
2
Keywords: Pd-Catalyzed, C-H Alkenylation, Arylvinyltriazole Nucleosides
In our quest for novel nucleoside analogues with potent antiviral and anticancer activities, we have been interested in developing arylvinyltriazole nucleoside analogues based on our discovery of the appealing biological activities of aryl appended triazole nucleosides [1-4] along with our desire and continued efforts to better understand
structure-activity relationships. In this work, we will report the first successful implementation of the oxidative C-H
alkenylation reaction, which makes use of C-H activation to directly couple a halogen-free triazole heterocycle with
a styrene derivative in the presence of a Pd(II) catalyst [5], to construct a series of structurally diverse novel arylvinyltriazole nucleoside analogues [6]. This oxidative C-H alkenylation is strikingly powerful and effective, affording
the corresponding and otherwise difficult to achieve arylvinyltriazole nucleosides with good yields and high stereospecificity. These results advocate the potential and practicality of this oxidative C-H alkenylation method for generating structurally challenging chemical entities in organic synthesis.
Fig. 1. Synthesis of Arylvinyltriazole Nucleosides Using Oxidative Heck Reaction
References
[1]
J. Wan, Y. Xia, Y. Liu, M. Wang, P. Rocchi, J. Yao, F. Qu, J. Neyts, J. L. Iovanna, L. Peng, J. Med. Chem. 52 (2009)
1144.
[2]
Y. Xia, F. Qu, L. Peng, Mini-Rev. Med. Chem. 10 (2010) 806.
[3]
Y. Xia, Y. Liu, P. Rocchi, M. Wang, Y. Fan, F. Qu, J. L. Iovanna, L. Peng, Cancer Lett. 318 (2012) 145.
[4] Y. Xia, M. Wang, O. Demaria, J. Tang, P. Rocchi, F. Qu, J. L. Iovanna, L. Alexopoulou, L. Peng, J. Med. Chem. 55 (2012)
5642.
5 For reviews of the Oxidative Heck reaction, see: (a) J. Le Bras, J. Muzart, Chem. Rev. 111 (2011) 1170. (b) B. Karimi, H.
Behzadnia, D. Elhamifar, P. F. Akhavan, F. K. Esfahani, A. Zamani, Synthesis. 9 (2010) 1399. (c) I. Moritani, Y. Fujiwara,
Synthesis. (1973) 524.
[6]
J. Tang, M. Cong, Y. Xia, G. Quéléver, Y. Fan, F. Qu, L. Peng, submitted.
P113
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May 55thth-6
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2014
On the self-condensation of aminoguanidine leading to 1,1,4,10,10-pentaamino2,3,5,6,8,9-hexaazadecan-1,3,5,7,9-pentaene (Structure elucidation through X-ray
powder diffraction)
B. Tasso*1, G. Pirisino2, F. Novelli1, Davide Garzon3, R. Fruttero4, F. Sparatore1, V. Colombo5, A. Sironi5
1
Università di Genova, Dipartimento di Farmacia, V.le Benedetto XV, 3, 16132 Genova
Università di Sassari, Dipartimento di Chimica e Farmacia, v. Muroni 23/a, 07100 Sassari
3
Università di Milano, Dipartimento di Scienze Farmaceutiche, v. Mangiagalli 25, 20133 Milano
4
Università di Torino, Dipartimento di Scienza e Tecnologia del Farmaco, v. Pietro Giuria 9, 10125 Torino
5
Università di Milano, Dipartimento di Chimica, v. Golgi 19, 20133 Milano
2
Keywords: Aminoguanidine; X-ray powder diffraction (XRPD); (polyaza)polymethines.
In 1892 J. Thiele[1] discovered aminoguanidine in the form of several salts, but he failed to obtain the free
base, isolating instead a reddish compound that was not further investigated.
Quite probably the same compound was obtained in 1913 by G. Ponzio and C. Gastaldi [2] by treating aminoguanidine hydrochloride with potassium hydroxyde. On the basis of analytical results, even if not well fitting for
the formula C2H4N6, these authors put forward the structure of 3,6-diamino-1,2,4,5-tetrazine for the isolated redviolet compound.
Later on, in 1954, Chao Han Lin et al. [3] prepared the 3,6-diamino-1,2,4,5-tetrazine by three indipendent and
unequivocal synthetic procedures, but the obtained compound resulted different from the one described by Ponzio
and Gastaldi, whose structure, therefore, must be considered undefined.
Presently, through a chemical and spectral (UV; 1H, 13C, 15N NMR; HRMS) study, the structure of
1,1,4,10,10-pentaamino-2,3,5,6,8,9-hexaazadecan-1,3,5,7,9-pentaene has been advanced for the relevant red-violet
compound, which is formed through the self-limited condensation of four molecules of aminoguanidine.
N
N
N
N
H 2N C
H 2N
H 2N
C NH2
C N NH2
H2N
NH2
NH2
C
N
N
C
C
N
N
C
N
NH2
NH2
H
N
The X-ray powder diffraction and lattice-constrained PBC-DFT optimization has confirmed the above structure, defining also the all-trans linear configuration.
Some structural analogies between the relevant compound and the potent antileukemic glyoxal bisguanylhydrazone suggest that also the former (and/or its derivatives) could be endowed with interesting biological
activities, which, indeed, are now under investigation.
References
1
J. Thiele, Ann.. 270 (1892) 1-63.
[2]
G. Ponzio, C. Gastaldi, Gazz. Chim. Ital., 43, II (1913), 129-137; idem 44, I, (1914) 257-268 and 277-282.
[3]
Chao Han Lin, E. Lieber, J. P. Horwitz, J Am. Chem. Soc. 76 (1954) 427-430.
P114
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May 55thth-6
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2014
New aminophosphorylated pH probes: synthesis, 31P NMR and ESR
characterization
S. Thétiot-Laurent*, M. Culcasi, A. Mercier, S. Pietri
Aix-Marseille Université, CNRS, ICR UMR 7273, Equipe “Sondes Moléculaires en Biologie et Stress Oxydant”
13397 Marseille Cedex 20, France.
Keywords: aminophosphonates, pH probes, 31P NMR, ESR
The pH value is a key determinant of cell energy and its study provides insights into viability and metabolism under
normal or pathological conditions. 31P NMR has become a standard, non invasive technique to determine the intracellular
pH (pHi) based on the chemical shift of inorganic phosphate (P i) of endogenous phosphorylated biomolecules [1].
However limitations appeared due to (i) Pi’s neutral pKa, that prevents strongly acidic or alkaline compartments (ie,
vacuoles, vesicles, mitochondria) to be reached, (ii) its low spectral sensitivity (AB~2.3 pH units between the acidic (A)
and basic (B) forms), and (iii) its poor concentration in subcellular compartments where it is hardly visible. Although
more sensitive, synthetic 31P NMR pH probes have been successfully used as bio-compatible alternatives to Pi (including
alkylated phosphonates [2] or aminophosphonic derivatives [3,4]), a decisive step was recently reached by aminophosphonates which demonstrated enhanced spectral sensitivity (AB~10 pH units) and allowed access to acidic
cell compartments not investigated before [5-7].
In this study we have developed a series of stable, non-toxic -phosphorylated linear nitroxides containing an
ionizable moiety and investigated their properties as electron spin resonance (ESR)-sensible pH probes. The principle of
pH-sensible ESR probes (see eg, [8]) exploits (i) the ca. three orders of magnitude increased sensitivity of ESR vs. NMR,
and (ii) the sensitivity to inductive effects (for aN) and conformation around the nitroxide function (for aP and aH in position to the aminoxyl function, see eg [9]) of the ESR coupling constants.
The synthesis of the new ESR pH probes (R1−R4 = H, alkyl) involved the Kabachnik-Fields reaction [10] starting
either from natural aminoacids methyl esters or synthetic -dialkylamino acids. We will present data on the pHdependency of (a) the 31P NMR chemical shift of their -aminophosphonates precursors, (b) and the aN, aP and aH ESR
coupling constants, and (c) the stability toward bio-reduction in a model biological milieu.
References
1
R.B. Moon, J.H. Richards, J. Biol. Chem. 248 (1973) 7276.
[2]
K. Bruynseels, N. Gillis, P. Van Hecke, F. Vanstapel, NMR Biomed. 10 (1997) 263.
[3]
F. Brénot, L. Aubry, J.-B. Martin, M. Satre, G. Klein, Biochimie 74 (1992) 883.
[4]
M. Satre, J.-B. Martin, G. Klein, Biochimie 71 (1989) 941.
[5]
S. Pietri, M. Miollan, S. Martel, F. Le Moigne, B. Blaive, M. Culcasi, J. Biol. Chem. 275 (2000) 19505.
[6]
S. Pietri, S. Martel, M. Culcasi, M.C. Delmas-Beauvieux, P. Canioni, J.L. Gallis, J. Biol. Chem. 276 (2001) 1750.
[7]
S. Martel, J.-L. Clément, A. Muller, M. Culcasi, S. Pietri, Bioorg. Med. Chem. 10 (2002) 1451.
[8]
B. Gallez, K. Mäder, H.M. Swartz, Magn. Reson. Med. 36 (1996) 694.
[9]
D.L. Haire, E.G. Janzen, G. Chen, V.J. Robinson, I. Hrvoic, Magn. Reson. Med. 37 (1999) 251.
[10] a) E.K. Fields, J. Am. Chem. Soc. 74 (1952) 1528; b) M.I. Kabachnick, T.Y. Medved, Dockl. Akad. Nauk. S.S.S.R. 84
(1952) 717; c) M.I. Kabachnick, T.Y. Medved, Izv. Akad. Nauk. S.S.S.R. Otd. Kim. Nauk. (1954) 314.
P115
7th JFIC-GIFC 2014, Turin, Italy
Surface investigation of the active sites in MgCl2 supported
Ziegler-Natta catalysts by in-situ FTIR spectroscopy
K.S. Thushara*, A. Piovano, E. Groppo and S. Bordiga
Dipartimento di Chimica, NIS Centre and INSTM, Università di Torino, Via Quarello, 15, 10135
Torino, Italy.
(*) Corresponding Author: [email protected]
MgCl2 supported Ziegler-Natta (Z-N) catalysts for the polymerizations of olefins have had
spectacular success in simplifying the polymerization process and improving polymer quality.
Identification of active site is one of the challenging problems in supported Z-N systems due to
the hygroscopic nature, oxygen affinity and low content of active sites. Investigation of surface
adsorption sites in both the active MgCl2 support and the MgCl2/TiCl4 (Z-N) catalysts can
provide an opportunity to correlate the surface structure and the catalytic activity in olefin
polymerization.
The present work deals a characterization of the surface sites present on different MgCl2 samples
and corresponding titanated MgCl2 pre-catalysts, by in-situ FTIR spectroscopy using CO as a
probe molecule. Active MgCl2 supports were prepared by chemical methods, starting from
MgCl2-alcohol adducts; among aliphatic alcohols, methanol and ethanol were chosen. FT-IR
spectroscopy of CO adsorbed at 100 K (Figure 1) reveals that the proportion of the MgCl2
exposed faces changes as a function of the synthesis procedure. Titanation, which was achieved
by interaction with TiCl4, either from vapour or liquid phase, preferentially involves the exposed
surface where Mg2+ cations are 4-fold coordinated. FT-IR spectroscopy of adsorbed CO is
complemented with the results obtained by means of various physicochemical and spectroscopic
techniques among which XRD, UV-Vis spectroscopy, TGA-DSC, N2 physisorption.
Figure 1. FT-IR spectra of CO adsorbed at 100 K on different MgCl 2 samples obtained by de-alcholation of different
adducts.
References:
1. G.A. Somorjai et al.
Langmuir, 2000, 16,
9414.
2. D. V. Stukalov et al. J.
Phys. Chem. C 2009, 113,
21376.
3. K.S.Thushara, et al. J.
Phys. Chem. C, 2011,
115, 1952.
4. E.Groppo et al. Catal. Sci.
Technol., 2013, 3, 858.
P116
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May 55thth-6
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2014
A versatile method for the oxidative chlorination of Pt(II) antitumour drugs
S. Tinello,1 E. Gabano,1 F. Fregonese,1 M. Ravera,1 D. Osella*,1
1
Keywords: Pt(IV) complexes, oxidative chlorination, antitumour drugs
Octahedral Pt(IV) complexes are usually considered antitumour prodrugs, that can be reduced in the hypoxic,
reducing tumour environment to their active square-planar Pt(II) metabolites through a two electron reduction,
which leads to the loss of their axial ligands. Pt(IV) complexes are more inert towards ligand substitution than their
Pt(II) counterparts and are engaged in fewer side reactions with biomolecules. While the choice of the equatorial
ligands is justified by the active metabolites to be released, the choice of the axial ligands is essential to modulate
the water solubility, the lipophilicity (and the related cellular uptake), the hydrolityc and the redox properties of
these complexes.
Since the axial ligands may have their own role as linkers for active or passive targeting and delivery vectors,
it could be useful to have different axial ligands to combine one reactive functionality with an inert ligand. Moreover, distinct axial ligands could impart features different (maybe intermediate) from those of the axially symmetric
complexes.
The synthesis of such asymmetric Pt(IV) complexes are generally rather difficult giving rise to mixtures of
mono- and difunctionalised complexes. The choice of the axial ligands is strictly related to the oxidation method of
the parent Pt(II) complexes. Pt(IV) complexes are usually prepared by oxidation of the corresponding Pt(II) counterparts, typically using hydrogen peroxide or chlorine. A different way to oxidize the Pt(II) compounds is represented by the use of N-chlorosuccinimide [1]. This method was developed to produce the asymmetric Pt(IV) octahedral complexes [PtA2Cl(glyc)X2] (A = amine; X = chlorido or carboxylato) but it proved to be quite versatile
towards the synthesis of other asymmetric complexes (Figure 1) depending on the conditions of the synthesis.
Fig. 1. Synthesis of Pt(IV) complexes through oxidative chlorination of the corresponding Pt(II) complexes with Nchlorosuccinimide in different media.
References
1
SANOFI-AVENTIS, FR 2 954 321 – A1 Patent.
P117
-GIFC, Turin,
Turin, Italy,
Italy, May
May 55thth-6
-6thth,, 2014
2014
7thth JFIC -GIFC,
Quinolizidinyl derivatives of bi- and tricyclic systems as potent multitarget ligands
with potential in Alzheimer’s disease.
M. Tonellia,*, M. Cattob, B. Tassoa, F. Novellia, L. Pisanib, C. Canua, G. Iuscoa, A. Sparatorec, V. Boidoa, A. Carottib, F. Sparatorea
a
Dipartimento di Farmacia, Università degli Studi di Genova, V.le Benedetto XV, 3, I-16132 Genova, Italy
Dipartimento Farmaco-Chimico, Università degli Studi di Bari, V. Orabona 4, I-70125 Bari, Italy
c
Dipartimento di Scienze Farmaceutiche “ . ratesi”, Università degli Studi di Milano, V. Mangiagalli 25, I-20133 Milano,
Italy
b
Keywords: quinolizidine derivatives, cholinesterase inhibitors, A-aggregation inhibitors
Alzheimer’s disease (AD) is a progressive neurodegenerative disorders, mainly characterized by the accumulation of aggregates of -amyloid (A) and tau proteins, with formation of extracellular amyloid plaques and intracellular fibrillary tangles, leading to cell death with particular loss of cholinergic neurons and consequent deficit of the
neurotransmitter acetylcholine (Ach). On the basis of the multifactorial pathogenesis of AD, a profitable approach
to its therapy may be the design of multi-target directed ligands, able to control symptoms and progression of the
disease. Thus, we have undertaken the synthesis of dual cholinesterases (AChE and BChE) or, even better, selective
BChE inhibitors, which, besides increasing the acetylcholine in the brain, could also reduce the formation of abnormal amyloid.
At the GIFC 2010 we already described a number of phenothiazine derivatives, and related tricyclic systems,
bearing the bulky, lipophilic and strongly basic quinolizidine ring linked through different kinds of spacers that
exhibited dual cholinesterase inhibition with low micromolar or sub-micromolar IC50 [1]. Pursuing our successful
approach, we now describe novel quinolizidine derivatives of other tricyclic systems, as thioxanthenone, xanthenone and anthraquinone and of the bicyclic naphthoquinone.
Once more, most compounds exhibit low micromolar or sub-micromolar inhibition of one or both cholinesterases and also of A-aggregation with similar potencies, thus fulfilling a fundamental requirement for a multi-target
mechanism of action against AD.
[1] B. Tasso, M. Catto, O. Nicolotti, F. Novelli, M. Tonelli, I. Giangreco, L. Pisani, A. Sparatore, V. Boido, A. Carotti, F. Sparatore. Quinolizidinyl derivatives of bi- and tricyclic systems as potent inhibitors of acetyl- and butyrylcholinesterase with potential in Alzheimer disease. Eur. J. Med. Chem. 46 (2011) 2170-2184.
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2014
7thth JFIC -GIFC,
Chiral Derivatives of 1,2-Benzenedisulfonimide as Efficient Brønsted Acid Catalysts in Strecker reaction.
Margherita Barbero1, Silvano Cadamuro1, Stefano Dughera*1, Roberta Torregrossa1
1
Universita di Torino, Dipartimento di Chimica, C.so Massimo d’Azeglio 48, 10125 Torino, Italy.
Keyword: Sulfonimides, Bronsted acids, Asymmetric catalysis, Strecker reaction, Atropisomerism.
Asymmetric catalysis is still one of the major challenges in modern organic chemistry and chiral Bronsted organic acid catalysis is, in particular, an emerging area. In fact, the asymmetric Bronsted acid catalysis has proved
itself to be a very efficient tool for the synthesis of chiral molecules as can boast of a number of impressive capabilities that contribute to obtaining the target products with very good enantioselectivity.
We have recently reported the use of o-benzenedisulfonimide (1; Fig. 1), in catalytic amounts, as a safe, nonvolatile and noncorrosive Bronsted acid in several acid-catalyzed organic reactions in very mild and selective conditions.[1]
The results and advantages of the use of 1 are very promising if one considers its applications in the field of
asymmetric catalysis.
The key to achieving good enantioselectivity results in the presence of strong chiral Bronsted acids as catalysts is the hydrogen bonding established between the protonated substrate and the conjugate chiral anion. Furthermore, a Bronsted acid should have the following attributes if it is to be considered a good chiral catalyst: adequate
acidity in order to catch up the substrate through hydrogen bonding without loose ion-pair formation, type C2
symmetry, and the presence of bulky substituents closer to the acidic function that increase the stereochemical
communication between catalyst and substrate..
So, we decided to synthesize a chiral derivative of o-benzenedisulfonimide, namely 4,5-dimethyl-3,6bis(o-tolyl)-1,2-benzenedisulfonimide (2; Fig. 1), which have two bulky groups in ortho positions and C2 symmetry; it has been easily synthetized in good overall yields (41%) by means of an eleven steps synthetic protocol
from commercially available 2,3-dimethyl-6-nitroaniline.
Fig. 1
After preparing chiral sulfonimide 2, the next step was the resolution of its atropisomers. The (-) atropisomer of 2 have been demonstrated to be efficient chiral catalysts in Strecker reaction (Fig. 1).
The presence of electron-donating or electron-withdrawing groups on the aromatic ring of 3 or 4 did not affect the
enantioselectivity of the reactions which generally provided excellent enantiomeric excecess (average ee 91%).[2]
References
1 M. Barbero, S. Cadamuro, S. Dughera , G. Ghigo, Org. Biomol. Chem., 10 (2012) 4058.
[2] M. Barbero, S. Cadamuro, S. Dughera , R. Torregrossa, Org. Biomol. Chem., submitted.
P119
th th th th
7th JFIC
-GIFC,
Turin,Turin,
Italy, Italy,
May 5May
-6 5, 2014
7th JFIC
-GIFC,
-6 , 2014
Development of LaFeO3 photocatalyst synthesized from soluble bio-organic substances for abatement of wastewater pollutants
M.L. Tummino1,2*, F. Deganello2, G. Magnacca1§, M.L. Testa2, P.Avetta1, D.Fabbri1 and
A. Bianco Prevot1
1
Università di Torino, Dipartimento di Chimica and §NIS Centre of Excellence, Via P. Giuria, 7 10125 Torino, Italy
2
Consiglio Nazionale delle Ricerche (CNR), Istituto per lo Studio dei Materiali
Nanostrutturati (ISMN), UOS-PA, via U. La Malfa 153, I-90146 Palermo, Italy
Keywords: LaFeO3, auto-combustion, photo-catalysis, soluble bio-organic substances
a)
Crystal Violet Abatement (%)
100
b)
80
60
40
t0
20
0
4-methylphenol Abatement (%)
In recent years, scientific research has been directed towards environment protection, because of increasing pollution problems. For this reason, it is necessary to find new eco-friendly synthesis methods for materials manufacture,
optimize technologies for energy production from renewable sources, remedy the already polluted waters and soils
and solve wastes accumulation problems by recycling. The present work concerns the production and characterization of LaFeO3, a perovskite-type oxide with photo-catalytic properties activated by visible light.
The oxide was synthesized by an auto-combustion method [1] using soluble bio-organic substances (SBO) extracted from composted urban wastes [2]. In this synthesis SBO replaced the traditional citric acid, as fuel, templating
and chelating agents, while metal nitrates represented metal sources and oxiders. The synthesis parameters (such as
pH, fuel-to-metal cations ratio and reducers-to-oxidizers ratio) were optimized and SBO (as they are or treated in
order to remove ashes) were employed to test how they can affect the synthesis products. Also the effect of inorganic residues present in SBO species and found in perovskite oxides was evaluated.
The morphologic, structural and chemical characterization of the samples was carried out by means of X-Ray Diffraction combined with Rietveld refinement, Scanning and Transmission Electron Microscopies, gas-volumetric N2
uptake at 77 K and FTIR spectroscopy. All samples showed 5-10 m2/g of specific surface area and limited mesoporosity, but a sonication treatment allows to largely increase these values causing the opening of closed porosities
formed during the auto-combustion process, as already evidenced in previous works [3,4]. LaFeO3 samples were
used as photo-catalysts for the abatement of two model contaminants: Crystal Violet, a cationic dye, and 4methylphenol, a representative phenolic compound that could be found in wastewaters. In the first case, pollutant
abatement reached 100% of yield at suspension pH of 9.8 (Fig. 1a), whereas the photo-degradation of 4methylphenol was less efficient and greatly influenced by pH, with abatement yield from 10% at pH=8 up to 33%
at pH=12 (Fig. 1b). These data suggest a different action mechanism of the photo-catalyst towards the two substrates. In particular different interactions between catalyst and substrates can be considered: in the case of Crystal
Violet, a direct interaction between photo-catalyst reactive oxygen anionic species and the cationic dye could occur,
whereas in the case of 4-methylphenol the interaction of the substrate with the catalyst is favored at pH=12, i.e.
when the phenate anionic form is preponderant: in this situation the anionic form of the pollutant can approach the
catalyst surface, favoured by the interaction with the cationic Fen+ and La3+ species of perovskite material.
0
2
30min 2h
4
4h
time (h)
6
8h
8
35
OH
30
O-
pH 12
32.8%
pKa=10
25
pH 10
14.8%
20
CH3
CH3
15
10
pH 8
10.6%
5
0
0
2
4
time(h)
6
8
Fig. 1. Abatement of Crystal Violet (a) and 4-methylphenol (b) with LaFeO3. Experiments performed in solarbox, with Xenon
lamp and cut-off filter for wavelengths below 340 nm. [Photocatalyst]=1200 mg/L, [Substrate]=10 mg/L.
References
1 F. Deganello, G. Marcì, G. Deganello, J. Eur Ceram. Soc., 29 (2009) 439–450.
[2] E. Montoneri, D. Mainero, V. Boffa, D.G. Perrone, C. Montoneri, Int.J.Global Environmental Issues, 11 (2011) 170.
[3] G. Magnacca, G. Spezzati, F.Deganello, M. L. Testa, 2013, RSC Adv. 3 (2013), 26352-26360.
[4] S. Jabariyan, M. A. Zanjanchi, Ultrason. Sonochem. 19 (2012) 1087–1093.
P120
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Turin, Italy,
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May 55thth-6
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2014
77thth JFIC
How odorant binding proteins interact with olfactory receptors?
M. Viano1, K. Soo-Kyung2, W.A. Goddard III2, C. de March1, J. Golebiowski1, S.
Fiorucci1*
1
2
Institut de Chimie de Nice, UMR 7272 Université de Nice Sophia-Antipolis, CNRS, Parc Valrose, 06108 Nice Cedex 2, France
Materials and Process Simulation Center (MC139-74), California Institute of Technology, 1200 E. California Blvd., Pasadena,
CA, 91125, USA
Keywords: Olfactory receptor, odorant binding protein, protein-protein interaction, molecular modeling
Olfactory receptors (OR) belong to the family of GPCR and participate to the recognition of odorants. Prior to
the activation of the OR, odorants are dissolved in the olfactory mucus by odorant binding proteins (OBP). [1]
Belonging to the family of lipocalins, they are small carrier proteins and are considered as non-specific binders. [2]
OBP would contribute to the olfaction process by carrying hydrophobic odorant molecules to the OR. Due to the
transmembrane nature of these receptors, it remains a hard task to obtain their crystal structure. Molecular modeling
represents a good way to gain insights on the structural features of OR/odorant complexes and understand how
OBP release odorants and participate to the modulation of OR activation.
We have built molecular models of hOR2T4 and rORI7 using both ab initio [3] and homology modeling
approaches. OR-OBP complexes were predicted based on a coarse-grained docking protocol (Figure 1). [4] We
propose models of interactions showing how the cavity gate of OBP (already identified as a highly conserved
position in OBP [5]) is connected to the binding pocket of ORs.
Fig. 1. OR (blue) / OBP (red) molecular model based on coarse-grained docking (B) with docking starting positions and lipid
bilayer (A).
References
[1] J. Golebiowski, L. Charlier, J. Topin, S. Fiorucci, S. Antonczak, chap. 96 in Flavour Sciences. (2013) 519-523.
[2] L. Charlier, C. Nespoulous, S. Fiorucci, S. Antonczak, J. Golebiowski. PhysChemChemPhys. 9 (2007) 5761-5771.
[3] J.K.Bray, R.Abrol, W.A. Goddard III, B. Trzaskowski, C.E.Scott, Proc. Natl. Acad. Sci. U.S.A. 111 (2014) E72-E78.
[4] S. Fiorucci, M. Zacharias, Proteins. 78 (2010) 3131-3139.
[5] J. Golebiowski, S. Antonczak, S. Fiorucci, D. Cabrol-Bass. Proteins. 67 (2007) 448-458.
P121
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2014
7thth JFIC -GIFC,
Acetone as probe molecule to investigate the acid/base surface property of ceria
and modified ceria -supported Au catalysts
F. Vindigni1*, M. Manzoli1, T. Tabakova2, V. Idakiev2, F. Boccuzzi1, A. Chiorino1
1
2
Department of Chemistry and NIS Centre of Excellence, University of Torino, Torino 10125, Italy
Institute of Catalysis, Bulgarian Academy of Sciences, “Acad. G. Bonchev” str., bl.11, 1113 Sofia, Bulgaria)
Keywords: gold catalyst, ceria, acid/base properties, FTIR, acetone
Cerium oxide has been extensively investigated because of its use in various catalytic and electrocatalytic applications [1], such as in three-way catalysts for purification of automobile exhaust gases, in ceria/zeolite catalysts
for heavy oil cracking, as well as electrolyte material in solid oxide fuel cell and as gas sensor. The success of CeO 2
in several applications is mainly due to its unique oxygen storage capacity (OSC) due to its ability to shift easily
between reduced and oxidized state (Ce3+ Ce4+) [2]. This ability, strictly connected to high oxygen defectivity,
makes CeO2 an appropriate support for precious metals, able to promote their activity and dispersion [3], to such an
extent that this oxide has become an essential support in many reactions, as the water-gas shift (WGS) reaction. In
fact, oxygen vacancies, that are the most relevant surface defects, play a crucial role for binding catalytically active
species. In particular, it was found that when Au nanoparticles are supported on ceria, the system exhibits a high
activity for the WGS reaction over a wide temperature range [4].
It is well accepted that the support surface morphology, strongly influenced by the preparation method, plays
a crucial role in the gold dispersion and, as a consequence, in the catalytic activity. For this reason, with the goal to
develop a ceria-based support which allows to obtain the best Au deposition and dispersion, ceria modified systems,
by the addition of dopants (i.e. Co, La, Zn) [5] or by the addition of other oxides (i.e. Fe 2O3, TiO2, ZrO2) [6], have
been proposed and widely studied.
Here we present new recent insighs on the correlation between the catalytic activity in the WGS reaction and
the surface property of gold supported on ceria and modified ceria systems. In particular, we report the results [7]
on gold-based catalysts, supported on ceria and mixed ceria-zirconia oxides, with quite similar Au dispersion, that
show different catalytic activity in the WGS reaction, evidencing that in some cases it is not possible to explain the
activity only taking into account the total amount of gold sites exposed at the support surface. Indeed, using the
FTIR spectroscopy, with acetone as probe molecule, we have evaluated the acid/base properties of ceria and mixed
ceria-zircona oxides, getting a correlation between the catalytic activity in the WGS reaction and the acid/base surface properties of the support oxides.
The same approcheas have been also used to investigate the surface properties of two gold catalysts supported
on two kinds of ceria, prepared by different techniques [8]. One of them is a coprecipitation method (CP), starting
from a solution of Ce(NO3)3.6H2O, the second method is a preparation via urea gelation coprecipitation (UGC). The
catalytic tests on the WGS reaction have shown that the gold catalysts supported on UGC samples have higher activity than those supported on CP. Moreover, many techniques (HRTEM, XRD, BET and FTIR with CO as probe
molecule), have evidenced that the urea assisted method gives rise to an increase in the specific surface area with a
defectivity enhancement, while no differences in the Au distribution have been detected. Interestingly, beside the
evaluation of the acid/base properties of the two differently prepared ceria, FTIR analysis with acetone have also
put in evidence that different kinds of Lewis acid sites (Ce 4+) are exposed on the surface of the two ceria supports.
As a result, on the basis of these findings, we report, also in this case a correlation between the WGS catalytic activity and the different surface properties of the differently prepared ceria supports.
References
1 a) R.M. Heck, R.J. Farrauto, Catalityc Air Pollution Control,(Ed: Van Nostrand Reinhold), New York, 1995; b) T.M. Tri, J.
Massandier, P. Gallezot, B. Imelik, In Proceedings of the 7th International Congress on Catalysis, (Eds: T. Seiyama and K.
Tanabe) Elsevier, Amsterdam, 1980, p. 266; c) M. Mogensen, N.M. Sammes, G.A. Tompsett, Solide State Ionics 127 (2000) 6394; d) R. Bene, I.V.; Perczel, F. Reti, F.A. Meyer, M. Fleisher, H. Meixner, Sens. Actuators B, 71 (2000) 36-41.
[2] A. Trovatelli, C. de Leitenburg, G. Dolcetti, Chem Tech., 27 (1997) 32-37.
[3] A. Trovarelli, in: A. Trovarelli (Ed.), Catalysis by Ceria and Related Materials, Imperial College Press, London, 2002, pp.
15-50.
[4] J. Kaspar, P. Fornasiero, in: A. Trovarelli (Ed.), Catalysis by Ceria and Related Materials, Imperial College Press, London,
2002, pp. 217-242.
[5] T. Tabakova, M. Manzoli, F. Vindigni, V. Idakiev, F. Boccuzzi, J. Phys. Chem. A, 114 (2010) 3909–3915.
[6] T. Tabakova, G. Avgouropoulos, J. Papavasiliou, M. Manzoli, F. Boccuzzi, K. Tenchev, F. Vindigni, T. Ioannides, Appl.
Catal. B: Env. 101 (2011) 256–265
[7] F. Vindigni, M. Manzoli, T. Tabakova, V. Idakiev, F. Boccuzzi, A. Chiorino, Appl. Catal. B-Env. 125 (2012) 507-515.
[8] F. Vindigni, M. Manzoli, V. Idakiev, F. Boccuzzi, A. Chiorino, PCCP, 15 (2013) 13400-13408.
P122
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A freely available software tool to predict the photodegradation of organic contaminants in surface waters
D. Vione,*1 C. Minero,1 M. Bodrato 2
1
University of Turin, Department of Chemistry, Via P. Giuria 5, 10125 Turin, Italy.
2
MambaSoft, Via S. Marino 118, 10137 Turin, Italy.
(*) E-mail: [email protected]
Keywords: surface-water photochemistry, xenobiotic phototransformation, sunlit waters, environmental modelling.
Photochemical reactions play an important role in the transformation of organic pollutants in surface waters. They
are usually divided into direct and indirect processes: in the former, absorption of sunlight by the pollutant triggers
transformation. In indirect photolysis, sunlight-absorbing molecules (e.g. chromophoric dissolved organic matter CDOM-, nitrate and nitrite) produce reactive transients including OH, 1O2, CDOM triplet states (3CDOM*) and
CO3 [1]. The rate and, therefore, the importance of photochemical reactions depend on several features of both the
environment and the pollutant, such as sunlight irradiance, water depth, chemical composition and absorption spectrum, and on pollutant photochemical reactivity (direct photolysis quantum yield and reaction rate constants with

OH, 1O2, 3CDOM* and CO3) [2]. We have recently developed a photochemical model to predict pollutant phototransformation kinetics as a function of water chemistry and depth, based on photochemical reactivity parameters of
the pollutant itself. The model has been validated towards the degradation of several xenobiotics in surface-water
environments [3,4,5].
Built on such basis, the APEX software (Aqueous Photochemistry of Environmentally-occurring Xenobiotics) [6]
predicts pollutant photodegradation kinetics, steady-state concentrations of photoreactive transients, as well as formation kinetics and yields of intermediates. Needed input data for APEX are direct photolysis quantum yields, reaction rate constants with OH, 1O2, 3CDOM* and CO3, and intermediate formation yields via each process. The
experimental protocol to derive such data has been described in detail in several publications [3,4,5]. The figures
below show the general structure of APEX, as well as the information flow among its various functions.
Standard quantities (sunlight
plotgraph.m
irradiance and spectrum, formation
quantum yields of transients)
Input data
Environmental variables
(water chemistry, depth, spectrum)
Substrate
reactivity
(quantum yield, reaction
rate constants, formation
yields of intermediates)
savetable.m
Input .csv file
Input data
apex.m
integral.m
Model
Numerical integration
Calculation
results
equations
plotgraph.m
savetable.m
OUTPUT DATA (first-order rate
constants, steady-state concentrations)
3D plot
Output table
The APEX code is based on the open software Octave (http://www.gnu.org/software/octave), and it is available for
free download at http://chimica.campusnet.unito.it/do/didattica.pl/Quest?corso=7a3d (click on "AA2012/2013"), or
as Electronic Supplementary Information (ESI) of reference [6] (ESI is freely downloadable also to non-subscribers
of the journal).
[1] S. Canonica et al., Environ. Sci. Technol. 39 (2005), 9182.
[2] Boreen et al., Aquat. Sci. 65 (2003), 320.
[3] D. Vione et al., Water Res. 45 (2011), 6725.
[4] P. R. Maddigapu et al., Environ. Sci. Technol. 45 (2011), 209.
[5] E. De Laurentiis et al., Environ. Sci. Technol. 46 (2012), 8164.
[6] M. Bodrato, D. Vione, Environ. Sci.: Processes Impacts 16 (2014), 732.
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P123
Bi(OTf)3-Catalysed Hydroarylation of Allenes and Dienes
G. Lemière, B. Cacciuttolo, E. Belhassen, E. Duñach *
Institut de Chimie de Nice, Université de Nice-Sophia Antipolis, CNRS, UMR 7272,
Parc Valrose, 06108 NICE CEDEX 2, France.
Keywords: metal triflate, bismuth, cycloisomerisation, diene, allene, hydroarylation
The development of catalytic, clean, efficient and mild synthetic methods to create CC bonds remains one
of the most important topics in the field of organic chemistry. In this context, catalytic Friedel-Crafts reactions have
gained a particular attention.[1] The hydroarylation, namely the addition of an arene CH bond across a multiple
bond, represents the most atom-economical way to functionalize aromatic nuclei since theoretically no waste is
produced during the reaction. Although the studies concerning the catalytic hydroarylation of alkynes and alkenes
have been well-undertaken, the extensions to related allenes and 1,3-dienes have been more disregarded. Hydroarylation of allenes has been mainly reported using noble transition-metal catalysts based on gold[2] and platinum[3]
derivatives. Despite their efficiency, these methodologies require the use expensive catalysts and are limited to the
functionalization of electron-rich arenes.
Our group has been interested in the development of new cycloisomerization processes catalyzed by triflate[4]
and triflimide[5] metal salts. We found that bismuth(III) triflate could be employed successfully to promote the intraand intermolecular hydroarylation of allenes and 1,3-dienes. A sequential bis-hydroarylation of the allene moiety
was also developed giving access to various interesting polycyclic structures (Figure 1).
R
EDG
+
•
or
R
Bi(OTf)3 (5 mol%)
EDG
CH3NO2, rt
30 min
References
[1] M. Rueping, B. J. Nachtsheim, Beilstein J. Org. Chem. 6 (2010) 6 and references therein
[2] (a) M. A. Tarselli, M. R. Gagne, J. Org. Chem. 73 (2008) 2439; (b) T. Watanabe, S. Oishi, N. Fujii, H. Ohno, Org. Lett 9
(2007) 4821.
[3]
J. Mo, P. H. Lee, Org. Lett. 12 (2010) 2570.
[4] (a) B. Cacciuttolo, S. Poulain-Martini, E. Duñach, Eur. J. Org. Chem. (2011) 3710; (b) J. Godeau, S. Olivero, S. Antoniotti,
E. Duñach, Org. Lett. 13 (2011) 3320.
[5] F. Grau, A. Heumann, E. Duñach, Angew. Chem. Int. Ed. 45 (2006) 7285;
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2014
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P124
Solar energy converted by flexible devices: photocured polymer electrolytes and
bendable nanotubes membranes
F. Bella*,1,2, A. Lamberti2, A. Sacco1, S. Bianco1, E. Tresso1,2, R. Bongiovanni2
2
1
Istituto Italiano di Tecnologia, Center for Space Human Robotics @Polito, Corso Trento 21, 10129 Torino, Italy
Politecnico di Torino, Department of Applied Science and Technology, Corso Duca degli Abruzzi 24, 10129 Torino, Italy
Keywords: Dye-sensitized solar cell, Polymer electrolyte membrane, TiO2 nanotubes, Photopolymerization, Flexible device
One of the possible applications of dye-sensitized solar cells (DSSCs) is the biasing of low-power portable
devices. In this framework, the cells should be flexible and adaptable to complex shapes. Therefore, it is necessary
to prepare suitable electrodic and electrolytic materials.
As regards electrolytes, we have recently proposed polymer electrolyte membranes (PEMs), as a good alternative to the traditionally used viscous gels. PEMs are prepared through a green, low-cost and fast process of photoinitiated polymerization, which allows obtaining a fast transformation of a liquid monomer or oligomer into a solid
membrane with tailored physico-chemical and mechanical properties. We present here several acrylic/methacrylic
PEMs, with emphasis also on unconventional fillers and redox couples [1,2].
As regards photoanodes, one the most critical aspect in the development of flexible DSSCs lies in the fabrication of a nanostructured TiO2 film with good adhesion to the conductive substrate, high surface area, excellent dye
loading capabilities and good electronic transport properties. The employment of mesoporous TiO 2 nanoparticles,
treated with low-temperature procedures, has been recently explored, but it did not guarantee the desired results. A
possible alternative way is based on the use of TiO2 nanotubes (NTs) grown by anodic oxidation. We have recently
reported that TiO2 NTs show a good adhesion to the starting substrate of growth and can provide performances
competitive with those of TiO2 nanoparticles, showing higher electron transport thanks to the quasi-one dimensional arrangement and high surface area for dye anchoring [3]. The as grown and thermally treated samples were deeply investigated in order to gain a whole understanding of their structural, physical and chemical properties.
Here we report for the first time the combination of a methacrylic crosslinked PEM (whose polymeric network
has been deeply characterized by charge-transfer measurements and dynamo-mechanical analysis) and vertically
oriented TiO2 nanotubes grown by anodic oxidation of flexible Ti mesh in order to fabricate a flexible and transparent DSSC. The photovoltaic behavior was exhaustively investigated by electrical measurements and impedance
spectroscopy. To the state-of-the-art, the appropriate selection and optimization of all the materials allowed us to
obtain the most efficient quasi-solid flexible DSSC ever produced.
Fig. 1. Novel electrode and electrolyte membranes: towards flexible dye-sensitized solar cell combining vertically aligned TiO2
nanotube array and light-cured polymer network.
References
1
F. Bella, A. Sacco, G.P. Salvador, S. Bianco, E. Tresso, C.F. Pirri, R. Bongiovanni, J. Phys. Chem. C. 117 (2013) 20421.
[2]
F. Bella, R. Bongiovanni, R.S. Kumar, M.A. Kulandainathan, A.M. Stephan, J. Mater. Chem. A 1 (2013) 9033.
[3]
A. Lamberti, A. Sacco, S. Bianco, D. Manfredi, F. Cappelluti, S. Hernandez, M. Quaglio, C.F. Pirri, Phys. Chem. Chem.
Phys. 15 (2013) 2596.
P125
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Italy, May
May 55thth-6
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2014
77thth JFIC
FT-IR and FT-Raman spectroscopic investigations of ancient Chinese wooden artifacts
Eliano Diana1, Arianna Favaretto1*
1
Università degli studi di Torino, Dipartimento di chimica, Via Pietro Giuria 7
Keywords: archaeological wood diagnosis; infrared spectroscopy; Raman spectroscopy
Wood is a renewable, complex material made up of hollow cells with a strong wall that consists mainly of three biopolymers:
cellulose, lignin, and hemicelluloses. Cellulose, hemicelluloses and lignin are the main macromolecular cell wall components. In
addition, wood may also contains, in greater or lesser quantities, low molecular-weight components, namely extractives and
mineral substances. Extractives include several classes of organic compounds such as sugars, flavonoids, tannins, terpenes, fats
or waxes. The relative concentration and the chemical composition of lignin and hemicelluloses differs between softwoods and
hardwoods, while cellulose is a uniform component of all wood species.
The chemical characterization of archaeological wood is of great importance, as it can not only reveal the degradation processes
that have occurred but it can also direct conservation practices, in order to choose the appropriate conservation method.
Since 1980s, Fourier Transform Infrared spectroscopy (FT-IR) and FT-Raman spectroscopy have been used for routine and
research laboratory analyses in the art conservation field. Both these analytical technique have been proved useful for studying
the chemistry of wood and wood decay, because very small quantities of wood and minimal manipulation of samples are required to provide detailed information. FT-IR spectroscopy has been extensively used to analyze the chemical changes in wood
that occur during weathering, decay, chemical treatments and biodegradation processes and to characterize the chemistry of
wood, obtaining quantitative data, mainly in the determination of lignin, whereas Raman spectroscopy have been usually employed to identify characteristic bands of wood and its chemical components such as carbohydrates, sugars, extractives and
resins.
In this work are presented the results of FT-IR and FT-Raman spectroscopic investigations conducted on wood samples taken
from three painted wooden artefacts, currently housed at the MAO (Museo d'Arte Orientale, Torino, Italy), shown in Fig. 1.
FT-IR and Raman spectra were collected from a single sliver of wood taken from the “Chariot” (C 1), two different slivers of
wood taken from the “Saddled wooden horse” (C 2, C 3), and some residual powder collected from the “Animal Unicorn
guardian of the Tomb” (C 4). The results highlight the state of conservation of the constituent wooden material and provide a
qualitative characterization of wood and its principal components.
(3)
(1)
(2)
Fig. 1. Painted Chinese wooden artefacts studied, named “Chariot” (1), “Saddled wooden horse” (2),
and “Animal Unicorn guardian of the Tomb” (3).
References
[1] Christensen M. et al., J. Raman Spectrosc. 2006; 37: 1171–1178;
[2] Sandak A. et al., Journal of Archaeological Science 2010; 37: 2093-2101;
[3] Emandi A. et al., INTERNATIONAL JOURNAL OF CONSERVATION SCIENCE, Volume 1, Issue 4, October-December
2010: 211-218;
[4] Petrou M., Anal Bioanal Chem 2009; 395: 2131-2138;
P126
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2014
7thth JFIC
New approaches for the preparation of micro- and nano-materials with selective
recognition properties
C.Giovannoli1, C. Passini1, F. Di Nardo1, L. Anfossi1, C. Baggiani1
1
University of Torino, Department of Chemistry
Keywords: molecular imprinting, molecular recognition, synthetic receptors, sacrificial silica, grafting
The most popular method for obtaining molecularly imprinted polymers consists in a bulk polymerisation
which produces a monolithic material that has to be crushed and sieved to obtain particles of the desired size distribution. Despite being a convenient approach, it shows many practical drawbacks, such as large losses of imprinted
material as submicrometer dust, limited solubility of template molecules in the porogenic solvents and morphological heterogeneity of the crushed materials.
With the purpose of overcoming these drawbacks, several alternative approaches based on the synthesis of
imprinted beads have been proposed in recent years. The main advantages of such approaches consist in the easy
preparation of spherical imprinted polymeric particles with narrow diameter and pore size distribution, particularly
indicated for separative applications such as liquid chromatography and solid phase extraction.
In this field, one of the most interesting methodologies consists in filling the pores of meso- or macroporous
silica beads with an imprinting mixture, polymerizing it and dissolving the inorganic support by corrosion with
hydrofluoric acid or ammonium fluoride, leaving porous imprinted beads as a negative image of the sacrificial silica beads. Templates can be introduced within the silica beads together with the pre-polymerization mixture or previously covalently grafted to the inner surface of the pores.
In this communication, we describe the effect of silica porosity, pore surface pre-treatment, presence of a porogenic solvent and polymerization conditions on the binding performances of the imprinted polymers with molecular recognition properties towards steroids, antibiotics, peptides and natural products. The influence of the template
grafting on the selectivity of the imprinted polymer is also reported. The use of sacrificial silica beads as microvessels for the synthesis of molecularly imprinted beads results to be an efficient alternative to emulsion, precipitation
or bulk polymerization. Moreover, it is particularly convenient when a fragmental or mimic template approach is
needed or when compatibility between template molecule and porogenic solvent does not exist.
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2014
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A hyerarchical approach as new strategy for protein imprinting
C. Passini1*, C. Giovannoli1, F. Di Nardo1, L. Anfossi1, C. Baggiani1
1
University of Torino, Department of Chemistry
Keywords: molecular imprinting, molecular recognition, synthetic receptors, proteins, sacrificial silica
Molecular imprinting is a bulk polymerizatrion technique that is used to create artificial receptors by the formation of a polymer network around a template molecule. This technique has proven to be particularly effective for
molecules with low molecular weight (<1500 Da), but recently the number of research articles on the imprinting of
larger template molecules is increasing considerably too. However, expanding this methodology toward efficient
imprinted materials for selective recognition of proteins appears to be extremely challenging, principally because of
the lack of binding site accessibility. Several approaches recently proposed in literature are based on surfaceimprinting methods or bulk-imprinting of short epitopic polypeptides related to the target proteins. Even if these
approaches seems to solve some of the well-known technical problems, producing highly reproducible imprinted
materials, they do not represent the optimal solution, as they are yet affected by several important drawbacks. In
fact, surface-imprinting produces imprinted layers characterized by a very low binding site density, not suitable for
separative applications, while epitope-imprinting is very expensive and technically coumbersome.
We propose here a novel approach based on the use of macroporous sacrificial silica monoliths as polymerization support to obtain macroporous protein-imprinted polymers characterized by good binding site accessibility,
target protein selectivity and technical feasibility. In this approach, small macroporous silica monoliths are prepared
from tetraethoxysilane basic hydrolysis in plastic molds. The obtained monoliths are functionalized by silanization
with a mixture of aminopropyltrimethoxysilane – hexamethyldisilazane, and a reactive spacer arm is introduced by
reaction with succinic anhydride and subsequently with a mixture of N-hydroxysuccinimide and diisopropylcarbodiimide. The target template – chicken egg ovalbumin – is then covalently bounded onto the surface of the silica
macropores by direct reaction in bicarbonate buffer. To obtain the imprinted polymer, the ovalbumin-grafted silica
monolith is filled with a mixture of functional monomer, cross-linker and radical initiator and subjected to thermal
polymerization. Then, the composite is treated with ammonium fluoride to dissolve the sacrificial silica and the
resulting monolith sequentially washed with acidic and basic buffers to remove the template protein.
The optimization of the polymerization mixture allowed us to easily prepare efficient and reproducible imprinted monolithic polymers with good binding properties towards the template protein and selectivity respect to
non ovalbumin-related proteins such as bovine serum albumin and bovine serum -globulins.
Indice degli autori
Index des auteurs
Abollino
Accomasso
Aceto
Agostino
Aime
Aina
Ait ahsaine
Ait-Lahmidi
Alama
Alberti
Alberto
Alessio
Alfei
Alfredsson
Al-Karadaghi
Alladio
Alloisio
Alloisio
Amirat
Andjouh
Andrson
Anfossi
Antonczak
Antonioli
Antoniotti
Appendino
Arata
Arena
Argirusis
Arrais
Artini
Assaud
Aussenac
Auteliano
Avetta
Avonto
Baggiani
Balaban
Balantseva
Baldovini
Balliano
Balotti
Banfi
O.
S.
M.
A.
S.
V.
H.
N.
A.
D.
G,
M.
S.
M.
S.
E.
M.
S.
S.
S.
J.A.
L.
S.
D.
S.
G.
S.
F.
C.
A.
C.
L.
F.
A.
P.
C.
C.
T.S.
E.
N.
G.
R.
L.
P60, P106
P25
COM8
COM8, P81
COM29, P14
COM12, COM25, P1, P2, P26, P67
P3
P62
COM10
COM29, P14
P4, P25
P86
P18
P97
P88
COM19
COM5
P18
P42
COM16
P26
P126, P127
INV2, P12
P55
COM13
P6, P19, P40, P72, P89
COM2
P104
P27
P5
INV4
COM20, P9
COM31
P6
P7, P79, P119
P40
P126, P127
PLE1
P8
COM26
P53
P71
COM10, COM27
Baranova
Barberis
Barbero
Barbero
Bardelli
Baricco
Barolo
Barr
Basso
Basso
Battezzati
Bearman
Belhassen
Bella
Benhida
Benlhachemi
Benzi
Bergé-Lefranc
Berlier
Bertinaria
Berto
Bertolotti
Bianchi
Bianco
Bianco
Bianco Prevot
Bignon
Binello
Bisio
Blache
Blanc
Boccaleri
Boccuzzi
Böckler
Bodoardo
Bodrato
Boggio
Boido
Bonandini
Bonarrigo
Bongiovanni
Bonino
Bonometti
E.A.
I.
M.
N.
C.
M.
C.
M.
A.
T.
M.
G.
E.
F.
R.
A.
P.
D.
G.
M.
S.
C.
C.L.
S.
A.
A.
E.
A.
C.
Y.
R.
E.
F.
F.M.
S.
M.
P.
V.
L.
I.
R.
F.
E.
P9
P39
P118
P45, P58
P40
P22
P33, P44, P45, P50 , P58, P91
P9
COM10, COM27
P113
P10
P66
P123
P124
P71
COM4, P3
P5
P52
P8, P77, P101
COM3
P30, P37
P103
P27
P124
P11
P55, P119
P12
P110
P13, P36, P101
COM16
P69
P5, P64
P67, P121
P53
P24
P122
COM29, P14
P117
P58
P86
P124
P48, P107
P15
Bordiga
Borretto
Bosca
Boschi
Bosson
Botavina
Botta
Botta
Bottinelli
Botton
Boulet
Bracher
Braschi
Brazeau
Bressy
Brigante
Brisset
Brullo
Brunelleschi
Bruni
Bruno
Burk
Buscaino
Buzzi
Cacciuttolo
Cadamuro
Calabrese
Calcio Gaudino
Calza
Canaparo
Caneva
Canonico
Cantamessa
Cantoni
Canu
Capannelli
Caporaso
Caprioglio
Capron
Capucci
Caputo
Caratto
Cardinale
S.
E.
F.
D.
J.
M.
M.
M.
E.
P.
F.
I.
N.
C.
M.
H.
C.
S.
G.
O.
P.
R.
L.
B.
S.
G.
M.
P.
R.
C.
F.
S.
D.
C.
G.
M.
D.
L.
V.
G.
V.
A.M.
COM15, P48, P107, P115
COM3
P51
P43, P88, P103
P16
P17
COM21, P23, P57
P20
COM18
COM11
P53
P101
P9
P78
P11
P78
COM14, COM23
P40
COM2
COM14, COM23
P108
P44, P58, P91, P102
P64
P123
P118
P70
P98
P7, P79
P45
P18
P64
P5
P19
P117
COM2
P98
P19
P94
P27
P77
P20, P105
P21
Carfora
Carlini
Carnaroglio
Carniato
Carotti
Casano
Casino
Castellano
Castellero
Castoldi
Catalano
Catto
Causone
Cena
Cerezo
Cerrato
Cesano
Chadwick
Charles
Chaspoul
Chavan
Chegaev
Chen
Chen
Chiantore
Chiarlone
P.
R.
D.
F.
A.
G.
S.
M.
A.
L.
F.
M.
D.
C.
M.
G.
F.
A.
L.
F.
S.
K.
C.
Y.
O.
A.
P91
P22
P110
P13, P23
P117
COM31
P24
COM17
P22
P75
COM25, P4, P25
P117
P55
P61
P71
COM12, P1, P2, P26, P27, P67
P28
P97
COM9
COM22
COM15
P35
P29
P92
P31, P32, P95
COM2
Chiavazza
Chiorino
Cielo
Cimino
Civalleri
Clément
Cocco
Colombo
Colombo
Coluccia
Cometto
Comite
Commeiras
Cong
Conterosito
Coquerel
E.
A.
D.
D.
B.
J.L.
M.
A.
V.
S.
C.
A.
L.
M.
E.
Y.
P30
P121
P58
P31, P32
COM15
P16
COM3
P31
P113
P8, P77
P54
COM2, COM10
P69
COM7, P112
P33
P93
Corno
Cortese
Cossi
Costa
Costa
Costenaro
Couturier-Tamburelli
Cravanzola
Cravotto
Cucinotta
Culcasi
D’Aleo
Damin
de la Rie
De Laurentiis
de March
De Negri
De Petrocellis
Deagostino
Deganello
Deguillaume
Deiana
Del Prete
Delle Piane
Dellepiane
Demarchis
Demaria
Desmurs
Di Corcia
Di Felice
Di Legami
Di Lupo
Di Marzo
Di Nardo
Di Stilo
Di Vona
Diaf
Diana
Diharce
Dimitrov
Djellal
Djenizian
Dubois
M.
D.
M.
G.A.
U.
D.
I.
S.
G.
F.
M.
A.
A.
R.E.
E.
C.A.
S.
L.
A.
F.
L.
C.
D.
M.
G.
L.
C.
J. R.
D.
R.
R.
F.
V.
F.
A.
M.L.
I.
E.
J.
D.
A.
T.
S.
P34
P35
P46 , P101
INV4, P20
P81
P36
COM30
P28
P110, P98
P47
P114, P87
COM24
P107
P31
P37, P38
COM26, P120
P74
P89
COM29, P14
P119
P11
P39 , P49, P85, P104
P40
P34
COM5
P41
P5
P76
COM19
COM2
COM17
P24
P89
P126, P127
COM3, P61
P82, P83
COM28, P80
P90, P125
INV2, P12
P68
P42
P96, P97
P69
Ducime
Ducime
Dughera
Duñach
Duñach-Clinet
Durrieu
Edwards
Ellena
Errahali
Estevão
Etgar
Ethiraj
Eyraud
Ezahri
Fabbiani
Fabbri
Fages
Fan
Fanciulli
Fasoli
Favaretto
Favaro
Fedeli
Federico
Felouat
Fenoglio
Feray
A.
A.
S.
E.
E.
G.
J.K.
S.
M.
B.M.
L.
J.
M.
M.
M.
D.
F.
Y.
C.
M.
A.
G.
E.
A.
A.
G.
L.
P43
P51
P118
COM1,P76, P80, P123
COM28
P63
COM13
P44, P45, P102
P46
P47
P36
COM15, P48
P97
P3
P39, P49
P7, P79, P119
COM24
COM7, P112
P22
P20
P125
P50
COM9
P51, P103
COM24
COM8
INV3
Fernand
Ferrante
Ferrari
Ferretti
Fiorucci
Flynn
Foglietta
Fontaine-Vive
Franceschi
Franco
Fregonese
Fresu
Fritzson
Frølund
Fruttero
D.
T.
A.M.
M.
S.
G.E.
F.
F.
E.
F.
F.
L.G.
I.
B.
R.
COM22, P52
P53
P8
P105
INV2, P120
P2
P45
COM13
P20
P54
COM6, P56, P116
P40
P88
P103
P35, P113
Gabano
Gabano
Gaino
Gal
Galatini
Galleano
Galliano
Gallina
Gallucci
Gamarra
Gambino
Garella
Garino
Garnier
Garzon
Gasco
Gastaldi
Gastaldo
Gatti
Gavarri
Genazzani
Geninatti-Crich
Gerace
Gervasio
Geuna
Ghedini
Ghibaudi
Giachino
Giacomino
Gianotti
Gianotti
Giauffret
Gibson
Gigmes
Ginepro
Giorgis
Giovannini
Giovannoli
Giraudo
Gobetto
Goddard
Godemert
Golebiowski
E.
E.
L.
J. F.
A.
I.
S.
C.
K.
C.
G.
D.
C.
C.
D.
A.
D.
F.
G.
J.R.
A.
S.
E.
G.
S.
E.
E.
C.
A.
E.
V.
J.
I.R.
D.
M.
M.
M.
C.
A.
R.
W.A.
J.
J.
COM6, P116
P56, P86
P57
COM1, P108
COM27
P88
P50, P58
P25
P75
COM8
COM21
COM3, P61
P54
P63
P113
P35
P64
P59
P5, P36, P46, P101
COM4, P3
P72
COM29, P14
COM19
P15
P25
P1
P84
P25
P106, P60
P20 , P47
P33
COM13
P2
COM9, P16
P111
P61
P59
P126, P127
P88
P54
P120
P93
INV2, COM26, P120
Gooyit
Gosetti
Graetzel
Groppo
Gugliotta
Guidotti
Guillaneuf
Guinneton
Hanbücken
Hayzoun
Héran
Heyman
Hioka
Hornebecq
Hutchings
Iacobucci
Iannarelli
Idakiev
Ilieva
Imrie
Irico
Isaia
Iusco
Ivancenko
Ivanov
Janda
Joffrin
Kaljurand
Kanellopoulou
Keller
Knauth
Koppel
Kuchta
Labate
Lacapra
Lalevée
Lamberti
Lamberti
Laus
Lavedrine
Lazzarini
Lebon
Lefay
M.
F.
M.
E.
G.
M.
Y.
F.
M.
H.
V.
H.
N.
V.
G.J.
C.
L.
V.
L.
F.E.
S.
M.
G.
P.
K.
K.D.
A.
I.
D.
M.
P.
I.
B.
M.
C.
J.
C.
A.
K.
B.
A.
A.M.
C.
P43
P62, P70
P36
P115, P65
COM21, P57
P13
P16
COM4, P3
COM20, P9
P63
P69
P89
P47
COM22 , P52
COM13
COM1
P79
P121
P68
P2
P64
P37
P117
P104, COM25
P68
P43
P80
P108
P27
P53
P82, P83, P96
P108
COM11
COM8
P100
P16
P124, P65
P124
P55
P31
P65
COM26
COM9
Leito
Lejars
Lemiere
Lenoble
Leofanti
Lietti
Lillerud
Liu
Llewellyn
Locardi
Loddo
Logiacco
Lolli
Lombardo
Lusvardi
Lyoussi
Maccagno
Macciò
Magistris
Magnacca
Mailhot
Malandrino
Malavasi
Manfredi
Manzoli
Marchese
Mardjan
Marengo
Marini
Marotta
Marset
Martina
Martinelli
Martinez Espinoza
Martini
Martra
I.
M.
G.
V.
G.
L.
K.P.
X.
P.
F.
R.
F.
M.L.
A.F.
G.
A.
M.
D.
C.
G.
G.
M.
G.
M.
M.
L.
M. I. D.
E.
E.
V.
A.
K.
J.
M.I.
M.
G.
Masala
Masini
Massa
Massi
Matarrese
Maurino
A.
R.
M.
L.
R.
V.
P108
P78
COM28, P123, P80
P63
P65
P75
COM15 , P107
P29
COM22
P20
P18
P18
P43, P51, P88, P103
P104
COM12, P2
COM4
COM5
P21
COM12, P1, P44
P7, P79, P119
P11
P30, P60, P106
COM12, P2
P66, P70
P67, P68, P121
P36, P46, P47, P101
P69
P62, P66, P70
P61
COM2
P72
P51
COM21
COM5
P20
PLE2, COM12, COM25, P1, P2, P4, P17,
P25, P39, P49, P85, P104
COM15
P20
COM14, COM23
COM1, P94
P75
P38, P73, P85
Mayeux
Mazzucco
Mehiri
Mele
Menabue
Menegazzo
Mercier
Merlen
Meta
Meyer
Miglio
Milanesio
Miletto
Miletto
Millet
Minassi
Minella
Minella
Minero
Minero
Minetti
MohammadHosseini
Moni
Montoneri
Morandi
Moreira
Moreo
Morizur
Moujjah
Mounier
Müller
Munteanu
Muolo
Muscuso
Musso
Mutch
Narducci
Nazeerudin
Nencini
Nervi
Nguema Edzang
Nielsen
Nilsson
C.
E.
M.
P.
L.
F.
A.
T.A.
E.
T.B.
G.
M.
L.
I.
A.
A.
M.
M.
C.
C.
R.
A.
L.
E.
S.
G.
A.
V.
D.
S.
C.
G.
M.L.
L.
G.
G.A.
R.
M.K.
L.
C.
R.
B.
U.J.
P108
P62, P70
P94
P22
COM12
P67
P114
P52, P92
COM14, COM23
P36
COM3
INV1, P33, P50
P20
P77
P71
P19, P72
P24, P38, P41
P73
P24, P38, P41, P109, P122
P54, P73
P74
COM11
COM27
P55
P26, P27, P75
COM9
P43
P76
P94
P63
P53
P68
INV4
P28
P77
P26
P82, P83
P36
P54
P54
P78
P103
P88
Nisticò
Nolibe
Notar Francesco
Novelli
Øien
Oliaro-Bosso
Olivero
Olsbye
Ondet
Operti
Osella
Oswald
Ouammou
Ouari
Pagani
Pagliai
Pagliero
Panzeri
Pardanaud
Parrain
Pascale
Pasquini
Passananti
Passaretti
Passerone
Passini
Patout
Paul
Pazzi
Peccati
Pellegrini
Pellegrino
Pellutiè
Pelzer
Peng
Perin
Petit Bon
Petrocchi
Petrova
Piccinelli
Pietri
Piétri
Pinna
R.
G.
I.
F.
S.
S.
S.
U.
P.
L.
D.
F.
A.
O.
A.
P.
A.
L.
C.
J.-L.
L.
L.
M.
F.
A.
C.
L.
G.
M.
F.
R.
E. M.
L.
K.
L.
E.
P.
C.
P.
A
S.
N.
F.
P7, P79
COM4
COM13
P113, P117
COM15
P53
COM1, P76
COM15
P80
COM8, P5, P81
COM6, P56, P86, P116
P36
P63
COM31
P6
COM2
P81
P20
P52
P69
P81
P82, P83
P11
P22
INV4
P126, P127
COM4
P101
P39
P34
P65
P84
P85
P82, P83
COM7 , P29, P112
P86
COM2
P87
P68
P43
P114, P87
COM30
P67
Piovano
Pippione
Pique
Pirisino
Pirola
Pirro
Pisani
Ploeger
Plylahan
Poli
Pollastro
Pradel
Presset
Priola
Priouzeau
Prosperini
Provasi
Qu
Quagliotto
Quéléver
A.
A.C.
V.
G.
C.
V.
L.
R.
N.
T.
F.
A.
M.
E.
F.
S.
M.
F.
P.
G.
P115
P43, P88
P87
P113
P27
COM19
P117
P31
P96
P31
P6, P89
P92
P93
P90
P94
P44, P91
P105
COM7 , P112
P91
COM7, P112
Rahmani
Rahmouni
Raimondo
Raimundo
Ravera
Record
Ren
Revel
Ribes
Ribotta
Riedo
Riesenmey
Riganti
Rinaldi
Riva
Robin
Robotti
Rocchi
Rocchi
Rodriguez
Rolando
Rollo
R.
H.
S.
J.M.
M.
M.-C.
Y.
J.
M.
V.
C.
M.
C.
L.
R.
M.
E.
P.
S.
J.
B.
G.
P69
P87
P25
COM7, P78
COM6, P116, P56, P86
P92
P93
P94
P92
P30
P31, P32, P95
P96, P97
P35
P98
COM10, COM27
P87
P62, P70
P29
P71
P93
P35
P32
Rosay
Rotolo
Rouquer
Rouquer
Rum
Sabourault
Sacchetto
Sacco
Saccone
Saccone
Sainas
Sakhno
Sakkas
Salamone
Sanguineti
Santinacci
Sauvée
Scalarone
Scarano
Schirinzi
Serpe
Shand
Shearer
Shor
Signoretto
Signorile
Sikk
Simonutti
Sironi
Smarra
Solokha
Soo-Kyung
Sordello
Sourkouni
Spallarossa
Spallarossa
Sparatore
Sparatore
Sparnacci
Stevanato
Stucchi
Sun
Sundin
M.
C.
F.
J.
S.
C.
V.
A.
A.
D.
S.
Y.
P.M.
A.
E.
L.
C.
D.
D.
G.F.
L.
M.
G.C.
P.
M.
M.
L.
R.
A.
A.
P.
K.
F.
G.
A.
M.
F.
A.
K.
L.
M.
C.
A.P.
COM31
COM14, P18
P99
P99
P100
P94
P101
P124
P21, P59, P74
P102
P103, P51
COM25, P39, P49, P104
P27
COM19
P20, P105
COM20, P9
COM31
P7, P79
P28
P106
P45
P26
COM15
P66
P1, P67
P107
P108
P31
P113
P58
P74
P120
P41, P109, P54
P27
INV5, P18
COM27
P113, P117
P117
P55
COM3
P27
P54
P88
Svelle
Tabakova
Tabasso
Tachoire
Tafur Marinos
Taglialatela-Scafati
Tang
Taoufyq
Tassano
Tasso
Tei
Testa
Thea
Thétiot-Laurent
Thushara
Tinello
Todeschini
Tonelli
Toppino
Tordo
Torregrossa
Toson
Toumi
Tresso
Truccato
Trunfio
Tummino
Ugliengo
Ulian
Valdrè
Valenza
Valmalette
Venturello
Versaci
Viano
Villa
Villa
Villain
Vincenti
Vindigni
Vione
Viscardi
Visentin
S.
T.
S.
H.
J.
O.
J.
A.
E.
B.
L.
M.L.
S.
S.
K.S.
S.
V.
M.
A.
P.
R.
V.
A.
E.
M.
G.
M.L.
P.
G.
G.
F
J.C.
P.
D.
M.
C.
P.L.
S.
M.
F.
D.
G.
S.
COM15
P121, P68
P110, P55
PLE3
P111
P89, P6
P112
COM4, P3
COM10
P117
P23, P46, P57
P119
COM5
P87, P114
P115
COM6, P116
P62
P117
COM29, P14
COM31
P118
P33
COM30
P124
P81
P104
P119
P34, P49
P34
P34
INV4
COM4
COM29
P24
P120
P100
P75
COM4
COM19, P39
P68, P121
P37, P38, P122
COM12, P1, P50, P58, P91
P45
Vitillo
Volpi
Weber
Wilcken
Wisztorski
Wolfgardt
Xia
Yu
Zanella
Zanellato
Zanicchi
Zecchina
Zelano
Zelano
J.G.
G.
R.T.
R.
M.
A.
Y.
T.
R.
I.
G.
A.
V.
I.
COM15, P48
P102
COM31
P53
P94
P53
COM7, P112
P29
P68
P86
P22
P28
P111
P60

Bimetallic catalysts are widely used in catalysis in the

Transcription

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