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ENERGY
Trends and Future Challenges
JORNADAS CICECO 2016
Book of Abstracts
INDEX
INDEX
1
FOREWORD
13
SPONSORS
14
ORGANIZING COMMITTEE
15
PROGRAMME
16
ORAL ABSTRACTS
18
Adélio Mendes
TOWARDS NEARLY ZERO ENERGY BUILDINGS
19
Carmen Freire
PROTEIN FIBRILS AS FUNCTIONAL NANOSTRUCTURES FOR
THE DEVELOPMENT OF INNOVATIVE BIOMATERIALS
20
Helena Alves, Daniela Rodrigues, Isabel de Schrijver, Ana I. S.
Neves, Monica Craciun
GRAPHENE-COATED TRANSPARENT CONDUCTING FIBERS
FOR SMART TEXTILES
21
Iola F. Duarte, Raquel Saborano, Thidarat Wongpinyochit, F.
Philipp Seib
REPROGRAMMING OF ENERGY METABOLISM IN
MACROPHAGES EXPOSED TO DIFFERENT NANOPARTICLES
22
J. S. Amaral, A. Davarpanah, J. M. Vieira, V. A. F. Costa, V. S.
Amaral
FERROIC MATERIALS FOR ENERGY GENERATION AND
THERMAL MANAGEMENT
23
João F. Mano
SOFT NATURAL-BASED BIOMATERIALS FOR HUMAN TISSUE
ENGINEERING
24
1
João Nunes, Susana Pereira, Rita Pontes
BIOECONOMY AND SMART REGIONS: THE BIOREFINA-TER
PROJECT
25
Jorge Frade, Nuno Vitorino, Aleksey Yaremchenko, Andrei
Kovalevsky
MATERIALS FOR HEAT STORAGE AND CONVERSION
26
Nuno Borges Carvalho, Alírio Boaventura, Ricardo Correia,
Daniel Belo
WIRELESS POWER TRANSMISSION AS AN ENABLER OF THE
INTERNET OF THINGS
27
Teófilo Rojo
RECENT ADVANCES, PRESENT CHALLENGES AND FUTURE
TRENDS ON BATTERY TECHNOLOGIES
28
Tiago L. P. Galvão, Cristina S. Neves, Ana P. F. Caetano, Alena
Kuznetsova, Alexandre C. Bastos, Andrei N. Salak, José R. B.
Gomes, João Tedim, Mário G. S. Ferreira
USING COMPUTATIONAL TOOLS TO UNDERSTAND THE
FORMATION AND PROCESSES OF LAYERED DOUBLE
HYDROXIDES
29
Valentin Valtchev, Svetlana Mintova
HIERARCHICAL AND NANO ZEOLITES: PROSPECTS
30
POSTER ABSTRACTS
31
A. Davarpanah, X. F. Miao, L. Caron, E. Brück, J. S. Amaral, V. S.
CHALLENGES AND OPPORTUNITIES FOR MAGNETIC
REFRIGERATION AND THERMAL MANAGEMENT: THERMAL
CONDUCTIVITY OF MAGNETOCALORIC MATERIALS
32
A. L. Costa, A. C. Gomes, M. Pillinger, I. S. Gonçalves, J. Pina
and J. S. Seixas de Melo
SUPRAMOLECULAR ASSEMBLY OF CONGO RED
AGGREGATES WITHIN A LAYERED DOUBLE HYDROXIDE.
DIRECT SYNTHESIS, PHYSICOCHEMICAL AND EXCITED
STATE CHARACTERISATION
33
A.F.V. Carvalho, J.Luís, L.S.O. Pires, J.M. Oliveira
PORCELAIN FORMULATIONS FOR ROBOCASTING 3D
34
Alexander Tkach, Paula M. Vilarinho, Abilio Almeida
GIANT DIELECTRIC PERMITTIVITY AND HIGH TUNABILITY IN
Y-DOPED STRONTIUM TITANATE CERAMICS AND THEIR
RELATION TO SINTERING ATMOSPHERE
35
Alexandre M. P. Botas, Rebecca J. Anthony, Jeslin Wu, Nuno J.
Silva, Uwe Kortshagen, Rui N. Pereira, Rute A. S. Ferreira
LIGHT EMITING CRYSTALLINE SILICON NANOPARTICLES
36
2
Alice Marciel, Miguel Neto, Joel Borges, Filipe Vaz, Manuel P.F.
Graça, Rui F. Silva
STRUCTURAL, CHEMICAL, OPTICAL AND ELECTRICAL
PROPERTIES OF MO-MOXOY THIN FILMS DEPOSITED BY
REACTIVE MAGNETRON SPUTTERING
37
Alyne C. L. Mendes, Rui F. Silva, Luísa M. R. Durães
INCORPORATION OF CARBON NANOSTRUCTURES IN SILICA
AEROGELS
38
Ana Bastos, Carlos Vicente, Luís D. Carlos, Mário Lima, Paulo S.
André and Rute A.S. Ferreira
DEVELOPMENT OF A LOW COST COHERENT RECEIVER
39
Ana C. Estrada, Fábio M. Silva, Sofia F. Soares, João A. P.
Coutinho, Tito Trindade
COPPER SULFIDE NANOCRYSTALS: SYNTHESIS AND
PHOTOCATALYTIC STUDIES
40
Ana C. Gomes, Patrícia Neves, Luís Cunha-Silva, Anabela A.
Valente, Isabel S. Gonçalves and Martyn Pillinger
OXIDOMOLYBDENUM COMPLEXES FOR ACID CATALYSIS
USING ALCOHOLS AS SOLVENTS AND REACTANTS
41
Ana Celina C. Lopes, Margarida Martins, João H. P. M. Santos,
Helena Abreu, João A.P. Coutinho, Sónia P.M. Ventura
PURIFICATION OF PHYCOBILIPROTEINS USING AQUEOUS
BIPHASIC SYSTEMS BASED IN CHOLINIUM IONIC LIQUIDS
42
Ana D. G. Firmino, Ricardo F. Mendes, Duarte Ananias, Sérgio
M. F. Vilela, Luís D. Carlos, João Rocha, João P. C. Tomé, Filipe
A. Almeida Paz
MICROWAVE-ASSISTED SYNTHESIS OF A
PHOTOLUMINESCENT METAL-ORGANIC FRAMEWORK BASED
ON A TETRAPHOSPHONATE ORGANIC LINKER
43
Ana M. Ferreira, Ana Cláudia Leite, Imran Khan, Mara G. Freire
and João A. P. Coutinho
MICELLE-MEDIATED EXTRACTION OF CHLOROPHYLLS FROM
SPINACH LEAVES USING AQUEOUS SOLUTIONS OF IONIC
LIQUIDS
44
Ana P.M. Tavares, Oscar Rodriguez, João A. P. Coutinho, Ana
Soto, Mara G. Freire
LACCASE PARTITION IN IONIC-LIQUID-BASED AQUEOUS
BIPHASIC SYSTEMS
45
Ana Rita R, Teles, Helga Correia, Guilherme J. Maximo, João A.
P. Coutinho, Luís P. N. Rebelo, Ana B. Pereiro and Mara G.
Freire
ALTERNATIVE SOLVENTS CONSTITUTED BY MIXTURES OF
FLUORINATED IONIC LIQUIDS
46
3
Ana Rondão, M.F. Évora, F.M.B. Marques
Mg-PARTIALLY STABILIZED ZIRCONIA, ELECTRICAL AND
STRUCTURAL CHARACTERIZATION
47
Ana S. Neto, José M.F. Ferreira
POROUS BIPHASIC CALCIUM PHOSPHATE SCAFFOLDS
DERIVED FROM CUTTLEFISH BONE
48
Andreia F Sousa, Maria João Soares, José Bastos, Carla Vilela,
Patrick-Kurt Dannecker, M. A. R. Meier, Armando J. D. Silvestre
A NEW POLYESTER BASED ON 2,5-FURANDICARBOXYLIC
ACID AND ALIPHATIC LONG CHAIN DIOL
49
Bruno Godinho, Ricardo Santos, Nuno Gama, Rui Silva, Ana
Timmons, Artur Ferreira
PURIFICATION OF CRUDE GLYCEROL, BY-PRODUCT OF
BIODIESEL PRODUCTION
50
C. O. Amorim, J. N. Gonçalves, D. S. Tavares, C. B. Lopes, A. S.
Fenta, T. Trindade, E. Pereira, J. G. Correia, V. S. Amaral
UTILIZATION OF PAC OF RADIOISOTOPE TRACKERS AND DFT
CALCULATIONS TO DETERMINE LOCAL ENVIRONMENT OF
Hg(II) IN DITHIOCARBAMATE FUNCTIONALIZED PARTICLES
FOR MAGNETIC REMOVAL OF Hg2+ FROM WATER
51
C.O. Amorim, F. Figueiras, J.S. Amaral, P. B. Tavares, M. R.
Correia, E. Alves, J. Rocha, and V. S. Amaral
PECULIAR HIGH TEMPERATURE MAGNETOELECTRIC
COUPLING IN BaTiO3:Fe113ppm
53
Carla Vilela, Tiago D.O. Gadim, Nataly Rosero-Navarro,
Francisco J.A. Loureiro, Armando J.D. Silvestre, Carmen S.R.
Freire, Filipe M.L. Figueiredo
POLY(4-STYRENE SULFONIC ACID) AND NANOCELLULOSE
COMPOSITE MEMBRANES: MORPHOLOGICAL ANISOTROPY
AND FUEL CELL TESTS
55
Catarina M. S. S. Neves, Artur M. S. Silva, João A. P. Coutinho,
Mara G. Freire
LIQUID-LIQUID EQUILIBRIUM OF SYSTEMS FORMED BY TWO
IONIC LIQUIDS
56
Catarina Marques, Susana Olhero, Luis F. Freitas, Bianca Silva,
José M. Ferreira
FABRICATION OF CERAMICS BY ROBOCASTING
57
Cláudia Batista Lopes, Carlos Vale, Eduarda Pereira, Tito
Trindade
SYNTHESIS AND CHARACTERIZATION OF MAGNETIC
GRAPHENE OXIDE FOR ENVIRONMENTAL APPLICATIONS
58
4
Cláudia Nunes, Ana Barra, M.A. Martins, Manuel A. Coimbra,
Paula Ferreira
CHITOSAN-GENIPIN/REDUCED GRAPHENE OXIDE
BIOCOMPOSITE FILM FOR ACTIVE FOOD PACKAGING
59
D.E.L. Vieira, A.V. Fedorchenko, E.L. Fertman, A. Feher, A.B.
Lopes, A.N. Salak, M.G.S. Ferreira
NANO-MAGNETS BASED ON LAYERED DOUBLE HYDROXIDES
60
D.M. Tobaldi, S.G. Leonardi, C. Piccirillo, R.C. Pullar, M.P.
Seabra, P.M.L. Castro, G. Neri, J.A. Labrincha
Ag-TiO2 NANO-HETEROSTRUCTURES EXHIBITING GAS
SENSING PROPERTIES, VISIBLE-LIGHT ACTIVATED
PHOTOCHROMISM WITH SIMULTANEOUS PLASMONENHANCED PHOTOCATALYSIS AND ANTIBACTERIAL
ACTIVITY
61
Daniela S. Tavares, Cláudia B. Lopes, Ana L. Daniel-da-Silva,
Armando C. Duarte, Carlos Vale, Tito Trindade, Eduarda Pereira
MAGNETIC NANOPARTICLES FOR MONITORING MERCURY IN
WATERS
63
Diana Julião, Ana C. Gomes, Martyn Pillinger, Rita Valença,
Jorge C. Ribeiro, Isabel S. Gonçalves, Salete S. Balula
HETEROGENEOUS OXOMOLYBDENUM(VI)@IONIC LIQUID
SYSTEMS AS EFFECTIVE CATALYSTS FOR OXIDATIVE
DESULFURIZATION
64
Duarte Ananias, Carlos D. S. Brites, Luís D. Carlos, João Rocha
CRYOGENIC NANOTHERMOMETER BASED ON THE MIL103(TB,EU) METAL ORGANIC FRAMEWORK
65
Emanuel V. Capela, Ana Rita R. Teles, Ana Filipa M. Cláudio,
Kiki A. Kurnia João A. P. Coutinho, Mara G. Freire
HYDROGEN-BOND ACIDITY AND BASICITY OF MIXTURES OF
IONIC LIQUIDS: EXPERIMENTAL AND COSMO-RS
APPROACHES
66
Emanuelle L. P. de Faria, Selesa V. Shabudin, Ana Filipa M.
Claúdio, João A. P. Coutinho, Carmen S. Barros, Fernando M. J.
Domingues, Armando J. D. Silvestre, Mara G. Freire
ENHANCED SOLUBILITY OF NATURAL TRITERPENIC ACIDS
AND PHENOLIC COMPOUNDS WITH AQUEOUS SOLUTIONS OF
IONIC LIQUIDS
67
F. G. Figueiras, D. V. Karpinsky, P. Tavares, J. A. Moreira, V. S.
Amaral
MAGNETOELECTRIC EFFECT ENHANCEMENT BY BREAKING
THE GEOMETRIC MAGNETIC FRUSTRATION IN LuMn1+zO3+δ
CONTROLLED OFF-STOICHIOMETRY
68
5
F. Mohseni, M. J. Pereira, A. Davarpanah, T. Santos, A. BarrosTimmons, V. A. F. Costa, J. S. Amaral, V. S. Amaral
HEAT@UA
THE THERMAL RESEARCH LABORATORY OF THE UNIVERSITY
OF AVEIRO
69
Filipa L. Sousa, A. V. Girão, S. Fateixa, A. Almeida, T. Trindade
MULTIPLE EMULSION TEMPLATING OF Ag@SiO2 CAPSULES
FOR ANTIBACTERIAL APPLICATIONS
70
Flávia A. Vieira, Ricardo J. R. Guilherme, Helena Abreu, Márcia
C. Neves, João A. P Coutinho, Sónia Ventura
SURFACTANTS AS ALTERNATIVE SOLVENTS IN THE
EXTRACTION OF BIOACTIVE COMPOUNDS FROM BROWN
MACROALGAE
71
Francisca A. e Silva, Rui M. C. Carmo, Andreia P. M. Fernandes,
João A. P. Coutinho, Sónia P. M. Ventura
AQUEOUS BIPHASIC SYSTEMS FORMED BY COPOLYMERS
AND BIOCOMPATIBLE IONIC LIQUIDS
72
Helena Passos, Andreia Luís, João A. P. Coutinho and Mara G.
Freire
TEMPERATURE-SWITCHABLE IONIC-LIQUID-BASED
AQUEOUS BIPHASIC SYSTEMS
73
Hugo F.D. Almeida, Mara G. Freire, Isabel M. Marrucho
IMPROVED EXTRACTION OF FLUOROQUINOLONES WITH
RECYCLABLE IONIC-LIQUID-BASED AQUEOUS BIPHASIC
SYSTEMS
74
Idalina Gonçalves, Ana Barra, Cláudia Nunes, Manuel A.
Coimbra, Paula Ferreira
POTATO INDUSTRY BYPRODUCTS: AN ALTERNATIVE
BIOPOLYMERS’ SOURCE FOR RENEWABLE PACKAGING
MATERIALS
75
Inês C. B. Martins, M. Teresa Duarte, Luís Mafra
CONTROLLING GABAPENTIN POLYMORPHISM: IONIC LIQUIDS
AS CRYSTALLIZATION MEDIA
76
Inês Oliveira, Miguel Neto, Nuno F. Santos, Bogdan Kulyk,
Alexandre F. Carvalho, Filipe J. Oliveira, António J.S. Fernandes,
Rui F. Silva, Florinda M. Costa
ALD DEPOSITION OF ALUMINA ON UNTREATED CVD
GRAPHENE
77
J. N. Gonçalves, N. M. Fortunato, J. S. Amaral, V. S. Amaral
VOLUME DEPENDENCE OF MAGNETIC PROPERTIES IN
Co2CrGa-BASED HEUSLER ALLOYS FOR MAGNETOCALORIC
APPLICATIONS: A FIRST-PRINCIPLES STUDY
78
6
Javier Macías, Aleksey Yaremchenko, B.R. Sudireddy, S. Veltze,
P. Holtappels, Jorge Frade
VANADIUM-SUBSTITUTED SrTiO3: FROM OXIDIZED PHASES
TO SOFC ANODES
79
Jessica Silva Barbosa, Filipe A. Almeida Paz, Susana Santos
Braga
CO-AMORPHOUS g-CYCLODEXTRIN:MONTELUKAST (1:1)
ADDUCT BY MECHANOCHEMISTRY PROCEDURES, WITH
RESOURCE TO PRE MILLING OF g-CYCLODEXTRIN
80
Joana L. Lopes, Karine L. Marques, Ana V. Girão, Eduarda
Pereira, Tito Trindade
ASSEMBLY OF METAL COLLOIDS ONTO SURFACE
FUNCTIONALIZED MAGNETITE PARTICLES
81
Joana Pereira, D. Queirós, P. C. Lemos, A. Xavier, L. S. Serafim
BIOPLASTICS PRODUCTION THROUGH MIXED MICROBIAL
CULTURES ECO-ENGINEERING
82
João H. P. M. Santos, Claúdia R. Martins, João A. P. Coutinho,
Sónia P.M. Ventura
RECOVERY OF PHENOLIC COMPOUNDS FROM SALICORNIA
RAMOSISSIMA USING POLYMER-BASED AQUEOUS BIPHASIC
SYSTEMS
83
João P. Trigo, João H. P. M. Santos, Élia Maricato, Cláudia
Nunes, Manuel A. Coimbra, Sónia P. M. Ventura
PURIFICATION AND CHARACTERIZATION OF
POLYSACCHARIDES FROM ISOCHRYSIS GALBANA USING
AQUEOUS BIPHASIC SYSTEMS BASED IN IONIC LIQUIDS
84
Kiryl Zakharchuk, Szymon Obrębowski, Eugene Naumovich,
Aleksey Yaremchenko
(La,Sr)(Fe,Co)O3-BASED CATHODE CONTACT MATERIALS FOR
INTERMEDIATE-TEMPERATURE SOLID OXIDE FUEL CELLS
85
L.Marques, M. Mezouar, J-L. Hodeau
TIME-RESOLVED DIFFRACTION STUDY OF THE
TRANSFORMATION OF C60 INTO GRAPHITE-LIKE CARBON
86
Leonor S. Castro, Inês S. Cardoso, Filipa A. Vicente, Luciana P.
Malpiedi, Francisca A. e Silva, Adalberto Pessoa Jr, João A.P.
Coutinho and Sónia P.M. Ventura
THERMOSENSITIVE MICELLAR SYSTEMS AS SELECTIVE
PLATFORMS OF PURIFICATION
87
Liliana P. Silva, Mónia A. R. Martins, Vanessa Vieira, Olga
Ferreira, Simão P. Pinho, João A. P. Coutinho
STUDIES ON CHOLINIUM CHLORIDE-BASED DEEP EUTETIC
SOLVENTS PHASE DIAGRAMS
88
7
M. A. O. Lourenço, C. Siquet, M. Sardo, L. Mafra, J. Pires, M.
Jorge, M. L. Pinto, P. Ferreira, J. R. B. Gomes
DESIGN OF AMINE MODIFIED-PERIODIC MESOPOROUS
ORGANOSILICAS FOR CO2/CH4 SEPARATION:
EXPERIMENTAL AND COMPUTATIONAL STUDIES
89
M. J. Pereira, J. S. Amaral, N. J. O. Silva, V. S. Amaral, F.
Albertini, F. Casoli
LOCALLY INDUCING AND MAPPING OF STRUCTURAL
TRANSFORMATIONS IN NI-MN-GA THIN FILMS BY SCANNING
THERMAL MICROSCOPY
90
M. M. Antunes, S. Lima, P. Neves, A. L. Magalhães, E. Fazio, F.
Neri, M. T. Pereira, A. F. Silva, C. M. Silva, S. M. Rocha, M.
Pillinger, A. Urakawa, A. A. Valente
ORDERED MICRO/MESOPOROUS Zr,Al-SILICATES FOR
INTEGRATED REDUCTION AND ACID-CATALYSED
CONVERSION OF FURFURAL
91
M. Sardo, I.C.B. Martins, J.A. Fernandes, D.C. Lazarte, N.
Masciocchi, S.M. Santos, A. Fernandes, A. Antunes, V. André,
M.T. Duarte, L. Mafra
SUPRAMOLECULAR SYNTHONS IN PHARMACEUTICAL COCRYSTALS STUDIED BY NMR CRYSTALLOGRAPHY
92
M. Starykevich, A.N. Salak, M.G.S. Ferreira
1D ZINC NANOSTRUCTURES OBTAINED BY
ELECTRODEPOSITION IN POROUS TITANIA
93
Manon Wilhelm, Alexandre C. Bastos, João Tedim, Mário G.S.
Ferreira
Ni-Fe LAYERED-DOUBLE-HYDROXIDES AS CATALYSTS FOR
OXYGEN EVOLUTION REACTION
94
Márcia C. Neves, Joana Antunes, Sandra Bernardo, João A. P.
Coutinho, Tito S. Trindade, Mara G. Freire
SUPPORTED IONIC LIQUIDS FOR THE PURIFICATION OF
IMMUNOGLOBULIN Y (IGY)
95
Margarida I. Rodrigues, Sofia F. Soares, Tito Trindade and Ana
L. Daniel-da-Silva
CHITOSAN-SILICA HYBRID NANOADSORBENTS FOR THE
UPTAKE OF PHARMACEUTICALS FROM WATER
96
Margarida Martins, Flávia A. Vieira, Helena Abreu, João A. P.
Coutinho, Sónia P. M. Ventura
IMPROVEMENT OF R-PHYCOERYTHRIN EXTRACTION FROM
RED MACROALGAE USING AQUEOUS SOLUTIONS OF IONIC
LIQUIDS
8
97
Maria A. Salvador, F.M. Figueiredo, P. Ferreira
HETEROGENEOUS DOPING OF WEAK ELECTROLYTES EFFECT
OF THE OXIDE COMPOSITION
98
Marina Matos, Andreia Sousa, Armando Silvestre
DEVELOPMENT OF NEW RENEWABLE AND BIODEGRADABLE
POLY(BUTYLENE FURANDICARBOXYLATE-CO-BUTYLENE
DIGLYCOLATE) COPOLYESTERS
99
Mengistie L. Debasu, Carlos D. S. Brites, Sangeetha
Balabhadra, Helena Oliveira, João Rocha and Luís D. Carlos
CELLULAR UPTAKE MONITORING OF HEATERTHERMOMETER NANOPLATFORMS USING HYPERSPECTRAL
IMAGING
100
Mohammadreza Kamali, Maria Elisabete V. Costa, Isabel Capela
ENHANCED CATALYTIC ACTIVITY OF MESOPOROUS ZEROVALENT IRON NANOPARTICLES PREPARED UNDER
SONOCHEMICAL IRRADIATION
101
N. M. Fortunato, J. N. Gonçalves, J. S. Amaral, V. S Amaral
TOWARDS FAST COMPUTATIONAL DESIGN OF
MAGNETOCALORIC MATERIALS
102
N. Vitorino, A. Kovalevsky, J.R. Frade
IN SITU FUNCTIONALIZATION OF CELLULAR
ALUMINOSILICATES
103
N. Vitorino, S.G. Patrício, J. R. Frade, F.M.B. Marques
FUNCTIONAL CELLULAR CERAMICS FOR SUSTAINABLE
ENERGY SYSTEMS
104
Nuno Sousa, Biljana Šljukić, David Cardoso, Diogo Santos, Filipe
L. Figueiredo
105
ELECTROCATALYSTS FOR SOLID ALKALINE FUEL CELLS
Nuno Sousa, Carla Vilela, Carmen S. R. Freire, Armando J. D.
Silvestre, Filipe L. Figueiredo
A BACTERIAL CELLULOSE NANOCOMPOSITE MEMBRANE
WITH OH- CONDUCTIVITY
Olena Okhay, Gil Gonçalves, Catarina Dias, Joao Ventura,
Manuel Fernando Ribeiro da Silva, Luís Miguel Valente
Gonçalves, Elby Titus, Alexander Tkach
THIN FILM VERSUS PAPER-LIKE REDUCED GRAPHENE OXIDE:
COMPARATIVE STUDY OF STRUCTURAL, ELECTRICAL, AND
THERMOELECTRICAL PROPERTIES
9
106
107
Oliveira M. P., Kallip S., Bastos A.C., Hack T., Nixon S., Ferreira
M.G.S., Zheludkevich M.L.
SYSTEMATIC STUDY OF GALVANIC CORROSION MITIGATION
ON Zn+Fe AND AA2024+CFRP JOINTS
108
P. C. Barbosa, M.R. Soares, M. Pinto, F. A. Almeida Paz, F. M.
Figueiredo
HIGH IONIC CONDUCTIVITY IN ZEOLITIC IMIDAZOLATE
FRAMEWORK 8
109
P. Mirzadeh Vaghefi, A. Baghizadeh, M. J. Pereira, M. Willinger,
V. S. Amaral
THICKNESS DEPENDENCY OF STRUCTURE AND MAGNETIC
PROPERTIES OF La 1-xSrxMnO3THIN FILMS ON SrTiO3
SUBSTRATE
110
Pankaj Bharmoria, Dibyendu Mondal, Matheus M. Pereira,
Márcia C. Neves, Mafalda R. Almeida, João A. P. Coutinho, Mara
G. Freire
GROWTH OF FUNCTIONAL PROTEIN FIBRILS FROM EGG
WHITE PROTEOME: EFFECT OF PROTEIN CROWDING
111
Patrícia Neves, Margarida M. Antunes, Sérgio Lima, Ana L.
Magalhães, Enza Fazio, Auguste Fernandes, Fortunato Neri,
Carlos M. Silva, Sílvia M. Rocha, Maria F. Ribeiro, Martyn
Pillinger, Atsushi Urakawa, Anabela A. Valente
ONE-POT CONVERSION OF FURFURAL IN THE PRESENCE OF
A Sn,Al-CONTAINING ZEOLITE BETA CATALYST
112
Paula C. Pinheiro, Tito Trindade
SERS-ACTIVE MAGNETIC SORBENTS FOR REMOVAL AND
OPTICAL DETECTION OF PENICILLIN G
113
Paula M. C. Torres, Ana Marote, Ana R. Cerqueira, António J.
Calado, João C. C. Abrantes, Susana Olhero, Odete A. B. da
Cruz e Silva, Sandra I. Vieira, José M. F. Ferreira
PROMISING CALCIUM PHOSPHATE CEMENTS FOR
VERTEBROPLASTY APPLICATION
114
Pedro J. Carvalho, João A. P. Coutinho
DISPELLING SOME MYTHS ABOUT THE CO2 SOLUBILITY IN
IONIC LIQUIDS
115
R. Vidyasagar, K. Romanyuk, G. da Cunha Rodrigues, S.
Luchkin, Ya. Kopelevich, A. Kholkin
NANOSCALE ELECTROMECHANICAL PROPERTIES OF
GRAPHENE
116
Reda M. Abdelhameed, Artur M. S. Silva, João Rocha, Luis D.
Carlos
BUILDING LIGHT-EMITTING METAL-ORGANIC FRAMEWORKS
BY POST-SYNTHETIC MODIFICATION
117
10
Ricardo F. Mendes, Margarida M. Antunes, Patrícia Silva,Paula
Barbosa,Filipe Figueiredo, Anthony Linden,João Rocha, Anabela
A. Valente, Filipe A. Almeida Paz
LAMELLAR COORDINATION POLYMER WITH A REMARKABLE
CATALYTIC ACTIVITY
118
Ricardo M. Silva, Nicola Pinna, Rui F. Silva
VERTICALLY ALIGNED CARBON NANOTUBES-SUPPORTED
MANGANESE OXIDE NANOCOMPOSITES AS BINDER-FREE
ELECTRODES FOR ELECTROCHEMICAL CAPACITORS
119
Ricardo Serrazina, Nuno Neves, Rosa Calinas, Venkata Ramana
E., Ana Senos, Paula M. Vilarinho
ZIRCONIA BASED CERMETS: ELECTRICAL, MAGNETIC AND
THERMAL CHARACTERIZATION
120
Rita Sousa, D. Queirós, J. Pereira, A. Xavier, L. S. Serafim
SHORT CHAIN FATTY ACIDS PRODUCTION THROUGH MIXED
MICROBIAL CULTURES ECO-ENGINEERING
121
Rui M. Novais, L.H. Buruberri, M.P. Seabra, D. Bajare, J.A.
Labrincha
HIGH BUFFER CAPACITY WASTE-CONTAINING
GEOPOLYMERS TO ENHANCE BIOGAS PRODUCTION
122
Rute A. Pereira, Joana F. B. Barata, Tito Trindade
HYBRID CONJUGATES OF CORROLE AND Fe3O4@SiO2
NANOPARTICLES FOR PHOTODYNAMIC THERAPY
123
S. P. Magalhães da Silva, P. S. Lima, J. M. Oliveira
CORK-POLYMER COMPOSITES FOR INJECTION MOULDING
APPLICATIONS
124
S.G. Patrício, A.I.B. Rondão, F.M.B. Marques
ELECTROCHEMICAL PERFORMANCE OF CERIA-BASED
(NANO)COMPOSITE ELECTROLYTES
125
Sandra F. H. Correia, A. R. Frias, R. Rondão, V. T. Freitas, P. S.
André, R. A. S. Ferreira, L. D. Carlos
ORGANIC-INORGANIC HYBRIDS FOR LUMINESCENT SOLAR
CONCENTRATORS
126
Sebastian Zlotnik, David M. Tobaldi, M. Paula Seabra, João A.
Labrincha and Paula M. Vilarinho
ALKALI NIOBATE AND TANTALATE PEROVSKITES.
ESTABLISHING PHOTOCATALYTIC ACTIVITY
11
127
Siriny Laumier, Sebastian Zlotnik, Pedro L. Marques, André
Santos, Jean-René Duclere, M. Elisabete Costa, Paula M.
Vilarinho
ROLE OF STRAINS ON THE STRUCTURAL,
MICROSTRUCTURAL AND ELECTRICAL BEHAVIOUR OF LEADFREE SODIUM POTASSIUM NIOBATE THIN-FILMS
128
Sofia F. Soares, Tito Trindade, Ana L. Daniel-da-Silva
BIOPOLYMER-SILICA HYBRID PARTICLES PREPARED BY A
NON-EMULSION METHOD FOR ENVIRONMENTAL
APPLICATIONS
129
Sofia M. Bruno, Ana C. Gomes, Tânia S. M. Oliveira, Margarida
M. Antunes, André D. Lopes, Anabela A. Valente, Isabel S.
Gonçalves, Martyn Pillinger
CATALYTIC ALCOHOLYSIS OF EPOXIDES USING METAL-FREE
CUCURBITURIL-BASED SOLIDS
130
Tânia E. Sintra, Samuel N. Rocha, Andreia Luís, Ana I.M.C. Lobo
Ferreira, Fernando Gonçalves, Luis M. N. B. F. Santos, Bruno
Miguel Neves, Sónia P. M. Ventura, Mara G. Freire, João A. P.
Coutinho
CHOLINIUM SALTS WITH INCREASED WATER-SOLUBILITY
AND ANTIOXIDANT PROPERTIES
131
Tatiana R. Amarante, Patrícia Neves, Anabela A. Valente, Filipe
A. Almeida Paz, Martyn Pillinger, Isabel S. Gonçalves
METAL OXIDE-TRIAZOLE HYBRIDS AS HETEROGENEOUS OR
REACTION-INDUCED SELF-SEPARATING CATALYSTS
132
Teresa B. V. Dinis, Helena Passos, Diana L. D. Lima, Valdemar I.
Esteves, João A. P. Coutinho, Mara G. Freire
AN ALTERNATIVE EXTRACTION/CONCENTRATION APPROACH
FOR AN IMPROVED DETECTION OF WATER POLLUTION
TRACERS
133
Teresa B. V. Dinis, Helena Passos, Mara G. Freire, João A. P.
Coutinho
MIXTURES OF IONIC LIQUIDS IN AQUEOUS BIPHASIC
SYSTEMS: TAILORING THEIR FORMATION ABILITY AND
EXTRACTION EFFICIENCY
134
V. S. Amaral and the MagLab team
AN INVITATION TO MAGNETISM
135
P. Barbosa, J. M. Campos, A. Turygin, V. Shur, A. Kholkin, A.
Barros-Timmons, F.M. Figueiredo
NOVEL BIOMEMBRANES BASED ON A PLA/CHOLINE BLEND
SYSTEM
136
12
FOREWORD
CICECO once more organises the yearly JORNADAS on the coming 8th and
9th of June, at the Complexo Pedagógico of the University of Aveiro.
Energy research is transversal to CICECO covering, among others, biofuels,
piezoelectric and thermoelectric energy harvesting, fuel cells and hydrogen,
carbon dioxide separation and capture, catalytic combustion, biomass and
photovoltaics.
It is the main objective of this year to provide an organised display of
CICECO’s activities in Energy materials and processes, and to discuss the
Challenges and Future Trends to our research, always seeking to stimulate
interactions and collaborations within CICECO and invited researchers
coming from other National and International Institutions.
The programme comprises normal scientific talks associated to a set of
invited lectures on relevant topics, which are complemented with posters
covering all the activities of CICECO. The National R&D policy in the present
context of change is highlighted by the Vice-President of Fundação para a
Ciência e Tecnologia, whereas the leverage of of funding opportunities is a
matter debated with representatives of Regional, National and European
programmes. The programme closes with a Panel Discussion bringing
together actors from companies and academia for a joint discussion with the
audience to help to clarify the complex interconnections between Fossil Fuels
and the Renewable and Low-Carbon Technologies and how they will integrate
in the near future.
We welcome you to the Jornadas CICECO 2016.
The Organizing Committee
13
SPONSORS
This event was developed within the scope of the project CICECO-Aveiro
Institute of Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID /CTM
/50011/2013), financed by national funds through the FCT/MEC and when
appropriate co-financed by FEDER under the PT2020 Partnership Agreement.
14
ORGANIZING
COMMITTEE
Filipe Figueiredo
Department of Materials and Ceramic Engineering
José R. B. Gomes
Department of Chemistry
Luís Mafra
Department of Chemistry
Susana Olhero
Department of Materials and Ceramic Engineering
15
PROGRAMME
Day 1: Wednesday, 8th June
11:00 Registration
13:30 Opening Session
13:40
IT1 - Valentin Valtchev (Laboratoire de Catalyse et Spectrochimie - University of Caen Normandy)
Hierarchical and Nano Zeolites: Prospects
14:20
OC1 - Tiago Galvão (Departamento de Engenharia de Materiais e Cerâmica, Universidade de Aveiro)
Using computational tools to understand the formation and processes of layered double
hydroxides
14:40
IT2 - João Nunes (Associação BLC3 - Plataforma para o Desenvolvimento da Região Interior Centro)
Bioeconomy and Smart Regions: The BioREFINA-TER Project
15:20
OC2 - Carmen Freire (Departamento de Química, Universidade de Aveiro)
Protein fibrils as functional nanostructures for the development of innovative biomaterials
15:40 Coffee break + Poster session
16:40
IT3 - Jorge Frade (Departamento de Engenharia de Materiais e Cerâmica, Universidade de Aveiro)
Materials for heat storage and conversion
17:20
OC3 - Iola F. Duarte (Departamento de Química, Universidade de Aveiro)
Reprogramming of energy metabolism in macrophages exposed to different nanoparticles
16:40
IT4 - João Mano (Departamento de Química, Universidade de Aveiro)
Soft natural-based biomaterials for human tissue engineering
16
Day 2: Thursday, 9th June
09:00 Registration
09:30
IT5 - Adélio Mendes (Faculdade de Engenharia, Universidade do Porto)
Towards Nearly Zero Energy Buildings
10:10
OC4 - Helena Alves (Departamento de Física, Universidade de Aveiro)
Graphene-coated conducting transparent fibres for smart textiles
10:30 Coffee break + Poster session
11:00
IT6 - Nuno Borges Carvalho (Departamento de Electrónica, Telecomunicações e Informática –
Universidade de Aveiro)
Wireless Power Transmission as an Enabler of the Internet of Things
11:40
OC5 - João Amaral (Departamento de Física, Universidade de Aveiro)
Ferroic materials for energy generation and thermal management
12:00
IT7 - Teófilo Rojo (CIC-Energigune, Power Storage, Batteries and Supercaps)
Recent advances, present challenges and future trends on battery technologies
12:40 Lunch
14:00
IT8 - Miguel Castanho (Vice-Presidente da Fundação para a Ciência e Tecnologia)
Lemas e dilemas do fomento ao progresso científico em Portugal
Discussion panel
Funding Opportunities: Structural Funds and the H2020
Moderator: Paula Pais (CICECO's Technology Transfer Interface, Universidade de Aveiro)
14:40 Panelists
- Sofia Azevedo (Gabinete de Promoção do Programa Quadro de I&DT, NCP Nanotecnologias,
Materiais Avançados e Fabrico e Processos Avançados e NCP Aspetos Legais & Financeiros)
- Conceição Carvalho (Comissão de Coordenação e Desenvolvimento Regional do Centro)
15:40 Coffee break
Discussion panel
Fossil Fuels and the Renewable and Low-Carbon Energy Technologies: Is there a Future on
Integration?
Moderator: Nelson Martins (Departamento de Engenharia Mecânica, Universidade de Aveiro)
Panelists
16:00 - Sérgio Salústio (R&D Director of Bosch Thermotechnology)
- Rui Baptista (GALP Energia)
- Teófilo Rojo (CIC-Energigune)
- Pedro Ferreira (EDP Inovação)
- Sandra Oliveira (Business Development Director, ENC ENERGY)
- Svetlana Mintova (Laboratoire de Catalyse et Spectrochimie (LCS) - University of Caen Normandy)
- Miguel Castanho (Vice-Presidente da Fundação para a Ciência e Tecnologia)
18:00 Closing session
20:00 Dinner
17
ORAL
ABSTRACTS
18
TOWARDS NEARLY ZERO ENERGY BUILDINGS
Adélio Mendes
E-mail: [email protected]
In 2015 the perovskite solar cell technology, which was born in 2009, broke a new
energy conversion record reaching an astonishing 20.1 % of certificated efficiency [1].
This thin film technology promises to bring down the price of the photovoltaic panels,
which presently is ca. 11 ¢€·kW -1·h-1 [2]. Moreover, perovskite solar cell technology is
efficient harvesting diffuse light [3] and it can be produced with various colours [4] and
patterns, promising a deep merging with buildings. However, PV electricity is not
dispatchable and it is necessary to couple the generation with the electricity storage
for a complete integration into buildings.
The redox flow battery technology aims to beat the competitors for stationary storage
with promising round trip costs of 3 ¢€·kW -1·h-1 by 2050. More recently, however, the
so-called solar redox flow batteries, that consider a photoelectrode for directly charging
a redox flow battery, integrate sunlight conversion into electrochemical storable energy
and into thermal energy, in a cogeneration system. This emerging technology
promises to bring dispatcheable sunlight electricity to unprecedented low prices.
This talk addresses these and related topics shedding light on the future of the energy.
References
[1] – http://www.nrel.gov/ncpv/images/efficiency_chart.jpg, accessed on November of
2015.
[2] - http://iet.jrc.ec.europa.eu/remea/sites/remea/files/reqno_jrc83366_jrc_83366_
2013_pv_electricity_cost_maps.pdf, accessed on November of 2015.
[3] – Ball, J., Stranks, S., Hörantner, M., Hüttner, S., Zhang, W., Crossland, E.,
Ramirez, I., Riede, M., Hohnston, M., Friend, R., Snaith, H., “Optical properties and
limiting photocurrent of thin-film perovskite solar cells”, Energy & Environmental
Science, 8, 602-609, 2015.
[4] – Zhang, W., Anaya, M., Lozano, G., Calvo, M., Johnston, M., Míguez, H., Snaith,
H., “Highly efficient perovskite solar cells with tunable structural color”, Nano Letter,
15, 1698-1702, 2015.
19
PROTEIN FIBRILS AS FUNCTIONAL NANOSTRUCTURES FOR THE
DEVELOPMENT OF INNOVATIVE BIOMATERIALS
Carmen Freire
CICECO - Aveiro Institute of Materials, Department of Chemistry, University of
Aveiro, 3810-193 Aveiro, Portugal
Protein fibrils, also known as amyloid fibrils, result from the self-assembly of
unfolded peptides or proteins, are characterized by a highly organized
quaternary structure consisting on conformed β-sheets, linked by hydrogen
bonds, that introduce a rigid internal order to the fibrils, and a morphological
appearance of bundles of unbranched filaments orthogonally twisted along the
axis of each nanofibril [1,2].
Naturally, protein fibrils are found in organs and tissues in the form of insoluble
deposits, and unlike other protein structures, they do not have any structural,
supportive or motility role, but it is believed that several protein fibrils have also
biological functions, besides the most known fact that they are associated with
several diseases known as amyloidosis [3]. Since the discovery of the direct
relation of protein fibrils formation with for example Alzheimer and Parkinson
diseases, research efforts were largely focused on preventing the formation of
the protein misfolds present on such diseases.
More recently, several studies on the in vitro synthesis of protein fibrils have
been engaged, aiming at exploring these nanostructures as a source of original
biomaterials. Due to their biological nature and unique properties [4], as
remarkable mechanical properties, thermal stability, insolubility in aqueous
media and the high resistance against chemical and biological degradation,
protein fibrils, like other biological nanofibers, have been explored particularly
for biomedical application, including the development of biosensors, drug
delivery systems, bioelectronics and tissue reparation. However, the
exploitation of protein fibrils in the development of new materials relies on their
efficient and timesaving preparation; the conventional methodologies to
produce protein fibrils involve normally quite long incubation periods.
This communication aims to report the production of protein fibrils following two
timesaving approaches, namely a microwave assisted synthesis (for insulin)
and the use of ionic liquids and deep eutectic solvents as incubation media (for
lysozyme). Preliminary results on the use of these bio-based fibrils to produce
innovative materials will be also highlighted.
[1] A. Portillo, M. Hashemi, Y. Zhang, L. Breydo, V.N. Uversky, Y.L.
Lyubchenko, BBA - Proteins Proteomics. 2014, 1854, 218–228.
[2] J. Greenwald, R. Riek, Structure 2010, 18, 1244–1260.
[3] D.J. Selkoe, Nature 2003, 426, 900–904.
[4] P. Knowles, A.W. Fitzpatrick, S. Meehan, H.R. Mott, M. Vendruscolo, C.M.
Dobson, et al., Science 2007, 318, 1900–1903.
20
GRAPHENE-COATED TRANSPARENT CONDUCTING FIBERS FOR
SMART TEXTILES
Helena Alves1, Daniela Rodrigues1, Isabel de Schrijver2, Ana I. S. Neves3,
Monica Craciun3
1CICECO,
Portugal
2Centexbel,
3University
Belgium
of Exeter, UK
The development of electronic textiles is one of the hottest topics in organic
electronics. There are already examples of smart textiles in garments for
monitoring physiologic and biomechanical signals. However, manufacturing
schemes for current applications rely on the integration of off-the-shelf
electronic components mounted on a textile substrate. Such components are
silicon-based, thus unsuitable for applications where flexibility and faulttolerance are required. Organic electronics is an alternative to conventional
silicon technology and can overcome these limitations. In this sense, graphene,
with high optical transparency and electrical conductivity, is a promising
material to be used as electrode.
We recently developed an approach consisted in coating specially designed
polypropylene and polylactide fibers with graphene. Monolayer graphene was
grown on copper foil by low pressure chemical vapor deposition (CVD) using
methane as the carbon source, and wet-transferred to the fibers after copper
etching. With this method we have demonstrated that transparent monolayer
graphene can coat textile fibers by wet transfer, forming a highly conductive
thread with negligible change in transparency [1].
The method is effective in other type of thermoplastic fibers, such as nylon,
polyethylene or polyamide, as well directly to multifilament fibers or fabrics. A
graphene solution was also developed, based on ultrasonic exfoliation of
graphite, which allowed textile coating by other solution methods such as drop
cast and dip coating. Conductance of textile coated with graphene solution is
lower than CVD graphene, yet it can be substantial improved by doping.
Resistance of graphene coated textiles varies with exposure to certain gases,
which adsorb to surface, demonstrating potential application to textile sensors.
In addition to electrical properties, fibers coated with graphene can also induce
antimicrobial propertied to textiles. These first transparent electrodes
completely embedded in a textile fiber can pave the way for the development
of devices for wearable electronics.
[1] A. I. S. Neves, T. H. Bointon, L. V. Melo, S. Russo, I. de Schrijver, M. F.
Craciun, H. Alves, Scientific Reports 2015, 5, 9866.
21
REPROGRAMMING OF ENERGY METABOLISM IN MACROPHAGES
EXPOSED TO DIFFERENT NANOPARTICLES
Iola F. Duarte1, Raquel Saborano1, Thidarat Wongpinyochit2, F. Philipp Seib2,3
1
Aveiro, 3810-193 Aveiro, Portugal.
2
3
Strathclyde Institute of Pharmacy and Biomedical Sciences, University of
Strathclyde, 161 Cathedral Street, Glasgow, G4 0RE, UK.
Leibniz-Institut für Polymerforschung Dresden e.V., Max Bergmann Centre for
Biomaterials Dresden, Hohe Strasse 6, 01069 Dresden, Germany.
Macrophages are important phagocytic cells of the immune system which, among
other functions, strongly determine the biological responses to foreign particles,
including nanoparticles (NPs) administered intravenously for therapeutic purposes.
Thus, knowledge on the interaction between macrophages and NPs is central to the
evaluation and design of more effective nanomedicines. Recent findings have
established metabolic reprogramming as a key element of macrophages’ functional
behaviour, rather than being simply involved in energy generation and biosynthesis
[1]. Therefore, assessment of changes in macrophages’ metabolism upon exposure to
NPs may potentially give new insights into biological outcomes such as inflammation
or toxicity, and provide important leads for the tailored design of nanomedicines.
In this work, we have looked at the metabolic responses of murine macrophages
(RAW 264.7 cells) to three types of nanoparticles currently being explored or
developed as drug carriers, namely poly(lactic-co-glycolic acid) (PLGA), silica and silk
NPs (ranging from 100 to 125 nm in diameter). The changes in the intracellular and
extracellular metabolome of macrophages, at different NP concentrations and
exposure times, were assessed by 1H NMR analysis of cell extracts and culture media.
The results showed evidence of increased glycolysis and reduced Krebs cycle activity,
consistently with a pro-inflammatory phenotype. Moreover, a number of other changes
in amino acids, osmoregulators and energy-related metabolites were unveiled.
Although the magnitude of some variations was clearly NP-dependent, most changes
were seen across all exposed cells, revealing a common metabolic signature for the
different NP types studied.
[1] L.A.J. O’Neill, E.J. Pearce, The Journal of Experimental Medicine 2015,
213, 15-23.
22
FERROIC MATERIALS FOR ENERGY GENERATION AND THERMAL
MANAGEMENT
J. S. Amaral1,2, A. Davarpanah1, J. M. Vieira3, V. A. F. Costa4, V. S. Amaral1
1Departamento
2IFIMUP
de Física and CICECO, Universidade de Aveiro, Portugal
and IN-Institute of Nanoscience and Nanotechnology, Universidade
do Porto, Portugal
3Departamento
4Departamento
de Engenharia de Materiais e Cerâmica and CICECO,
Universidade de Aveiro, Portugal
de Engenharia Mecânica and TEMA, Universidade de Aveiro,
Portugal
A viable and sustainable global energy ecosystem relies heavily on the efficiency of
generation and consumption processes. In terms of energy generation, diversification
is crucial to avoid geopolitical issues and weaknesses to changing environmental
factors. In both the US [1] and Europe [2], energy production is over 50% fossil fuelbased, while renewable sources amount to less than 25%. The desired decrease in
fossil fuel dependence must come with an increase of competitiveness of alternative
energy sources. In terms of energy use, both commercial and residential building
sectors have an energy end-use of over 50% in thermal management (space heating
and cooling, water heating, refrigeration) [3].
In this talk, we will discuss applications of ferroic materials (ferroelectrics, ferroelastics,
ferromagnets) for energy generation by thermal motors and heat management by heatpumps. An overview of the challenges and opportunities of these technologies is
presented, with a particular focus on magnetic materials and devices. We also discuss
the applicability of these materials as heat switches, for advanced structural and device
heat-flow management.
[1] U.S. Energy Information Administration, 2015.
[2] Eurostat, 2013.
[3] U.S. Department of Energy Buildings Energy Data Book, 2010.
23
SOFT NATURAL-BASED BIOMATERIALS FOR HUMAN TISSUE
ENGINEERING
João F. Mano
Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro,
Portugal.
The possibility of regenerating organs and tissues would bring new possibilities
of improving current treatments or find solutions for untreatable situations.
Tissue Engineering (TE) has been integrating principles of engineering,
materials science, biology and health sciences in order to develop regenerativebased therapeutic strategies combining stem cells and biomaterials.
Biodegradable polymeric materials have been proposed to support cellular
activity and new tissue formation in TE strategies. In particular, natural-based
macromolecules offer beneficial biological signals and structural properties to
be used in such applications. Their typical hydrophilic character also permits to
prepare hydrogels or other soft biomaterials that can recapitulate the high
hydrated environment of native tissues. Examples are presented on hydrogel
systems prepared from marine-derived polysaccharides, that can be used to
encapsulate living cells. Taking into account the large variety of choices among
such kind of materials, high-throughput methodologies have been developed to
probe large number of combinations of biomaterials-cells interactions,
permitting to select more promising formulations.
Natural-based biomaterials may be processed into a variety of shapes.
Examples are shown on the fabrication of spherical-based devices that could
have well designed characteristics to be used in regenerative medicine.
Particles may be used to support cellular organization over their surface, acting
as cells supports for injectable scaffolds. By decorating the surface with
antibodies these particles are able to recruit specific cell populations, enhancing
the therapeutic potential of such system. In another strategy, liquefied capsules
protected by a nanostructured permselective shell can be fabricated to entrap
viable cells. The presence of solid microparticles inside such capsules offers
adequate surface area for adherent cell attachment increasing the biological
performance. The liquid environment allows for a free-organization in the space
of the cells towards the formation of new microtissues. Though still a long-term
goal, advances based on the presented technologies may have potential in the
development of future devices for advanced regenerative therapies.
24
BIOECONOMY AND SMART REGIONS: THE BIOREFINA-TER PROJECT
João Nunes1, Susana Pereira1, Rita Pontes1
1BLC3
Association - Technology and Innovation Campus, Rua Nossa
Senhora da Conceição, 2 Lagares, 3405-155 Oliveira do Hospital
The European Union 2020 Strategy, announced in 2010, includes Bioeconomy as an
important component with three major strategic priorities: smart growth; sustainable
growth; and, inclusive growth. Bioeconomy refers to the sustainable production and
transformation of organic natural resources in a variety of bioproducts, food,
biomolecules, other industrial products and energy. Includes all industries, sectors,
management operations and any other way to use natural resources, including organic
wastes. In this way, the BioREFINA-TER project has emerged.
BioREFINA-TER represents a multidisciplinary project of R&D designed to apply
advanced technologies, within a network, to the conversion of wastes from forest
exploration and farming, and also from land which does not have any farming potential,
to 2nd generation biofuels intended to replace fossil fuels. Being a crucial project for
the development of “Bioeconomy and Smart Regions” in territories with specific
economic development needs, low population density and in menace.
The present project has managed to bring together an international knowledge network
of 55 R&D organizations from 9 European countries. Starting in 2001, the first stage,
allowed progression of the scientific and technical knowledge regarding the conversion
of heathland biomass and forest residues to 2nd generation advanced biofuels.
The main aim of BioREFINA-TER project is the construction of an industrial
demonstration biorefinery unit, with a capacity of 25 million litters per year of 2nd
generation biofuels. The pilot territory will cover the cities of Arganil, Góis, Oliveira do
Hospital and Tábua, and this pilot unit will be used for replication throughout Portugal.
Internationally, this project also aims to create the first country with full energy
autonomy, meaning that the natural resources existent are enough to generate power
for the current economic activity consumption.
This innovation project, aspires to rejuvenate and revitalize the socio-economic fabric
of the region, being also considered an alternative to the fight of large-scale forest fires
and the mitigation of the environmental, economic and social impacts caused by this
paradigm. According to a recent survey made by BLC3, forest fires may represent a
national economic loss of 800 to 1,000 million euros [1]. An annual saving of 4.500 to
6.000 million euros in petroleum import will allow Portugal to tackle two of the major
problems currently facing - forest fires and petroleum dependency.
[1] J. M. S. Nunes, Modelo de avaliação de sustentabilidade integrado e
global para ecossistemas florestais: Bioenergia, produtos derivados de
madeira e co-produtos 2015, PhD Thesis, Faculty of Sciences and Technology,
University of Coimbra.
25
MATERIALS FOR HEAT STORAGE AND CONVERSION
Jorge Frade1, Nuno Vitorino1, Aleksey Yaremchenko1, Andrei Kovalevsky1
1CICECO
– Aveiro Institute of Materials, University of Aveiro, 3810-193
Aveiro, Portugal
Utilization of solar heat is marginal if one considers industrial needs (pulp &
paper, metallurgy, cement, ceramics, glass), and domestic consumption (hot
water, heating); this is often limited by gaps between consumer needs and
availability of renewable or waste heat.
Thus, heat storage and conversion are strategic to raise the share of
renewables. A promising concept is latent heat storage in PCMs for delayed
heat uses or thermal management. One derived reliable solutions for latent heat
charge/discharge, and established selection criteria for representative
requirements of high energy density, high power, fast response, etc., including
specific temperature ranges. Key limitations of known PCMs stimulated novel
concepts such as self-organization of highly conducting inclusions, shape
stabilization in emulsified PCMs, etc.
Thermoelectric conversion is also currently limited by poor efficiency and
insufficient stability. Thus, our research on oxide thermoelectrics seeks
prospects to operate at much higher temperatures and under different redox
conditions. Guidelines to boost performance are based on structural,
microstructural and defect chemistry engineering, with positive impact on
electrical properties, while minimizing also thermal leakage.
26
WIRELESS POWER TRANSMISSION AS AN ENABLER OF THE
INTERNET OF THINGS
Nuno Borges Carvalho1, Alírio Boaventura1, Ricardo Correia1, Daniel Belo1
1Instituto
de Telecomunicações, Departamento de Electrónica,
Telecomunicações e Informática, Universidade de Aveiro Email: nbcarvalho@ ua.pt
Society is evolving toward creating smart environments where a multitude of
sensors and devices are interacting to deliver an abundance of useful
information.
Essential to the implementation of this Internet of things is the design of energy
efficient systems aiming toward a low-carbon-emission society.
Within this context, wireless power transfer appears as an alternative to
providing these sensors and devices with self-sustained operation.
The concept of power transmission by electromagnetic waves initially appeared
in the works of Hertz and Tesla [1]. The circuit that is used to convert
electromagnetic power to dc power is the rectenna, which was patented by
W.C. Brown in 1969 and consists of an active antenna combining a radiating
element (antenna) with a rectifier circuit [2].
Initial applications of microwave power transmission focused on applications for
RFID (RF Identification) and specially designed circuits. Today this concept is
already engaged in charging gadgets batteries, electrical car batteries and more
recently in powering up wireless sensors. [3]
Nevertheless there are still a significant number of issues to resolve and a
multitude of cross-disciplinary engineering themes to address, specially by
combining electrical and material engineering [3-4].
In this talk some of these issues will be explored further and some new vision
on this field will be presented.
[1]
[1] W. C. Brown, “The history of power transmission by radio waves,”
IEEE Trans. Microwave Theory Tech., vol. 32, no. 9, pp. 1230–1242, 1984.
[2]
[2] W. C. Brown, R. H. George, and N. I. Heeman, “Microwave to dc
converter,” U.S. Patent 3 434 678, Mar. 25, 1969.
[3]
N. B. Carvalho, A. Boaventura, et al “Wireless Power Transmission: R&D
Activities within Europe”, Trans. Microwave Theory and Techniques, Trans.
Microwave Theory and Techniques, p.p.: 1031 - 1045 ,Vol. 62, Issue 4, April
2014.
[4]
L.R. Roselli, N.B.C. Carvalho, F.A. Alimenti, P. M. Mezzanotte, G.O.
Orecchini, M. V. Virili, C. M. Mariotti, R. Gonçalves, P. Pinho, Smart Surfaces:
Large Area Electronics Systems for Internet of Things Enabled by Energy
Harvesting, Proceedings of the IEEE, Vol. 102, No. 11, pp. 1723 - 1746,
November, 2014.
27
RECENT ADVANCES, PRESENT CHALLENGES AND FUTURE TRENDS
ON BATTERY TECHNOLOGIES
Teófilo Rojo
Departamento de Química Inorgánica. Facultad de Ciencia y Tecnología.
UPV/EHU, P.O. Box 644, 48080, Bilbao, Spain. e-mail [email protected]
CIC energiGUNE, Parque Tecnológico de Álava, Albert Einstein 48, 01510,
Miñano, Spain.
Energy storage possesses an important role in order to rationalize the use of
both fossil and renewable energy sources. Electrochemical Energy Storage
(EES) is a valuable approach for improving the reliability and overall use of the
entire power system (generation, transmission and distribution). Between the
EES system, the batteries could bring significant improvements in pollution
reduction and efficient use of renewable energy sources. Rechargeable
batteries have actually played a key role of the technological progress in recent
years. A clear example of this is the indispensable role of the rechargeable Liion batteries in facilitating the revolution of portable electronics.
Li-ion batteries ,however, have almost reached their limits in terms of energy
density (75-200 Wh/kg) , cycle life (1000 cycles at > 80% of capacity), and
charge/discharge rate capabilities (1C).To satisfy the industrial needs such as
electrical vehicle(EV) and/or stationary grid storage developing of new batteries
is required. Metal-oxygen/air batteries are considered the most attractive
alternative to Li-ion batteries when high energy density is a critical requirement.
Performance requirements of electrochemical energy storage (EES) for
stationary use depend on the application markets that are broad and varied in
power and energy ratings , the ratio of power to energy , the discharging time
,etc. The reliability, durability, and safety of energy storage systems must be
addressed for stationary applications. However, cost is probably the most
important and fundamental issue of EES for a broad market penetration. A
number of battery technologies such as leadacid, Ni-metal, were developed
over the last century. Recently, interest has growing in redox flow batteries and
sodium-sulfur batteries, even Li-ion batteries were stacked to a few MW levels
for grid demonstration. An important effort to improve the safety in the Na-S and
Zebra technologies has been carried out by reducing the operating
temperature. It is worth mentioning the evolution of the research developed in
the last four years in the non aqueous sodium ion systems. The results obtained
in the prototyping of these batteries allow us to deduce an interesting future for
this low cost emerging technology.
In this talk we will present a general overview of the current challenges and
future trends on battery technologies and the work developed at CICEnergigune on these technologies.
28
USING COMPUTATIONAL TOOLS TO UNDERSTAND THE FORMATION
AND PROCESSES OF LAYERED DOUBLE HYDROXIDES
Tiago L. P. Galvão1, Cristina S. Neves1, Ana P. F. Caetano1, Alena
Kuznetsova1, Alexandre C. Bastos1, Andrei N. Salak1, José R. B. Gomes2,
João Tedim1, Mário G. S. Ferreira1
1CICECO-Aveiro
Institute of Materials, Department of Materials and Ceramic
Engineering, University of Aveiro, 3810-193 Aveiro, Portugal
2CICECO-Aveiro
Institute of Materials, Department of Chemistry, University of
Layered double hydroxides (LDHs) are able to intercalate different functional
molecules in the anionic form and are used in a wide range of applications
including corrosion sensing and protection, catalysis for energetic applications
and biocompatible drug delivery.
Hydrogeochemical modeling and periodic density functional theory (DFT)
calculations have been used to gain insights into LDHs’ formation, structure and
morphology.
The first modeling tool rendered insights into the mechanisms of crystallite and
particle growth. It can be a promising tool to model and optimize the synthesis
of layered double hydroxide-based materials for industrial applications [1].
Whereas periodic DFT calculations have been used to understand the
immobilization of functional molecules to be released upon demand, the typical
plate-like morphology of LDH particles, their exfoliation to obtain nanosheets
and the interface of LDH films grown on metallic surfaces.
[1] T. L. P. Galvão, C. S. Neves, A. P. F. Caetano, F. Maia, D. Mata, E.
Malheiro, M. J. Ferreira, A. C. Bastos, A. N. Salak, J. R. B. Gomes, J. Tedim,
M. G. S. Ferreira, J. Colloid Interface Sci. 2016, 468, 86.
29
HIERARCHICAL AND NANO ZEOLITES: PROSPECTS
Valentin Valtchev,1,2 Svetlana Mintova2
1
2
Department of Chemistry, Jilin University, Changchun, China
Normandie Univ, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et
Spectrochimie, 6 boulevard Maréchal Juin, 14000 Caen, France
E -mail: [email protected]
Microporous zeolite-type materials are widely used as catalysts and adsorbents
since they contain regular channels and cavities with sizes below 2 nm, large
specific surface area and acid-base properties. However, the catalytic and
separation reactions often face severe diffusion limitations that lead to pore
blocking. Decreasing the diffusion path by use of nano-sized or introduction of
a system of larger (meso- and/or macro-) pores in micron-sized zeolite crystals
are commonly used approaches to circumvent the diffusion limitation. This
presentation will provide a broad overview of the advantages and
disadvantages of bottom up (nano crystals synthesis) and top down
(demetallation) approaches for optimization of zeolite performance.
The first part of the talk will provide an overview of the post-synthetic treatments
for hierarchical zeolites preparation. Further a newly developed approach,
based on etching with fluoride solutions, will be highlighted. Buffering HF
solutions with NH4F is shown to shift the equilibrium to the most reactive
species (FHF-), which are not Al/Si selective. Thus, after a proper adjustment
of HF and NH4F concentrations, non-selective chemical etching of the zeolite
framework is achieved. The formation of secondary pore system takes place
without change of the chemical composition of zeolites, and a negligible
increase in the zeolite external surface without formation of extra framework
species is observed. Hence, the zeolite textural and compositional properties
can be decoupled, in sharp contrast to the multifarious consequences of
existing demetallation processes.
The second part of the talk will summarize recent findings in the understanding
of zeolite nucleation in organic template-free hydrogel systems. Special
attention will be paid to Na-rich aluminosilicate systems yielding zeolites with
FAU-, EMT- and LTA-type framework topology. New insights in: i) the
relationship chemical composition - gel structure; and ii) the temporal and
spatial location of proto zeolite nuclei will be reported. These new insights are
used to synthesize nanosized zeolites with narrow particle size distribution and
novel properties.
30
POSTER
ABSTRACTS
31
CHALLENGES AND OPPORTUNITIES FOR MAGNETIC REFRIGERATION
AND THERMAL MANAGEMENT: THERMAL CONDUCTIVITY OF
MAGNETOCALORIC MATERIALS
A. Davarpanah1, X. F. Miao 2, L. Caron 2, E. Brück 2, J. S. Amaral 1, V. S.
Amaral 1
1
Department of Physics / CICECO - Aveiro Institute of Materials, University of Aveiro
(Aveiro,Portugal)
2
Department of Radiation Science & Technology, Delft University of Technology
(Delft, The Netherlands)
E-mail: amin.davarpanah@ ua.pt
Magnetocaloric materials as the most crucial element of the magnetic refrigeration
systems should have a strong magnetocaloric effect, together with optimized thermal
properties. While enhancing the MCE of refrigerant materials has been the object of
extensive efforts [1], studies on thermal conductivity of magnetocaloric materials are
seldom reported [2]. In this work the temperature dependence of the thermal
conductivity K(T) of two families of magnetocaloric materials and its impact on device
efficiency is studied. As presented in Fig. 1, the thermal conductivity measured from
245 K up to 400 K, spanning the magnetic transitions, is of the same order of
magnitude for Mn-Fe-P-Si (between 1.5 to 4 W/m/K) and La-Ca-Sr-Mn-O samples (1
to 3.2 W/m/K), with contrasting behaviour.
Thermal conductivity W/m/K
4.0
Mn1.3Fe0.65P0.4Si0.6
Mn Fe P Si
1.25
0.7 0.45
0.55
-------------------------------------
3.5
La2/3(Ca1-xSrx)1/3MnO3
X=0.00
X=0.30
X=0.06
X=1.00
X=0.15
3.0
2.5
2.0
1.5
1.0
250
270
290
310
330
350
370
390
Temperature (K)
Figure 1. Thermal conductivity of Mn1.25Fe0.7P0.45Si0.55 and Mn1.3Fe0.65P0.4Si0.6 and La2/3(Ca1x= 0, 0.06, 0.15, 0.3, and 1
xSrx)1/3MnO3,
Thermal conductivity trends are correlated to the magnetic transition, emphasizing
the effect of magnetic transition type on the rate of thermal conductivity change in the
vicinity of the Curie temperature (TC). We show that the thermal conductivity change
of the two families of magnetocaloric refrigerants within their working temperature
range can exceed 50% of their value at TC. For a given device geometry, the observed
changes of K within a 20K operating span around TC may induce a cooling power loss
exceeding 50% due to optimal frequency changes during operation. In addition, the
sharp change of K close to TC is a promoting property to be implemented in thermal
switches and diodes. It is highlighted that in order to optimize magnetic refrigeration
devices and magnetocaloric materials, a full description of the temperature and fielddependence of thermal conductivity is needed and should be adequately considered.
[1]
[2]
Brück et al, J. Magn. Magn. Mater. 2007, 310, 2793.
Turcaud et al, Scr. Mater. 2013, 68, 510.
32
SUPRAMOLECULAR ASSEMBLY OF CONGO RED AGGREGATES
WITHIN A LAYERED DOUBLE HYDROXIDE. DIRECT SYNTHESIS,
PHYSICOCHEMICAL AND EXCITED STATE CHARACTERISATION
A. L. Costa1,2, A. C. Gomes2, M. Pillinger2, I. S. Gonçalves2, J. Pina1
and J. S. Seixas de Melo1
1
2
Coimbra Chemistry Centre, University of Coimbra
CICECO – Aveiro Institute of Materials, University of Aveiro
In this work we provide insights into the photophysical properties of Congo Red
(CR) in solution and have demonstrated that the anionic dye can be
incorporated into a layered double hydroxide (LDH) by the direct coprecipitation
method.
The very low fluorescence quantum yield (~10-4) for CR in solution (H2O,
DMSO) together with the absence of a triplet state indicates that internal
conversion (IC) is the dominant deactivation route with more than 99.99% of
the quanta loss. No evidence for an excited state proton transfer was observed
from fs-transient absorption data. The high IC value is associated to the energy
gap law.
The absorption and fluorescence emission spectra of the LDH-incorporated dye
were compared with data for CR in the solid-state and in solution. The results
point to the presence of slipped cofacial J-type aggregates of the dye in the
intercalation compound (see Figure).
Acknowledgements: Funding by the FCT, FEDER, COMPETE, PT2020 is thanked:
Coimbra Chemistry Centre (PEst-OE/QUI/UI0313/2014), CICECO-Aveiro Institute of
Materials (POCI-01-0145-FEDER-007679, FCT ref. UID/CTM/50011/2013), Project
FCOMP-01-0124-FEDER-029779 (FCT ref. PTDC/QEQ-SUP/1906/2012), grants to
A.L.C. (SFRH/BD/88806/2012), A.C.G. (SFRH/BPD/108541/2015) and J.P.
(SFRH/BPD/108469/2015).
33
PORCELAIN FORMULATIONS FOR ROBOCASTING 3D
A.F.V. Carvalho1, J.Luís1, L.S.O. Pires1,2,3, J.M. Oliveira1,2
1School
2
3
of Design, Management & Production Technologies Northern Aveiro,
University of Aveiro, Oliveira de Azeméis, PT
CICECO-Aveiro Institute of Materials, University of Aveiro, PT
Dept. Materials & Ceramic Engineering, University of Aveiro, PT
In recent years, additive manufacturing has suffered a remarkable growth with
the development of new technological solutions. These technologies allow the
fabrication of complex models that are difficult, time consuming or impossible
to produce recurring to traditional manufacturing processes. Regardless of
being a valuable tool in the development of prototypes, additive technologies
are now being used as fabrication techniques. The additive manufacturing of
ceramics has a lot of potential to readily produce near-final shape pieces with
3D free form. Robocasting 3D (R3D) is a liquidbased technique able to produce
ceramics. This technique uses a system based on plastometers, robotically
controlled in which materials, in form of suspension, pastes or liquids are
deposited layer by layer.[1,2]
The main goal of the present work is to develop industrial ceramic formulations
with suitable rheological parameters to be apply in R3D.
Porcelain paste-like suspensions with high solid contents and proper
pseudoplastic behavior were prepared to allow fast drying and form retention
during the additive construction process.
A Fab@home robocasting model 3 – Dual syringe was used. The syringe has
an inner diameter of ~1000 µm. The robocasting settings were adjusted as a
function of the rheological properties of the suspensions.
Paste-like suspensions and printed models were characterized by
Thermogravimetry
(TG) and Differential Thermal Analysis (DTA), Coulter Counter method,
Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). The
viscosity was measure by Brookfield DV-E Viscometer.
The printed models were sintered in air at 1350 oC for 2 hours. The final
products exhibited high density and good mechanical properties. Robocasting
provided the possibility to manufacture porcelain products based on industrial
pastes, suggesting its potential as a 3D fabrication technique.
U. Scheithauer, E. Schwarzer, H.J. Richter, T. Moritz. Thermoplastic 3D
Printing—An Additive Manufacturing Method for Producing Dense Ceramics,
International Journal of Applied Ceramic Technology 12 (2015) 26-31.
[2]
J. N. Stueckera, J. Cesarano III, D. A. Hirschfeld. Control of the viscous
behavior of highly concentrated mullite suspensions for robocasting, Journal of
Materials Processing Technology 142 (2003) 318-325.
[1]
34
GIANT DIELECTRIC PERMITTIVITY AND HIGH TUNABILITY
IN Y-DOPED STRONTIUM TITANATE CERAMICS
AND THEIR RELATION TO SINTERING ATMOSPHERE
Alexander Tkach1, Paula M. Vilarinho1, Abilio Almeida2
1
CICECO – Aveiro Institute of Materials, Department of Materials and Ceramic
Engineering, University of Aveiro, 3810-193 Aveiro
2
IFIMUP and IN – Institute of Nanoscience and Nanotechnology, Department of
Physics and Astronomy, Faculty of Science of University of Porto, Rua do Campo
Alegre, 687, 4169-007 Porto
Development of giant-permittivity and high-tunability dielectric materials has
attracted great interest because of growing demand for smaller and faster
electronic devices. A number of materials displaying the giant dielectric
permittivity, mainly arising from extrinsic contributions of polarization such as
Maxwell-Wagner interfacial polarization or internal barrier layer capacitor effect,
and important for supercapacitor applications has previously been reported.
Many materials have also been indicated to possess a high tunability of the
dielectric permittivity by dc electric field at temperatures near the permittivity
peak of intrinsic ferroelectric or relaxor-type origin.
Here, a material processing concept based on Sr1-1.5xYxTiO3 (SYT) with x =
0.005 and 0.010 is reported, which yields the low-temperature dielectric
permittivity up to ~209 000 at 10 kHz, when SYT is fired in nitrogen, and relative
tunability up to ~74% under 20 kV/cm, when SYT is fired in oxygen atmosphere.
The high low-temperature tunability is attributed to polar clusters formed by offcentral displacement of small Y3+ ions on large Sr sites, whereas the giant lowtemperature permittivity is explained by conducting electrons, created by Y3+
substitution for Sr2+ ions, and their coupling to relaxation mode related to the
polar clusters. In comparison, CaCu3Ti4O12, considered as one of the most
promising giant-permittivity materials at room temperature, reveals the lowtemperature permittivity below 100 without any substantial tunability. However,
most intriguingly, we obtained in oxygen-fired SYT the relative tunability up to
~34% even at room temperature, whereas the room-temperature permittivity of
nitrogen-fired SYT is as high as ~96 000 at 10 kHz. Moreover, the permittivity
does not drop and loss tangent does not rise for few orders approaching to the
frequency of 300 kHz, as it is usually occurs for the giant permittivity materials,
but shows superior values of ~89 000 and ~0.06, respectively. This discovery
opens a new development window for high frequency electronic and
microelectronic device applications.
35
LIGHT EMITING CRYSTALLINE SILICON NANOPARTICLES
Alexandre M. P. Botas1,2, Rebecca J. Anthony3, Jeslin Wu3, Nuno J. Silva1,
Uwe Kortshagen3, Rui N. Pereira2,4, Rute A. S. Ferreira1
1
2
Department of Physics and CICECO − Aveiro Institute of Materials,
University of Aveiro, 3810–193 Aveiro, Portugal
Department of Physics and I3N, University of Aveiro, 3810−193 Aveiro,
Portugal
3
4
Department of Mechanical Engineering, University of Minnesota
Minneapolis, MN 55455, USA
Walter Schottky Institut and Physik − Department, Technische Universität
München, Am Coulombwall 4, Garching 85748, Germany
The discovery of room temperature light emission from porous silicon, in 1990,
gathered much interest in light emission of nanoscale silicon materials. Crystalline
silicon nanoparticles (SiNPs) have received increasing attention in the last years as
multi-function materials with unique properties, such as tunable and efficient
luminescence [1, 2], which make them attractive for application in fields as bioimaging
[3] or light emitting devices [4].
To enable a comparative study of the role of surface terminal groups on the
optical properties, we investigated SiNPs ensembles with the same mean NP diameter
but differing on the surface termination, namely organic-functionalized with 1dodecene (SiNPs-C12) and H-terminated (SiNPs-H). Through photoluminescence
spectroscopy in time-resolved and steady-state modes as well as quantum yield
measurements, we elucidate the role of the surface termination. We show that the
surface functionalization changes the photoluminescence properties with respect to
SiNPs-H by changing the inter-NP exciton transfer. Both the exciton recombination
lifetimes and quantum yields display a pronounced dependence on the surface
termination. Exciton lifetimes and quantum yields are found to be significantly lower in
SiNPs-H compared to SiNPs-C12. This difference is due to distinct non-radiative
recombination probabilities resulting from inter-NP exciton migration, which in SiNPsC12 is inhibited by the wider energy barriers imposed by the bulky surface groups.
This also results in a higher quantum yield observed in SiNPs-C12 compared to SiNPsH. We also found that the surface oxidation of SiNPs-C12 leads to the appearance of
a phenomenon of exciton transference from to the NPs crystalline Si core to oxiderelated states that contribute to light emission.
[1] A. M. P. Botas, R. A. S. Ferreira, R. N. Pereira, R. J. Anthony, T. Moura, D. J.
Rowe, U. Kortshagen, J. Phys. Chem. C 2014, 118, 10375.
[2]
A. Gupta, M. T. Swihart, H. Wiggers, Adv. Funct. Mater. 2009, 19, 696.
[3] N. H. Alsharif, C. E. M. Berger, S. S. Varanasi, Y. Chao, B. R. Horrocks, H. K.
Datta, Small 2009, 5, 221.
[4] K. Y. Cheng, R. Anthony, U. R. Kortshagen, R. J. Holmes, Nano Lett. 2010, 10,
1154.
36
STRUCTURAL, CHEMICAL, OPTICAL AND ELECTRICAL PROPERTIES
OF MO-MOXOY THIN FILMS DEPOSITED BY REACTIVE MAGNETRON
SPUTTERING
Alice Marciel1, Miguel Neto1, Joel Borges3, Filipe Vaz3, Manuel P.F. Graça2,
Rui F. Silva1
1
CICECO - Aveiro Institute of Materials, Department of Materials and
Ceramic Engineering, University of Aveiro, 3810-193 Aveiro, Portugal
2
I3N, Physics Department, University of Aveiro, Campus de Santiago, Aveiro,
Portugal
3
Univ Minho, Ctr Fis, P-4710057 Braga, Portugal
Molybdenum oxides especially in thin film form are interesting for their
electrochromism, photochromism, among other physical properties and already found
use as gas sensors, capacitors, lithium batteries, etc., and in other areas of technology
including chemical catalysis, and energy. The diversity of these applications can be
attributed to the wide range of molybdenum oxidation states (+2, +3, +4, +5 or +6) and
the easy manipulation of those states via oxidation or reduction. Of particular interest
are the Mo-MoxOy films for electrochromic applications where structure, electrical and
optical performances play an important role.
In this study molybdenum oxide films were deposited by reactive magnetron
sputtering (RMS) from a molybdenum target in a reactive environment, where the flow
rate of oxygen was varied from 0 sccm to 16 sccm, the total pressure and the current
density of the molybdenum target being kept at 4x103 mbar and 88Am-2, respectively.
The depositions were performed in a ground and at room temperature, resulting in a
range of structures, from crystalline to amorphous. The resulting films were
characterized by X-ray diffraction (XRD), energy dispersive X ray photoelectron
spectroscopy (XPS), scanning electron microscopy (SEM),
UV-VIS optical
spectroscopy and electrical resistivity measurements.
The amount of reactive oxygen available during deposition controls the
composition of the film, changing from Mo metallic to fully stoichiometric MoO3. XRD
studies revealed a highly crystallinity character dependence on oxygen flows rate.
SEM results evidence a granular/sponge morphology of the films with a columnar
growth typically of the PVD process. Optical transmittance results shown that only the
film formed at 16 sccm of oxygen was transparent with an average transmittance
higher than 72 in visible region. Electrical resistivity increases with the increase of
oxygen flux, which is compatible with the transition from metallic film to oxide films, as
confirmed by XRD and XPS.
37
INCORPORATION OF CARBON NANOSTRUCTURES IN SILICA
AEROGELS
Alyne C. L. Mendes 1,2, Rui F. Silva 2, Luísa M. R. Durães 1
1
CIEPQPF – Chemical Process Engineering and Forest Products Research
Centre, Department of Chemical Engineering, University of Coimbra, 3030-790
Coimbra, Portugal
2 CICECO - Aveiro Institute of Materials, Department of Materials and
Silica aerogels aroused a great interest due to the advantages associated with
the method of obtaining these materials, such as low process temperatures,
highly homogeneous products and the ability to control the surface chemistry
[1]. These materials possess exceptional properties such as high porosity and
specific surface area, low bulk density and thermal conductivity. In contrast,
these aerogels have some limitations in their mechanical strength. This limits
their applications in areas such as aerospace, since their intrinsic fragility
imposes severe restrictions to support loads [2]. However, they allow an easy
doping of their structure with different compounds. This versatility permits
obtaining materials with different characteristics when compared to the native
silica aerogels, which may lead to the development of new materials with
properties not yet found in existing materials.
An interesting alternative to the mechanical reinforcement of the silica aerogel
is the modification with carbon-based nanomaterials, such as carbon
nanotubes and graphene. These carbon nanostructures have well-founded
characteristics, namely a high electrical conductivity and, especially, high
mechanical strength [3, 4]. These properties, combined with the characteristics
of the silica aerogels can lead to the development of an extremely lightweight,
porous material with high mechanical strength and robustness.
The synthesis steps strongly influence the characteristics of the gels, so any
change is important in the development of differentiated properties of silica gels.
Considering these interactions, this proposal arises from the need to
understand the relationships between the intrinsic variables of silica-carbon
aerogels synthesis, in order to obtain a material with increased mechanical
resistance, which could be used as thermal insulator for aeronautics (re-entry
rockets and space vehicles), and as supercapacitors.
[1] M. Houmard, D.C.L. Vasconcelos, W.L. Vasconcelos, G. Berthomé, J.C.
Joud, M. Langlet. Surf. Sci., 2009, 603, 2698-2707.
[2] H. Maleki, L. Durães, A. Portugal. J. Non-Cryst. Solids, 2014, 385, 55-74.
[3] M.M. Shokrieh, R. Rafiee. Mech. Compos. Mater., 2010, 46, 155-172.
[4] R.J. Young, I.A. Kinloch, L. Gong, K.S. Novoselov. Compos. Sci. Technol.,
2012, 72, 1459–1476.
38
DEVELOPMENT OF A LOW COST COHERENT RECEIVER
Ana Bastos1,2, Carlos Vicente1,2, Luís D. Carlos1, Mário Lima3, Paulo S.
André4* and Rute A.S. Ferreira1
Physics Department and CICECO − Aveiro Institute of Materials, University of
Aveiro, Portugal
2
Instituto de Telecomunicações, University of Aveiro, Portugal
3
Department of Electronics, Telecommunications and Informatics and Instituto de
Telecomunicações, University of Aveiro, Portugal
4
Department of Electrical and Computer Engineering and Instituto de
Telecomunicações, Instituto Superior Técnico, University of Lisboa, Portugal
1
The volume of communication traffic is exploding, due to ever increasing
subscriber numbers and the rise of multimedia based applications [1]. Future
disruptive solutions to cope with the increase bandwidth are based on coherent
Passive Optical Network (PON) technology, which is characterized by the
absence of active equipment between subscribers and the operator location,
thereby representing a significant breakthrough in the architecture of an fibre
network. One of the coherent PON solution is the coherent optical system that
uses multilevel modulation formats, like the quadrature phase shift keying
(QPSK). This modulation format utilizes the transmission of phase information
instead of amplitude modulation, requiring an integrated QPSK receiver. The
receiver allows the I and Q phase components of the signal to be extracted as
a result of the interference generated by a local oscillator. Taking this into
account, this work proposes a coherent receiver based on flexible organicinorganic hybrids for low cost photonic integrated circuits. The organicinorganic hybrid is UV self-patterned without the need of photo initiators,
enabling the fabrication of PICs using direct-UV laser writing, and reducing the
production cost.
[1] A. Bogoni, IEEE Journal of Selected Topics in Quantum Electronics 2011,
vol. 17, pp. 472-479.
39
COPPER SULFIDE NANOCRYSTALS: SYNTHESIS AND
PHOTOCATALYTIC STUDIES
Ana C. Estrada, Fábio M. Silva, Sofia F. Soares, João A. P. Coutinho,
Tito Trindade
Department of Chemistry, CICECO, Aveiro Institute of Materials, University of Aveiro,
3810-193 Aveiro, Portugal
Semiconducting transition metal chalcogenides have attracted great attention owing to
their size-dependent properties and their potential applications which include sensors,
solar cells, catalysts and optoelectronic devices [1]. In particular, copper sulfide, a
well-known p-type semiconductor, have attracted great attention because of their
stoichiometry-dependent band-gap [2]. These solids crystallize in a variety of phases
that exhibit distinct optical properties including different optical band gaps in the visible
region. The crystalline phases are associated to unique properties shown by
semiconductor nanocrystals that could be exploited to produce new photocatalysts
with tuned optical behavior. Motivated by this, in the present study we demonstrate
that copper sulfide NCs with well-controlled stoichiometry can be prepared through a
single source approach by thermolysis of Cu(II) dialkyldithiocarbamate complexes in
ionic liquids. The photocatalytic activity of the ensuing water dispersible copper sulfide
nanomaterials has been evaluated using rhodamine B (RhB) solutions under visiblelight irradiation with the assistance of hydrogen peroxide. The results indicate that the
ionic liquid route described have impact on the copper sulfides produced and thereby
on their performance as photocatalysts.
Figure 1. TEM images of copper sulfide nanocrystals with rhombohedral structure.
The authors acknowledge FCT Project UTAP-ICDT/CTMNAN/0025/2014 and the project
CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID /CTM
/50011/2013), financed by national funds through the FCT/MEC and when appropriate cofinanced by FEDER under the PT2020 Partnership Agreement. Ana C. Estrada also thanks
FCT for a post-doctoral grant (SFRH/BPD/86780/2012).
[1]
T. Trindade, P. J. Thomas in Comprehensive Inorganic Chemistry II: From Elements
to Applications (Eds.: J. Reedijk, K. Poeppelmeter), Elsevier, Oxford, 2013, vol. 4, pp. 343.
[2]
Y. Zhao, H. Pan, Y. Lou, X. Qiu, J. Zhu, C. Burda, J. Am. Chem. Soc., 2009, 131,
4253.
40
OXIDOMOLYBDENUM COMPLEXES FOR ACID CATALYSIS USING
ALCOHOLS AS SOLVENTS AND REACTANTS
Ana C. Gomes1, Patrícia Neves1, Luís Cunha-Silva2, Anabela A. Valente1,
Isabel S. Gonçalves1 and Martyn Pillinger1
1
Department of Chemistry, CICECO - Aveiro Institute of Materials, University of
Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro
2
REQUIMTE-LAQV, Departamento de Química e Bioquímica, Faculdade de
Ciências, Universidade do Porto, 4169-007 Porto
Over the years dichloridodioxidomolybdenum(VI) chelate complexes have been
intensively investigated as catalysts for liquid-phase olefin epoxidation. In this work the
catalytic potential of such complexes for acid catalysis has been studied by applying a
representative complex in alcoholysis and acetalisation reactions.[1]
Complex [MoO2Cl2(L)] (1) with L = 4,4'-di-tert-butyl-2,2'-bipyridine was chosen as
(pre)catalyst and, depending on the reaction conditions, 1 either remained structurally
intact or was transformed into different metal species, the structures of which were
determined on the basis of single-crystal X-ray diffraction, spectroscopic techniques,
and elemental analysis. In the presence of ethanol, the MoVI oxidoalkoxido complex
[MoO2Cl(OEt)(L)] (2) was isolated, which is the first example of a mixed-ligand complex
of the type [MoO2X(OR)(L)], where X = halide or alkyl group, and is very unusual in
exhibiting an all-cis geometric configuration instead of the cis-oxido,trans-X,cis-L
configuration usually seen for complexes of the type [MoO2X2(L)] (X = anionic ligand).
Mechanistic considerations of the formation of the metal species are made.
Funding is acknowledged for the projects FCOMP-01-0124-FEDER-029779 (FCT ref.
PTDC/QEQ-SUP/1906/2012) (FEDER/COMPETE), CICECO - Aveiro Institute of
Materials, POCI-01-0145-FEDER-007679 (FCT ref. UID/CTM/50011/2013) (PT2020),
and REQUIMTE-LAQV (UID/QUI/50006/2013) (PT2020). The FCT and the EU are
acknowledged for grants to A.C.G. (SFRH/BPD/108541/2015) and P.N.
(SFRH/BPD/73540/2010) (MCTES, the European Social Fund, POPH/QREN).
[1] A. C. Gomes, P. Neves, L. Cunha-Silva, A. A. Valente, I. S. Gonçalves, M.
Pillinger, Catal. Sci. Technol. 2016, in press, DOI: 10.1039/C5CY02052B.
41
PURIFICATION OF PHYCOBILIPROTEINS USING AQUEOUS BIPHASIC
SYSTEMS BASED IN CHOLINIUM IONIC LIQUIDS
Ana Celina C. Lopes1, Margarida Martins1, João H. P. M. Santos1, Helena
Abreu2, João A.P. Coutinho1, Sónia P.M. Ventura1
1CICECO
- Aveiro Institute of Materials, Department of Chemistry, University of
2ALGAplus Lda, Travessa Alexandre da Conceição 3830-196 Ílhavo, Portugal
Macroalgae are a source of bioactive compounds, such as phycobiliproteins, which
are antennae-protein pigments involved in light harvesting. R-Phycoerythrin is the
most abundant phycobiliprotein from red macroalgae. It shows peculiar spectral and
fluorescence properties and it is known by its stability regarding changes of pH,
temperature and time of storage [1]. The major drawback associated with the
phycobiliproteins (including the R-phycoerythrin) purification is the demand for
effective and low cost purification methods capable to isolate the target protein from
the biomass, while maintaining its stability. With this purpose, aqueous biphasic
systems (ABS) emerge as relatively simple and efficient techniques that maintains the
bioactivity of several biomolecules, including proteins [2]. In this work, the purification
of phycobiliproteins through the use of ABS composed of polypropylene glycol 400
(PPG 400), cholinium-based ionic liquids and the McIlvaine buffer (fixed pH) was
investigated. New binodal curves were determined and stablished for four choliniumbased ILs, respectively cholinium chloride ([Ch]Cl), cholinium acetate ([Ch][Ac]),
cholinium dihydrogenosphosphate ([Ch][DHP]), and cholinium bicarbonate ([Ch][Bic]).
The results showed that the most promising purification results were found for the
system composed of [Ch]Cl (EE% = 87% and S = 3.4).
[1]
M. Munier, S. Jubeau, A. Wijaya, M. Morançais, J. Dumay, L. Marchal, P. Jaouen,
and J. Fleurence, “Physicochemical factors affecting the stability of two pigments: Rphycoerythrin of Grateloupia turuturu and B-phycoerythrin of Porphyridium cruentum,” Food
Chem., 2014, vol. 150, pp. 400–407.
[2]
M. G. Freire, A. F. M. Cláudio, J. M. M. Araújo, J. a. P. Coutinho, I. M. Marrucho, J. N.
C. Lopes, and L. P. N. Rebelo, “Aqueous biphasic systems: a boost brought about by using
ionic liquids”, Chem. Soc. Rev., 2012, vol. 41, no. 14, p. 4966.
Acknowledgments: This work was developed within the scope of the project CICECO-Aveiro
Institute of Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM/50011/2013),
financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER
under the PT2020 Partnership Agreement. The authors are also grateful to Fundação para a
Ciência e a Tecnologia (FCT) for the post-doctoral and doctoral grants SFRH/BPD/79263/2011
and SFRH/BD/102915/2014 of S.P.M. Ventura and J. H. P. M. Santos and for the research
fellowship within the project “Optimization and Scale-up of Novel Ionic-Liquid-based Purification
Processes for Recombinant Green Fluorescent Protein produced by Escherichia coli” of M.
Martins.
ALGAplus activities were supported by the project SEACOLORS, LIFE13 ENV/ES/000445.
42
MICROWAVE-ASSISTED SYNTHESIS OF A PHOTOLUMINESCENT
METAL-ORGANIC FRAMEWORK BASED ON A TETRAPHOSPHONATE
ORGANIC LINKER
Ana D. G. Firmino1,2, Ricardo F. Mendes1, Duarte Ananias1,3, Sérgio M. F. Vilela1,2,
Luís D. Carlos3, João Rocha1, João P. C. Tomé2,4, Filipe A. Almeida Paz1
1 Department
of Chemistry, CICECO – Aveiro Institute of Materials, University of Aveiro,
2 Department of Chemistry, QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal
3 Department of Physics, CICECO – Aveiro Institute of Materials, University of Aveiro, 3810193 Aveiro, Portugal
4 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av.
Rovisco Pais, 1049-001 Lisboa, Portugal
Metal-phosphonate based compounds have been the subject of intense research in
recent years due to their novel and fascinating architectures, as well as their
remarkable and varied applications. Studies mainly include fundamental syntheses of
materials; tunable design and evaluation of properties for applications. As a
continuation of our previous research [1] and following an increasing trend in the
discovery and investigation of functional luminescent Metal-Organic Frameworks
(MOFs) [2], we are interested in the synthesis of new multidimensional MOFs based
on lanthanide centers and multipodal phosphonate based ligands. In this work
microwave-assisted synthesis was used to prepare a new organic building block and
a MOF based on this unit. The tetrapodal organic linker [1,1’-biphenyl]-3,3’,5,5’tetrayltetrakis(phosphonic acid) (H8btp) was combined with lanthanide cations
affording
the
isotypical
2D
lanthanide-organic
frameworks
[Ln4(H6btp)2(H4btp)2(H8btp)(H2O)16]·12H2O [where Ln3+ = La3+ (1), (La0.9Eu0.1)3+ (2) and
(La0.9Tb0.1)3+ (3)]. 1 was isolated as large single-crystals and its crystal structure was
unveiled from single-crystal X-ray diffraction studies. Phase identification of the Eu3+(2) and Tb3+-based (3) materials was performed by powder X-ray diffraction.
Compound 1 consists of two-dimensional double-deck layers, characterized by an
unprecedented tetranodal 2,4,4,4-connected layered network. Supramolecular π–π
interactions exist both within and between layers. 1-3 were fully characterized in the
solid-state and photoluminescence properties of the optically-active mixed-lanthanide
materials 2 and 3 reveal that the employed H8-xbtp-x residues are better suited to
sensitize Tb3+ than Eu3+, with the measured lifetimes being of 0.83±0.01 and 0.22±0.01
ms, respectively.[3]
Acknowledgements: We wish to thank Fundação para a Ciência e a Tecnologia
(FCT, Portugal), the European Union, QREN, FEDER through Programa Operacional
Factores de Competitividade (COMPETE), CICECO - Aveiro Institute of Materials,
POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM/50011/2013), and QOPNA (FCT
UID/QUI/00062/2013), financed by national funds through the FCT/MEC and when
appropriate co-financed by FEDER under the PT2020 Partnership Agreement. We
also thank FCT for funding the R&D project FCOMP-01-0124-FEDER-041282 (Ref.
FCT EXPL/CTM-NAN/0013/2013). FCT is also gratefully acknowledged for the Ph.D.
grants Nos. SFRH/BD/84495/2012 and SFRH/BD/84231/2012 (to ADF and RFM,
respectively), and the post-doctoral research grants Nos. SFRH/BPD/94381/2013
and SFRH/BPD/95032/2013 (to SMFV and DA, respectively).
[1] S. M. F. Vilela, J. A. Fernandes, D. Ananias, L. D. Carlos, J. Rocha, J. P. C.
Tomé, F. A. Almeida Paz, CrystEngComm, 2014, 16, 344.
[2] Y. Cui, Y. Yue, G. Qian, B. Chen, Chemical Reviews, 2012, 112, 1126.
[3] A. D. G. Firmino, R. F. Mendes, D. Ananias, S. M. F. Vilela, L. D. Carlos, J. P.
C. Tomé, J. Rocha, F. A. Almeida Paz, Inorganica Chimica Acta (accepted).
43
MICELLE-MEDIATED EXTRACTION OF CHLOROPHYLLS FROM
SPINACH LEAVES USING AQUEOUS SOLUTIONS OF IONIC LIQUIDS
Ana M. Ferreira1, Ana Cláudia Leite1, Imran Khan1, Mara G. Freire1 and João
A. P. Coutinho1
1
Aveiro, Aveiro, Portugal
Chlorophylls a and b are natural photosynthetic pigments responsible for the
characteristic green colour of fruits and vegetables [1]. Chlorophylls of higher plants
consist of chlorophyll a and chlorophyll b pigments, which are usually present in a ratio
of 3:1 [2]. Chlorophylls display ubiquitous properties, such as protective features
against toxins, the ability to ameliorate some drug side effects in humans, among
others. Thus, due to these valued properties, chlorophylls are currently used by the
food, pharmaceutical and cosmetic industries [2]. However, chlorophylls extracted
from natural sources are quite expensive because the classical methods typically used
for their extraction result in low efficiency yields and low purity levels. Moreover, most
of the organic solvents commonly used are hazardous to human health and
environment. In this context, the use of ionic liquids (ILs) as alternative solvents can
be foreseen as a promising approach due to their intrinsic characteristics, such as a
negligible vapour pressure, non-flammability, high thermal and chemical stabilities,
and an enhanced solvation ability for target biomolecules [3,4].
In this work, aqueous solutions of surface-active ILs were studied for the extraction of
chlorophylls from spinach leaves envisaging the development of a “greener” costeffective technology. To improve the extraction yields and purification factors several
operational parameters (concentration of IL, contact time and solid–liquid ratio) were
optimized, employing a surface response methodology. This work shows that aqueous
solutions of surface-active ILs are enhanced solvents for the extraction of chlorophylls
from bioresources, e.g. spinach leaves. The time and temperature of extraction were
greatly reduced while providing higher extraction yields when compared to
conventional methods using volatile and organic solvents. Furthermore, very low
concentrations of ILs are needed for effective extractions. The recovery of chlorophylls,
and the reusability and recyclability of the IL solutions were also attempted to support
the economic viability and weak environmental footprint of the proposed methodology.
The obtained results support the applicability of the proposed technique for large-scale
applications.
[1] C. Jubert, G. Bailey, J. Chromatogr. A. 2007, 1140, 95-100.
[2] M. Hojnik, M. Škerget, and Ž. Knez, Sep. Purif. Techn., 2007, 57, 37-46.
[3] A. F. M. Cláudio, A. M. Ferreira, M. G. Freire and J. A. P. Coutinho, Green Chem.,
2013, 15, 2002-2010.
[4] K. Bica, P. Gaertner, and R. D. Rogers, Green Chem., 2011, 13,1997-1999.
Acknowledgements: This work was financed by national funding through the projects
EXPL/QEQ-PRS/0224/2013 and PEst-C/CTM/LA0011/2013. This work was
developed in the scope of the project CICECO-Aveiro Institute of Materials (Ref. FCT
UID /CTM /50011/2013), financed by national funds through the FCT/MEC and when
applicable co-financed by FEDER under the PT2020 Partnership Agreement. A. M.
Ferreira acknowledges FCT for the PhD grant SFRH/BD/92200/2013.
44
LACCASE PARTITION IN IONIC-LIQUID-BASED AQUEOUS BIPHASIC
SYSTEMS
Ana P.M. Tavares1, Oscar Rodriguez2, João A. P. Coutinho1, Ana Soto2, Mara
G. Freire1
1
CICECO-Aveiro Institute of Materials, Chemistry Department, University of Aveiro,
2
Department of Chemical Engineering, Universidade de Santiago de Compostela,
Santiago de Compostela, Spain
Oxidative enzymes, for instance laccases, catalyze oxidative reactions for a wide
variety of organic substrates. These enzymes are widely used in biotechnological
processes, such as detoxification of industrial effluents, polymer synthesis, wine and
beverage stabilization, or in the manufacturing of anticancer drugs and cosmetics [1,
2]. Recently, their potential use in nanobiotechnology was also proposed [3]. However,
large amounts of enzyme with a high purity level are required for these applications.
Microbial fermentation is the most viable production method; yet, the enzyme’s
recovery and purification from the fermentation broth involve several steps. Thus, their
production cost still remains extensively high. This work envisages the investigation of
aqueous biphasic systems (ABS) composed of ionic liquids (ILs), as biocompatible
water-rich media [4], for the extraction and purification of laccase. The main goal is to
obtain high laccase extraction yields while not leading to enzyme denaturation and, at
the same time, to develop a cost-effective and sustainable platform for laccase
purification. For this purpose, studies on the enzyme partitioning in IL-based ABS were
carried out. ABS composed of several ILs based on imidazolium, pyridinium,
phosphonium, ammonium and cholinium families, combined either with salts or
polymers were investigated. For some systems, notable extraction efficiencies of
laccase were obtained in a single-step. The best systems for laccase partition were
finally selected and the ABS composition and protein concentration were optimized
envisaging their application in real fermentation broths.
Acknowledgements: This work was developed in the scope of the project CICECOAveiro Institute of Materials (Ref. FCT UID/CTM /50011/2013), financed by national
funds through the FCT/MEC and co-financed by FEDER under the PT2020
Partnership Agreement. Ana P.M. Tavares acknowledge the financial support from the
National Council for Scientific and Technological Development (CNPq) Brazil for the
Postdoctoral Fellowship (Ref. 201834/2015-4) and also acknowledges the Short Term
Scientific Mission grant (ECOST-STSM-CM1206-110116-068796) and financial
support from COST-IL. Mara G. Freire acknowledges the European Research Council
(ERC) for the Starting Grant ECR-2013-StG-337753.
1. S. R. Couto, S. and J.L. Toca Herrera, Biotechnol. Adv. 2006, 24, 500-513.
2. A.P.M. Tavares, et al., J. Chem. Technol. Biotechnol. 2009, 84, 442-446.
3. A. Kunamneni, et al., Recent Pat. Biotechnol. 2008, 2, 10-24.
4. M.G. Freire, et al., Chem. Soc. Rev. 2012, 41, 4966-4995.
45
ALTERNATIVE SOLVENTS CONSTITUTED BY MIXTURES OF
FLUORINATED IONIC LIQUIDS
Ana Rita R, Teles1, Helga Correia1, Guilherme J. Maximo2, João A. P.
Coutinho1, Luís P. N. Rebelo3, Ana B. Pereiro3 and Mara G. Freire1
1
CICECO - Aveiro Institute of Materials, Department of Chemistry, University
of Aveiro, 3810-193 Aveiro, Portugal
2
Laboratory of Extraction, Applied Thermodynamics and Equilibrium, School of
Food Engineering, University of Campinas, Campinas, São Paulo, Brazil
3
Instituto de Tecnologia Química e Biológica António Xavier (www.itqb.unl.pt),
UNL, Av. República, Apartado 127, 2780-901 Oeiras, Portugal
Currently, a wide number of studies has been reported regarding the characterization
of the physicochemical properties of ionic liquids (ILs). In particular, a large interest
has been devoted to fluorinated ILs (FILs) due to their physicochemical properties and
potential applications, e.g., as refrigerants, surfactants, fire retardants, lubricants,
among others.[1] The interest on these fluids results mainly from their ionic nature and
tunable character, which allow ILs to be designed for specific applications. This feature
is even more expanded if mixtures of ILs are considered.[2] In this context, the goal of
this work consists on the enlargement of the advantageous features afforded by FILs
by the characterization of their binary mixtures, namely by the determination of their
solid-liquid phase diagrams and physicochemical properties. Four binary mixtures of
FILs were investigated, comprising the following FILs: 1-butyl-1-methylpyrrolidinium
perfluorobutanesulfonate,
1-butyl-1-methylpyrrolidinium
bis(nonafluorobutylsulfonyl)imide,
1-ethyl-1-methylpyrrolidinium
bis(nonafluorobutylsulfonyl)imide,
(2-hydroxyethyl)trimethylammonium
perfluorobutanesulfonate and 1-ethyl-1-methylpyrrolidinium triflate. The gathered
phase diagrams also allow to infer on the (non)ideality behavior of mixtures of FILs.
The Conductor like Screening Model for Real Solvents (COSMO-RS) was additionally
used to describe the solid-liquid phase behavior of the mixtures investigated. In
summary, the use of mixtures of FILs, and through the characterization of their
eutectic-like phase diagrams, allows to enlarge the number of FILs that are liquid at
room temperature and to boost their applications.
[1] Pereiro, A. B., Araújo, J. M. M., Martinho, S., Alves, F., Nunes, S., Matias,
A., Duarte, C. M. M., Rebelo, L. P. N., Marrucho, I. M., ACS Sustain. Chem.
Eng., 2013, 1, 427–439.
[2] Máximo, Guilherme J., Santos, Ricardo J. B. N., Brandão, Paula,
Esperança, José M. S. S., Costa, Mariana C., Meirelles, Antonio J. A., Freire,
Mara G., Coutinho, João A. P., Crystal Grow Design, 2014, 14, 4270 –4277.
46
Mg-PARTIALLY STABILIZED ZIRCONIA, ELECTRICAL AND
STRUCTURAL CHARACTERIZATION
Ana Rondão1, M.F. Évora1, F.M.B. Marques1
1
Dept. of Materials and Ceramic Eng./CICECO, University of Aveiro, 3810-193
Aveiro, Portugal
Magnesium partially stabilized zirconia materials (Mg-PSZ) have excellent fracture
toughness. This explains their wide range of applications, most of them involving
demanding conditions [1-2]. The crystallographic composition is determining with
respect to the mechanical and electrical properties. Mg-PSZ materials may include
different zirconia polymorphs: cubic (C), tetragonal (T) and monoclinic (M). The
proportion of the three phases is determined by the chemical level of stabilization, the
maximum sintering temperature and strongly by the cooling temperature profile.
In the present work Mg-PSZ samples with variable magnesium content (<10 mol%),
were prepared by solid state reaction, with peak sintering temperatures in the order of
1700 °C, and experiencing distinct sintering profiles. XRD patterns obtained both on
sintered specimens and powders from milled samples were analyzed by the Rietveld
method. Impedance spectroscopy in air and scanning electron microscopy (SEM) were
used to complement this study.
In agreement with what was expected, all crystalline phases exist in variable amounts
in all sintered samples, depending on their composition and cooling conditions. After
milling the fired samples, only the C and M phases were found, because of the
displacive nature of the T to M transformation that can be easily triggered by the impact
energy. Considerably distinct microstructures including massive numbers of needletype precipitates (presumably T and/or M) within large grains (presumably C) were
observed. The latter often were also surrounded by smaller grains (presumably M).
This seems to indicate that variable cooling rates affect the diffusional processes
needed to reach thermodynamic equilibrium, either enhancing phase nucleation or
allowing grain growth.
The impedance spectroscopy revealed that phase composition is not the only and
major criterion in determining the electrical performance of these materials. In fact,
while the C and even the T phases are usually good oxide-ion conductors, the M phase
is mostly insulating. The latter, if dispersed as isolated particles or covering C grains,
will impact the electrical conductivity in distinct manners. Impedance spectroscopy can
thus be used to obtain some insight on the (electrical) microstructure of Mg-PSZ
materials.
[1]
R.H.J. Hannink, R.C. Garvie, J. Mat. Sci.,1982, 17, 2637-2643;
[2]
J. Chevalier, L. Gremillard, A.V. Virkar, D.R. Clarke, J. Am. Ceram. Soc., 2009,
92, 1901-1920.
47
POROUS BIPHASIC CALCIUM PHOSPHATE SCAFFOLDS DERIVED
FROM CUTTLEFISH BONE
Ana S. Neto, José M.F. Ferreira
Department of Materials and Ceramics Engineering, CICECO Email: E-mail: [email protected]
Cuttlefish bone (CB) is an inexpensive, worldwide available and morphological
complex natural material. Its lamellar matrix is highly porous and mainly
composed of aragonite (CaCO3). It is worthy to note that the pore size and
interconnectivity of this natural architecture are beneficial for bone ingrowth and
vascularization [1,2].
In this study CB were successfully converted into porous biphasic calcium
phosphate (BCP) scaffolds with a range of hydroxyapatite (HA) and β-tricalcium
phosphate (β-TCP) composition. The process involves the emersion of CB into
a phosphoric acid (H3PO4) and 2-propanol solution and subsequently its
transformation in an autoclave at high temperature and pressure. The resulting
material was treated at high temperature in air to obtain inorganic scaffolds.
The crystalline phases of the BCP scaffolds were identified by X-ray diffraction
(XRD) and its unique architecture was observed by scanning electron
microscopy (SEM).
The ability to tailor the composition of this BCP scaffolds allows the
development of individualized implants with a controlled biodegradation.
[1]
J.H.G. Rocha, A.F. Lemos, S. Agathopoulos, P. Valério, S. Kannan, F.N.
Oktar, J.M.F. Ferreira, Bone 2005, 37, 850-857.
[2]
P. Sarin, S. Lee, Z.D. Apostolov, W.M. Kriven, Journal of American
Ceramic Society 2010, 94, 2362-2370.
48
A NEW POLYESTER BASED ON 2,5-FURANDICARBOXYLIC ACID AND
ALIPHATIC LONG CHAIN DIOL
Andreia F Sousa1,2, Maria João Soares1, José Bastos1, Carla Vilela1, PatrickKurt Dannecker3, M. A. R. Meier3, Armando J. D. Silvestre1
1
CICECO and Department of Chemistry, University of Aveiro, 3810-193 Aveiro,
Portugal
2
CEMUC, Department of Chemical Engineering, University of Coimbra,3030-790
Coimbra, Portugal
3
Karlsruhe Institute of Technology, Institute of organic Chemistry, Fritz-Haber-Weg
6, 76131 Karlsruhe, Germany
Polymers are everywhere in the everyday life, however they are still mainly produced
from fossil resources raising several sustainability issues. In this vein, 2,5furandicarboxylic acid based polyesters emerged in the polymer scene as some of the
most valuable alternatives to non-renewable fossil resources [1,2].
One of the most promising renewable-based polyesters is poly(ethylene 2,5furandicarboxylate) (PEF) [3], due to its resemblance to the well-known poly(ethylene
terephthalate) (PET),however, PEF lacks ofbiodegradability.Indeed turning furanbased polyesters (bio)degradable, while maintaining their high performance
properties, is a huge challenge which is worth pursuing. This is particularly important
in some critical domains of applications which involve the large scale production of
plastics like for example in packaging.
The present study was precisely conducted with the specific aim of developing a
novelpolyester from FDCAwith enhanced thermal and mechanical properties and
being biodegradable. Therefore, FDCA and a long chain aliphatic diol obtained from
vegetable oils, namely1,20-eicosanediol, were polymerised in the melt to afford the
poly(eicosilene2,5-furandicarboxylate) polyester (PC20F). This entirely renewable
homopolyester was characterised in detail my means of several structural, thermal and
mechanical techniques. Additionally, PC20F showed high thermo-mechanical
performance, and is potentially degradable.
[1] A. F. Sousa, C. Vilela, A C. Fonseca, M. Matos, C. S. R. Freire, G.-J. M. Gruter,
J. F. J. Coelho, A. J. D. Silvestre PolymChem2015, 6,5961.
[2] A. F. Sousa, A. C. Fonseca, A. C. Serra, C. S. R. Freire, A. J. D. Silvestre, J. F.
J. CoelhoPolymChem2016, 7, 1049.
[3] A. Gandini, A. J. D. Silvestre, C. P. Neto, A. F. Sousa, M. GomesJ. PolymSci
A2009, 47, 295.
49
PURIFICATION OF CRUDE GLYCEROL, BY-PRODUCT OF BIODIESEL
PRODUCTION
Bruno Godinho1, Ricardo Santos1, Nuno Gama1, Rui Silva2, Ana Timmons1,
Artur Ferreira3
1
Department of chemistry, CICECO - Aveiro Institute of Materials, University of
Aveiro, Aveiro – Portugal
2
Sapec-Química SA, Ovar, Portugal
3
CICECO-Aveiro Institute of Materials, Escola Superior de Tecnologia e Gestão de
Águeda, Águeda, Portugal
In the last years, the biodiesel fuel technology has attracted researchers worldwide as
a possible alternative to fossil fuel consumption. The biodiesel production increment
has resulted in a severe waste disposal crisis, as around 1 kg of crude glycerol is
created per 10 kg of biodiesel produced [1]. Typically, the resulting crude glycerol
includes various impurities and low value. Therefore, it is essential to find solutions to
add value to this by-product. Ion exchange purification and filtration by membranes
techniques can remove several types of impurities such as fatty acid, inorganic salt
and free ion from crude glycerol, but for salt contents of 5% or more, problems of
fouling and saturation turn these techniques inefficient or impracticable.
It is known and well documented that the addition of an organic solvent to an aqueous
solution could reduce the solubility of some inorganic solutes and lead to their
precipitation. This process is called extractive crystallization and it’s considered as an
alternative to evaporation in processes for the purification of salts [2, 3, 4].
This work describes the process for removing salts from a crude glycerol solution by
extractive crystallization. The process comprises mixing the crude glycerol solution
with kosmotropic proprieties solvents to promote the precipitation of salts. Three forms
of crude glycerol were used and three solvents were applied in desalinization process
in different quantities. The purity of glycerol obtained after this method can be higher
than 97%.
[1] C. Quispe, C. J. Coronado and J. Carvalho, Glycerol: Production, consumption,
prices, characterization and new trends in combustion. Renew. Sustain. Energy Rev.,
2013, 27, 475–493
[2] D. Weingaertner, S. Lynn and D. N. Hanson, Extractive crystallization of salts
from concentrated aqueous solution, Ind. Eng. Chem. Res., 1991, 30, 490–501.
[3] H. Chen, M. Dou and S. Nan, Liquid-liquid equilibria for saturated aqueous
solution of glycerol+1-butanol+water+sodium chloride at 303.15K, 323.15K and
343.15K, Fluid Phase Equilib., 2011, 305, 83–87.
[4] A. Ferreira, B. Godinho, R. Santos, A. Barros-Timmons, N. Gama and R. Silva,
Crude glycerol purification process, 2015, Patent: P 302.5 WO
50
UTILIZATION OF PAC OF RADIOISOTOPE TRACKERS AND DFT
CALCULATIONS TO DETERMINE LOCAL ENVIRONMENT OF Hg(II) IN
DITHIOCARBAMATE FUNCTIONALIZED PARTICLES FOR MAGNETIC
REMOVAL OF Hg2+ FROM WATER
C. O. Amorim1, J. N. Gonçalves1, D. S. Tavares2, C. B. Lopes2, A. S. Fenta1,3,
T. Trindade2, E. Pereira2, J. G. Correia3, V. S. Amaral1
1. Physics
Department and CICECO, University of Aveiro, 3810-193 Aveiro,
Portugal
2. Department
of Chemistry, CICECO and CESAM, Aveiro Institute of
Nanotechnology, University of Aveiro, 3810-193 Aveiro, Portugal
3. KU
Leuven, Instituut voor Kernen Stralingsfysica, 3001 Leuven, Belgium
4. Centro
de Ciências e Tecnologias Nucleares, Instituto Superior Técnico,
Universidade de Lisboa, 2686-953, Sacavém, Portugal
The application of nanoparticles in water treatment technology has attracted
growing interest due to their high specific surface area and ability for surface
chemical functionalization. In particular, functionalized iron oxide nanoparticles
have been very promising sorbents because several pollutants can be
adsorbed and then removed from the solution resorting to the application of an
external magnetic field [1-2].
It has been reported a new strategy for the surface modification of magnetite
particles that resulted into magnetic sorbents with silica shells enriched in
dithiocarbamate groups, with the finality of removing heavy metals from water
(in particular the highly toxic mercury) [3-4].
The importance of dithiocarbamate groups for an effective Hg(II) uptake as well
as operational parameters (such as sorbent dose, initial Hg concentration,
equilibration time, and pH) have already been studied, however the chemical
mechanism behind the adsorption of all the possible nanoparticles are currently
unknown.
Using Perturbed Angular Correlations (PAC) Spectroscopy [5] of 199Hg
radioisotope we were able to identify different local environments that
characterize the position where the Hg is retained during the adsorption. These
local environments and their specific electric field gradients (EFG) were than
compared with theoretical scenarios and respective DFT calculations (LDA and
GGA-PBE calculations).
This crossover between PAC experimental data analysis and DFT calculations
allow us to infer the mechanism which gives rise to the absorption of the
different nanoparticle functionalizations.
We also present an alternative method to determine the adhesion/uptake of the
Hg(II) by the different types of nanoparticles, resorting to direct tracking of
tracking of the radioisotope. This method shows many advantages when
comparing with indirect quantification since it requires much less mass of
analyzed sample and allows us to study directly what happens to the Hg(II)
51
when the Nanoparticles are manipulated prior to the Hg uptake. This paves the
way to studies regarding the nanoparticles recycling and manipulation
conditions as well as studies of the path taken by heavy metals in flora and
fauna.
[1] Ritu D. Ambashta, Mika Sillanpää, Water purification using magnetic
assistance: A review, Journal of Hazardous Materials, Volume 180, Issues 1–
3, 15 August 2010, Pages 38-49
[2] Byoung Chan Kim, Jinwoo Lee, Wooyong Um, Jaeyun Kim, Jin Joo, Jin
Hyung Lee, Ja Hun Kwak, Jae Hyun Kim, Changha Lee, Hongshin Lee, R.
Shane Addleman, Taeghwan Hyeon, Man Bock Gu, Jungbae Kim, Magnetic
mesoporous materials for removal of environmental wastes, Journal of
Hazardous Materials, Volume 192, Issue 3, 15 September 2011, Pages 11401147
[3] Daniela S. Tavares, Cláudia B. Lopes, Ana L. Daniel-da-Silva, Armando C.
Duarte, Tito Trindade, Eduarda Pereira, The role of operational parameters on
the uptake of mercury by dithiocarbamate functionalized particles, Chemical
Engineering Journal, Volume 254, 15 October 2014, Pages 559-570
[4] Penka I. Girginova, Ana L. Daniel-da-Silva, Cláudia B. Lopes, Paula
Figueira, Marta Otero, Vítor S. Amaral, Eduarda Pereira, Tito Trindade, Silica
coated magnetite particles for magnetic removal of Hg2+ from water, Journal
of Colloid and Interface Science, Volume 345, Issue 2, 15 May 2010, Pages
234-240
[5] G. Schatz and A. Weidinger, Nuclear Condensed Matter Physics: Methods
and Applications (John Wiley and Sons Ltd., Sussex, 1996).
52
PECULIAR HIGH TEMPERATURE MAGNETOELECTRIC COUPLING IN
BaTiO3:Fe113ppm
C.O. Amorim1, F. Figueiras1,2, J.S. Amaral1,2, P. B. Tavares3,
M. R. Correia4, E. Alves5, J. Rocha5, and V. S. Amaral1
1-Physics Department & CICECO, University of Aveiro, 3810-193 Aveiro,
Portugal
2-IFIMUP-IN, Science Faculty; Porto University, 4169-007 Porto, Portugal
3-Chemistry Center, Tr´as-os-Montes & Alto-Douro University, 5001-801 Vila
Real, Portugal
4-Physics Department & I3N, Aveiro University, 3810-193 Aveiro, Portugal
5-C2TN, Instituto Superior Técnico, Campus Tecnológico e Nuclear, EN10,
2695-066 Bobadela LRS
Multiferroics is one prominent area of Physics due to the outstanding
applications that arise from these materials which led to the study of composites
of ferroic materials, namely composites of ferromagnetic and ferroelectric
archetypes [1-3].
We show results regarding polycrystalline BaTiO3 which contained an overall
113 ppm of Fe. This specific kind of composite is a high-temperature extrinsic
ME multiferroic, with very large relative spontaneous magnetization changes
up to ∆M/M ≈ 32% and therefore corresponding to a ME coupling of α ≈ 10−2
G·cm/V.
This results originate from magnetic phase transitions which are correlated with
the BaTiO3 ferroelectric phase transitions, at temperatures confirmed by
Raman Spectroscopy analysis of the 520cm-1 (T≈373K) and the 487cm-1
(T≈330K) vibrational modes [4].
STEM/EDS mapping reveals that Fe distribution through the BaTiO3 is quite
inhomogeneous, tending to aggregate in specific locations, namely in the
vicinity (between/inside) of the grain boundaries which should have a
preponderant role in the reported magnetoelectric coupling [4]. BaTiO3 thermal
treatments show that the magnetoelectric coupling persists for temperatures as
high as 1200ºC. Although, for T≥1300ºC treatments the abrupt variations of the
magnetization vanish and the magnetic curve assumes the shape of a typical
paramagnetic Curie curve, suggesting the dispersion of the Fe ions all over the
BaTiO3 matrix [5]. Fe ion implantation in BaTiO3 single crystals confirms the
importance of grain boundaries and in fact even for local Fe concentrations as
high as 1% do not show any signs of a magnetoelectric coupling in the
magnetization curve, having instead a magnetization behavior similar to the one
obtained for the T≥1300ºC thermal treatments [5].
To unveil the microscopic mechanism behind the observed sharp increase in
magnetization near the structural transition temperatures of the BaTiO3 matrix,
a density functional theory study was made. We considered an atomic layer of
Fe forming an interface with bulk BaTiO3. For a particular metastable Fe atomic
53
configuration, it was found that a low-spin to high-spin transition occurs in Fe,
when the BaTiO3 matrix changes from cubic to tetragonal. This surprising
effect, due to the distorted octahedral environment of the Fe ions in the BaTiO3
interface, would promote a sharp increase in the observed magnetization, in
accordance with experimental data.
This work paves the way for a new kind of extrinsic ME multiferroic that could
be applied in devices/industry when mass production of optimized BaTiO3:Fe
nanoparticles with the same characteristics as the ones presented in this work
is achieved. Their applications would be a breakthrough since this
magnetoelectric multiferroic operates well above room temperature.
This work was developed within the scope of the project CICECO-Aveiro
Institute of Materials (Ref. FCT UID /CTM /50011/2013), financed by national
funds through the FCT/MEC and when appropriate co-financed by FEDER
under the PT2020 Partnership Agreement..
[1] Cheong, S. W., & Mostovoy, M. (2007). Multiferroics: a magnetic twist for
ferroelectricity. Nature materials, 6(1), 13-20.
[2] Ramesh, R., & Spaldin, N. A. (2007). Multiferroics: progress and prospects
in thin films. Nature materials, 6(1), 21-29.
[3] Eerenstein, W., Mathur, N. D., & Scott, J. F. (2006). Multiferroic and
magnetoelectric materials. nature, 442(7104), 759-765.
[4] Amorim, C. O., Figueiras, F., Amaral, J. S., Vaghefi, P. M., Tavares, P. B.,
Correia, M. R., Alves, E., Rocha J., & Amaral, V. S. (2015). Peculiar
Magnetoelectric Coupling in BaTiO3: Fe113 ppm Nanoscopic Segregations.
ACS applied materials & interfaces, 7(44), 24741-24747.
[5] Figueiras, F. G., Amorim, C. O., Amaral, J., Moreira, J. A., Tavares, P. B.,
Alves, E., & Amaral, V. S. (2016). Magnetoelectric effect probe through ppm Fe
doping in BaTiO3. Journal of Alloys and Compounds, 661, 495-500.
54
POLY(4-STYRENE SULFONIC ACID) AND NANOCELLULOSE
COMPOSITE MEMBRANES: MORPHOLOGICAL ANISOTROPY AND
FUEL CELL TESTS
Carla Vilela1, Tiago D.O. Gadim2, Nataly Rosero-Navarro2, Francisco J.A.
Loureiro2, Armando J.D. Silvestre1, Carmen S.R. Freire1, Filipe M.L.
Figueiredo2
1
CICECO – Aveiro Institute of Materials, Department of Chemistry, University of
2
Nanocomposite proton exchange membranes consisting of poly(4-styrene sulfonic
acid) (PSSA) cross-linked within a reinforcement matrix of bacterial cellulose (BC)
combine an environmentally friendly origin and low cost with visco-elastic properties
and protonic conductivity higher or comparable to state-of-the-art perfluorosulfonic
acid polymers [1]. Here the effect of the preferential orientation of the host BC nanofibrils and of the PSSA bulk domains along the membrane plane is reported. Data
obtained by impedance spectroscopy show that the in-plane conductivity at 98%
relative humidity (RH) is 20 to 50% higher than when measured through-plane,
demonstrating the key role of water in ensuring proton transport through the BC layers.
For 40% RH, the in-plane conductivity is more than half order of magnitude higher, and
should thus approach the intrinsically high protonic conductivity of the PSSA
polyelectrolyte. The use of these membranes is demonstrated by a fuel cell test in H2air gradient, which proves their feasibility as proton exchange membranes.
[1] T.D.O. Gadim, A.G.P.R. Figueiredo, N.C. Rosero-Navarro, C. Vilela, J.A.F.
Gamelas, A. Barros-Timmons, C.P. Neto, A.J.D. Silvestre, C.S.R. Freire, F.M.L.
Figueiredo, ACS Appl. Mater. Interfaces 2014, 6, 7864.
This work was developed within the scope of the project CICECO-Aveiro Institute of
Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM/50011/2013), financed
by national funds through the FCT/MEC and when appropriate co-financed by FEDER
under the PT2020 Partnership Agreement, CelFuelCel (EXPL/CTM-ENE/0548/2012),
HyPEM (PTDC/CTM-CER/109843/2009), SFRH/BPD/84168/2012, IF/01407/2012,
and IF/01174/2013.
55
LIQUID-LIQUID EQUILIBRIUM OF SYSTEMS FORMED BY TWO IONIC
LIQUIDS
Catarina M. S. S. Neves1, Artur M. S. Silva2, João A. P. Coutinho1, Mara G.
Freire1
1
Departamento de Química, CICECO, Universidade de Aveiro, 3810-193
Aveiro, Portugal
2
Departamento de Química & QOPNA, Universidade de Aveiro, 3810-193
Aveiro, Portugal
E-mail: catarinasn@ ua.pt
Ionic liquids are organic salts with melting temperatures below 100°C. Their
unique properties, such as a negligible vapour pressure, high chemical and
thermal stabilities, wide liquidus temperature range, and the possibility of fine
tuning their properties through appropriate cation/anion combinations make
them viable candidates to replace common organic and volatile solvents
currently used in an extensive range of industrial applications [1]. In fact, there
are circa 600 organic solvents used by industry while there are one million of
possible combinations of ions to create different ionic liquids [1]. In particular,
ionic liquids have been designated as potential solvents for “clean” liquid-liquid
extractions [2]. Therefore, the search on novel biphasic systems composed of
two ionic liquids, while comprising the determination of their liquid-liquid
equilibrium, allows the creation of a new plethora of separation processes
constituted only by non-volatile solvents. In this work, novel mixtures of
cholinium- and phosphonium-based ionic liquids were investigated and their
liquid-liquid phase diagrams were determined from 40°C to 150°C. Nuclear
Magnetic Resonance (NMR) was used as the analytical technique for the
quantification of each ion/ionic liquid and for the evaluation of ions exchange
amongst the two-phases in such mixtures.
Acknowledgements: This work was developed in the scope of the project
CICECO-Aveiro Institute of Materials (Ref. FCT UID/CTM/50011/2013),
financed by national funds through the FCT/MEC and when applicable cofinanced by FEDER under the PT2020 Partnership Agreement. Thanks also
to FCT for funding the QOPNA Research Unit (Ref UID/QUI/00062/2013).
Catarina M. S. S. Neves also acknowledges FCT for her postdoctoral grant
SFRH/BPD/109057/2015. The research leading to reported results has
received funding from the European Research Council under the European
Union’s Seventh Framework Programme (FP7/2007-2013)/ERC grant
agreement no. 337753.
[1] N. V. Plechkova and K. R. Seddon Chem. Soc. Rev., 2008, 37, 123.
[2] H. Passos, M. G. Freire, and J. A. P. Coutinho Green Chem., 2014, 16,
4786.
56
FABRICATION OF CERAMICS BY ROBOCASTING
Catarina Marques, Susana Olhero, Luis F. Freitas, Bianca Silva, José M.
Ferreira
1Department
of Materials Engineering and Ceramics, CICECO-Aveiro Institute
of Materials, University of Aveiro
Additive manufacturing (AM) means the sequential deposition and assembly of
individual layers to directly obtain three-dimensional (3D) structures according
to a computer-aided design model (CAD), without the need of patterns, dies
and subsequent machining. While the AM concept is well implemented in the
processing of polymers or metals, in the case of ceramic materials it has been
mostly explored for the production of scaffolds for bone regeneration based on
well-established biomaterials (bioglass, calcium phospates, etc.). Although
most of the traditional ceramic industry sectors are still reluctant in profiting from
these technologies, there are increasing needs for the introduction of AM
technologies in ceramic industry to face the limitations of the actual shaping
techniques. The production of small series or individual parts, such as
customized designs or prototypes, is often very expensive and time spending,
and the fabrication of complex parts is very difficult due to the limited
capabilities of conventional forming techniques, requiring high tool wear. On the
other hand, the development of new ceramic products as design changes can
only be implemented and realized in a laborious and time-consuming manner.
Robocasting, also called direct-write assembly, is a suitable additive
manufacturing technique for producing ceramic components with a variety of
architectures and gradients of properties, without the need for sacrificial support
materials or mould.
This work reports on the recent developments in the fabrication of ceramic
scaffolds using the robocasting equipment of CICECO. High solids loading
aqueous suspensions were prepared and transformed into extrudable pastes.
The relevant rheological properties of the systems (the flow behaviour of the
starting suspensions and the viscoelastic properties of the pastes) were
characterized and controlled. Different ceramic materials, geometries, shapes
and sizes, densities, pore sizes and pore size distributions, have been explored
for different target applications.
[1] P. J. Bártolo, A. H. Almeida, A. R. Rezende, T. Laoui, B. Bidanda,
Advanced processes to fabricate scaffolds for tissue engineering. Chap. 8,
pages 149-170 of: Virtual Prototyping & Bio Manufacturing in Medical
Applications. Springer, 2008.
[2] P. Miranda, A. Pajares, E. Saiz, A.P. Tomsia, F. Guiberteau, J Biomed Mater
Res 2007, 83A: 646–655.
57
SYNTHESIS AND CHARACTERIZATION OF MAGNETIC GRAPHENE
OXIDE FOR ENVIRONMENTAL APPLICATIONS
Cláudia Batista Lopes1,2, Daniela S. Tavares1,3, Joana Lopes1, Carlos Vale2,
Eduarda Pereira3, Tito Trindade1
1University
of Aveiro and CICECO-Aveiro Institute of Materials/Chemistry
Department, Aveiro, Portugal
2
CIIMAR - Interdisciplinary Centre of Marine and Environmental Research, Rua dos
Bragas 289, 4050-123 Porto, Portugal
3University
of Aveiro and CESAM/Chemistry Department, Aveiro, Portugal
Graphene is the newest type of carbon nanostructures and the potential of this
material in current technologies has raised general attention. Surprisingly, the
use of graphene-based nanostructures in environmental applications has been
less investigated despite the availability of relatively cheap derivatives such as
graphene oxide (GO) and graphene flakes. In this context, the big challenge of
this study is to prepare and then apply graphene-based adsorbents for
removing organic and/or inorganic contaminants from several environmental
compartments.
In this particular presentation, two facile methods for synthesis of magnetic
graphene oxide nanosheets are introduced and compared. The GO and the
magnetic GO obtained were fully characterized with appropriate techniques
(e.g. scanning electron microscopy, transmission electron microscopy, Raman
spectroscopy, Fourier transform infrared spectroscopy,) and the results are
presented and compared.
A preliminary adsorption assay showed that the GO materials have, under
some operational conditions, good performance for cupper adsorption from
water.
58
CHITOSAN-GENIPIN/REDUCED GRAPHENE OXIDE BIOCOMPOSITE
FILM FOR ACTIVE FOOD PACKAGING
Cláudia Nunes1,2, Ana Barra1, M.A. Martins1, Manuel A. Coimbra2, Paula
Ferreira1
1
CICECO - Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro,
Portugal
2
QOPNA, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
Nowadays, the development of active and intelligent food packaging able to interact
with food, thus contributing for its protection and extension of self-life under safety
conditions, has become extremely attractive. Moreover, alternatives to fossil resource
plastics need to be achieved, including biodegradable bio-based materials. Chitosan
films cross-linked with genipin have antioxidant and antimicrobial properties, being
used in food conservation. Also, reduced graphene oxide has recently attracted
attention due to their mechanical properties with biocompatibility, having potential
application as biomaterials.
The present work aimed to prepare composite films of graphene in a chitosan-genipin
matrix. Genipin-cross-linked chitosan films were prepared with several concentrations
of graphene oxide reduced by caffeic acid. The physicochemical and biochemical
properties of all films were evaluated.
The results obtained show an increase in the elongation percentage (88% higher) and
Young’s modulus (50% higher) for the biocomposite films in comparison with the
control film (genipin-cross-linked chitosan film). These films had also a slightly lower
(10%) solubility in water. The incorporation in chitosan of the reduced graphitic material
allowed obtaining a film with 70% higher antioxidant activity. This result indicates that
the caffeic acid used for the reduction may be linked to chitosan, influencing positively
the antioxidant properties of the films.
The mechanical and chemical properties of these novel genipin-cross-linked
chitosan/reduced graphene oxide biocomposite films show promising applications as
active food packaging. However, as microscopy analysis of the graphitic material
showed that it was heterogeneously dispersed within the chitosan, optimization of the
films preparation to ensure a good dispersion of the graphitic materials is still required.
Acknowledgements: FCT/MEC for the financial support to CICECO (FCT UID/CTM/
50011/2013;
POCI-01-0145-FEDER-007679)
and
QOPNA
(FCT
UID/QUI/00062/2013) through national founds and when applicable co-financed by
FEDER (PT2020 Partnership Agreement). Also, FCT by the grants
(SFRH/BPD/100627/2014; SFRH/BPD/89563/2012; IF/00327/2013).
59
NANO-MAGNETS BASED ON LAYERED DOUBLE HYDROXIDES
D.E.L. Vieira1, A.V. Fedorchenko2,3, E.L. Fertman3, A. Feher2, A.B. Lopes1,
A.N. Salak1, M.G.S. Ferreira1
1
Department of Materials and Ceramic Engineering, CICECO – Aveiro Institute of
Materials, University of Aveiro, Aveiro 3810-193, Portugal
2
Institute of Physics, Faculty of Science, P.J. Šafárik University in Košice, 9 Park
Angelinum, 04154 Košice, Slovakia
3
B.Verkin Institute for Low Temperature Physics and Engineering of NAS of Ukraine,
Prospekt Nauky, 47, 61103 Kharkiv, Ukraine
Layered double hydroxides (LDHs) are materials whose crystalline structure is built up
from linked oxygen octahedra containing metal cations [1]. The general formula of the
most common LDHs can be represented as [M2+1-xM3+x(OH)2]x+(Az-)x/z·nH2O where n is
an amount of crystal water per formula unit. LDHs are composed of positively charged
parallel hydroxide layers and charge-compensating anions Az- intercalated into
interlayer space. The interlayer distance can vary over a wide range depending on
nature and orientation of the intercalated anions as well as on amount of crystal water.
The use of LDHs with different cationic and anionic content for various applications
has been reported [2]. In particular, LDH materials containing magnetic transition
metals (Fe, Ni, among others) can be potentially used as sustainable and recycled
catalysts, adsorbents and ion exchangers. It has recently been shown that same
specific distortions that modify magnetic order could appear in a framework of the facelinked octahedra [3]. This can be considered as a theoretical basis to discover new
magnetic systems including those based on LDHs.
Magnetic properties of some LDHs containing Co2+, Ni2+, Fe3+ were studied [4]. It was
demonstrated that the onset temperature for spontaneous magnetization (2-15 K)
depends on the interlayer distance. However, no long-range magnetic ordering was
revealed and those LDHs were considered as spin glasses. It should be noticed that
no attempt to order paramagnetic cations in oxygen octahedral layers has been made.
It has been shown that the presence of paramagnetic atoms in LDH structure allows
an alignment of the anisotropic particles in external magnetic field even at ambient
temperature. A successful magnetic-field-assisted assembly of Co-Fe LDH films has
been reported [5].
In this work, LDHs with different ratios of Co2+ as a bivalent cation to Al3+ as a trivalent
cation ([1-x]/x=2,3 and 4) were prepared and intercalated with inorganic anions of
different size and nature using co-precipitation as a main method. Magnetic properties
of these LDHs were correlated to the interlayer distance and to the magnetic nature of
the involved cations and their ratio in the hydroxide layers.
References
[1] X. Duan, D.G. Evans, Layered double hydroxides, series Structure & Bonding,
Springer-Verlag, Berlin Heidelberg (2006),119, 234 p.
[2] A.I. Khan, D. O’Hare, J. Mater. Chem. (2002), 12. 3191.
[3] K.I. Kugel, D.I. Khomskii, A.O. Sboychakov, S.V. Streltsov, Phys. Rev. B (2015),
91, 155125.
[4] M. Intissar, R. Segni, C. Payen, J.P. Besse, F. Leroux, J. Solid State Chem.
(2002), 167, 508.
[5] M. Shao, M. Wei, D.G. Evans, X. Duan, Chem. Commun. (2011), 47, 3171.
60
Ag-TiO2 NANO-HETEROSTRUCTURES EXHIBITING GAS SENSING
PROPERTIES, VISIBLE-LIGHT ACTIVATED PHOTOCHROMISM WITH
SIMULTANEOUS PLASMON-ENHANCED PHOTOCATALYSIS AND
ANTIBACTERIAL ACTIVITY
D.M. Tobaldi1, S.G. Leonardi2, C. Piccirillo3, R.C. Pullar1, M.P. Seabra1,
P.M.L. Castro3, G. Neri2, J.A. Labrincha1
1
Department of Materials and Ceramic Engineering/CICECO–Aveiro Institute of
Materials, University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro,
Portugal
2
Department of Engineering, University of Messina, C. Da Di Dio, 98158 Messina,
Italy
3
Universidade Católica Portuguesa, CBQF – Centro de Biotecnologia e Química
Fina – Laboratório Associado, Escola Superior Biotecnologia, Rua Arquiteto Lobão
Vital, Apartado 2511, Porto, Portugal
Achieving advanced multifunctional materials displaying several coexisting properties
is nowadays one of the most exciting and innovative research topics. In this study, we
showed that Ag-TiO2 nano-heterostructures exhibited visible-light activated
photochromism with simultaneous plasmon-enhanced photocatalysis and antibacterial
activity. Furthermore, this material proved itself to be highly sensitive for detection of
acetone vapours at low concentrations.
Photochromic materials show reversible colour changes upon light exposure, and
could play a significant role in advanced devices such as photoswitches, photo-optical
sensors, smart windows, photo-electronics and optical storage memories. Visible-light
induced photochromism of these silver-modified (1-10 mol% Ag) titanium dioxide
(titania) nanoparticles (NPs) was monitored, and the change in colour experienced by
the specimens was thoroughly investigated, with both spectroscopic and colourimetric
analyses. Both the amount of silver present in the Ag-TiO2 nano-heterostructure, and
the visible-light irradiation time, dictated the degree and tuneability of the colour
change, from pale yellow to dark blue/violet in Ag-modified specimens. The colour
change was more rapid and extreme with increasing amounts of Ag, and the intensity
and wavelength of the surface plasmon resonance (SPR) induced under visible light
also increased [1].
Furthermore, as noble-metal-modified metal oxide nanoparticles (NPs) are well known
as visible-light harvesters for photocatalytic and antibacterial applications, the
photocatalytic and antibacterial activity were assessed. The former versus the
abatement of nitrogen oxides (NOx, major atmospheric pollutants), the latter against
Gram-positive and Gram-negative bacterial strains. Results showed that the silver
modified TiO2 possessed higher photocatalytic and antibacterial activity – when
stimulated by a visible-light source – than commercial Degussa P25 [1,2]. This
indicated the suitability of our material for use in health care, helping to greatly reduce
the spread of Gram-negative type bacteria such as E. coli.
Sensing properties of the designed materials were also assessed, against acetone, a
volatile organic compound (VOC) whose presence in indoor environment can cause
severe health risks. Our sensing tests showed that Ag-TiO2 sensor exhibited the
highest normalised response to acetone vapours at very low concentrations (<1 ppm)
compared to previous TiO2-based sensors reported in the literature [3].
61
[1] D.M. Tobaldi, M.J. Hortigüela Gallo, G. Otero-Irurueta, M.K. Singh, M.P.
Seabra, R.C. Pullar, and J.A. Labrincha, J. Phys Chem C, submitted.
[2] D.M. Tobaldi, C. Piccirillo, R.C. Pullar, A.F. Gualtieri, M.P. Seabra, P.M.L.
Castro, and J. A. Labrincha, J Phys Chem C, 2014, 118, 4751-4766.
[3] D.M. Tobaldi, S.G Leonardi, R.C Pullar, M.P. Seabra, G. Neri, and J.A.
Labrincha, J Mater Chem A, submitted.
62
MAGNETIC NANOPARTICLES FOR MONITORING MERCURY IN
WATERS
Daniela S. Tavares1, Cláudia B. Lopes1,2, Ana L. Daniel-da-Silva1, Armando
C. Duarte1, Carlos Vale2, Tito Trindade1, Eduarda Pereira1
1
University of Aveiro, CESAM and CICECO-Aveiro Institute of Materials/Chemistry
2 CIIMAR - Interdisciplinary Centre of Marine and Environmental Research, Rua dos
Bragas 289, 4050-123 Porto, Portugal
The Water Framework Directive (WFD) (200/60/EC) classifies mercury compounds as
priority hazardous substances and imposes maximum levels in water that need to be
well controlled. Several methodologies have been used to monitor the amount of
mercury in water, however a broad variation of mercury levels are reported in the
literature. This is mainly due to the complexity of the environmental matrices and
inadequate use of analytical techniques, transport and pre-treatment of water samples
that increase the risk of sample contamination or loss of analyte (high volatility and
sorption of Hg species on container surfaces). In addition, the ultra-trace concentration
of analyte is also a limitation that makes the reliable determination of Hg a major
analytical challenge. Hence, the development of reliable methods for the accurate
quantification of mercury in aquatic systems has been an interesting area of research.
Sorbents that result from recent nanotechnological research can have the potential to
contribute to the development of new technologies for water purification and
monitoring. In the present work, sorbents based on silica coated magnetite
nanoparticles have been functionalized with dithiocarbamate groups [1,2], in order to
remove and preconcentrate ultra-trace amounts of mercury from natural waters.
Compared with traditional sorbents, a distinct advantage of the tested material is that
the magnetic sorbents can be easily separated from aqueous solution by the
application of a magnetic gradient, thus allowing the removal of the contaminant from
contaminated water. The sorbent material investigated here have shown good
efficiency to promote mercury decrease in water from spiked synthetic and natural
waters such as estuarine and sea waters. Results also show the adequability of the
sorbent to quantify with trueness the concentrations of the metal in solutions even at
low levels (20 ng/L).
The authors thank the National Funding for Science and Technology (FCT) through doctoral
grants to D.S. Tavares (SFRH/BD//103828/2014) and University of Aveiro, FCT/MEC for the
financial support
to
CESAM,
CICECO
and
CIIMAR
(UID/AMB/50017/2013;
UID/CTM/50011/2013; UID/Multi/04423/2013), through national funds and, where applicable,
co-financed by the FEDER, within the PT2020 Partnership Agreement.
[1] D. S. Tavares, A. L. Daniel-da-Silva, C. B. Lopes, N. J. O. Silva, V. S. Amaral, J.
Rocha, E. Pereira, T. Trindade, J. Mater. Chem. 2013, 1, 8134-8143.
[2] D. S. Tavares, C.B. Lopes, A.L. Daniel-da-Silva, A.C. Duarte, T. Trindade, E.
Pereira Chem. Eng. J. 2014, 254, 559-570.
63
HETEROGENEOUS OXOMOLYBDENUM(VI)@IONIC LIQUID SYSTEMS
AS EFFECTIVE CATALYSTS FOR OXIDATIVE DESULFURIZATION
Diana Julião1,2, Ana C. Gomes1, Martyn Pillinger1, Rita Valença3, Jorge C.
Ribeiro3, Isabel S. Gonçalves1, Salete S. Balula2
3
1
Department of Chemistry, CICECO - Aveiro Institute of Materials, University of
Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal
2
REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências,
Universidade do Porto, 4169-007 Porto, Portugal
Galp Energia, Refinaria de Matosinhos, 4452-852 Leça da Palmeira, Matosinhos,
Portugal
Environmental concerns related with the sulfur compounds present in fuels have
introduced a need for complementary or alternative processes to the current
desulfurization method applied in the petroleum refining industry, referred as
hydrodesulfurization (HDS), which requires severe conditions, such as high
temperatures (300 to 400 °C) and high H2 pressures (3.0 to 5.0 MPa) to effectively
remove refractory sulfur compounds, such as dibenzothiophenes and derivatives. One
of the most promising methods to complement or replace HDS is oxidative
desulfurization (ODS). In ODS, the sulfur compounds are efficiently and selectively
removed from the fuel by oxidation/extraction under very mild reaction conditions.[1]
The production of sulfur-free fuels with this process has been described using ionic
liquids (ILs) as environmentally benign extraction solvents and H2O2 as a “green”
oxidant in the presence of several catalysts. Examples of effective catalysts for
application in ODS systems are transition metal-oxo species with active Mo(VI)
centers.[2,3]
In the present work, the complex [MoO2Cl2(4,4′-di-tert-butyl-2,2′-bipyridine)] was used
as a homogeneous catalyst for oxidation and removal of sulfur compounds present in
a model oil and an untreated diesel, using ILs as reaction medium and extraction
solvents and H2O2 as oxidant. The system comprising the complex proved to be
effective and capable of being recycled for several ODS cycles without losing
efficiency.
Acknowledgements:The FCT is thanked for support through the REQUIMTE/LAQV
(UID/QUI/50006/2013)
and
CICECO
(POCI-01-0145-FEDER-007679,
UID/CTM/50011/2013) projects, and for the grants to D.J. (SFRH/BD/102783/2014)
and A.C.G. (SFRH/BPD/108541/2015).
[1]
V.C. Srivastava, RSC Advances 2012, 2, 759.
[2]
J. Eber, P. Wassercheid, A. Jess, Green Chemistry 2004, 6, 316
[3] W. Zhu, H. Li, Q. Gu, P. Wu, G. Zhu, Y. Yan, G. Chen, Journal of Molecular
Catalysis A: Chemical 2011, 336, 16.
64
CRYOGENIC NANOTHERMOMETER BASED ON THE MIL-103(TB,EU)
METAL ORGANIC FRAMEWORK
Duarte Ananias1, Carlos D. S. Brites2, Luís D. Carlos2, João Rocha1
1
Department of Chemistry, CICECO – Aveiro Institute of Materials, University
2
Department of Physics, CICECO – Aveiro Institute of Materials, University of
Normalized Integrated Intensity
Microporous metal organic framework MIL-103 doped with Tb3+ and Eu3+, formulated
as [(Tb0.95Eu0.05)(BTB)(H2O)]⋅(solv)x (H3BTB = 1,3,5-tris-(4-carboxyphenyl)benzene;
solv = H2O, CH3OH) is shown to be a good platform for luminescent ratiometric
thermometry.[1] Although operative in a wide range of temperatures (10 – 320 K, see
Figure below) this material exhibits, in the cryogenic range (<100 K), one of the best
performances among metal organic frameworks, with a relative thermal sensitivity of
2.85 %⋅K−1, at 14 K. The material presents itself in the form of nanoparticles, suitable
for nanothermometry applications (e.g., microfluidics). Moreover, as MIL-103 is
nanoporous its use as a multisensing platformdeserves further consideration in the
near future. This work adds to the mounting evidence that metal organic frameworks
bearing trivalent lanthanides present considerable potential in nanothermometry and,
indeed, as multisensing platforms since they combine light emission and nanoporosity.
1.6
b)
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
10
60
110
160
210
260
310
Temperature (K)
Figure 1. a)Emission spectra (excited at 340 nm) of MIL-103(Tb0.95,Eu0.05) in the 14-300 K
range; b) Dependence of the corresponding integrated intensities of the Tb3+5D4→7F5 (green)
and Eu3+5D0→7F2(red) emission transitions.The areas were computed by integrating
numerically the emission spectra in the 537-570 nm and 600-635 nm ranges, respectively. The
corresponding errors result from the maximum difference between the integrated areas
computed when the integration limits of each transition is increased or decreased by 1 nm. The
maximum relative errors are 0.7% (5D0→7F2, at 25 K) and 8% (5D4→7F5 at 280 K).
Acknowledgments: Work financed by national funds through Fundação para a Ciência e a
Tecnologia (FCT), [project CICECO, reference number FCT UID/CTM/50011/2013 and
potdoctoral Grant to D. A. (SFRH/BPD/95032/2013)], and when applicable co-financed by the
Fundo Europeu de Desenvolvimento Regional (FEDER) under the PT2020 Partnership
Agreement.
[1] D. Ananias, C. D. S. Brites, L. D. Carlos, J. Rocha, Eur. J. Inorg. Chem. 2016,
1967-1971.
65
HYDROGEN-BOND ACIDITY AND BASICITY OF MIXTURES OF IONIC
LIQUIDS: EXPERIMENTAL AND COSMO-RS APPROACHES
Emanuel V. Capela1, Ana Rita R. Teles1, Ana Filipa M. Cláudio1, Kiki A.
Kurnia2 João A. P. Coutinho1, Mara G. Freire1
1
2
Center of Research in Ionic Liquids, Department of Chemical Engineering,
Universiti Teknologi PETRONAS, Tronoh 31750, Perak, Malaysia
In the past decade, ionic liquids (ILs) have been the focus of intensive research
regarding their use as potential and alternative solvents in many chemical
applications [1]. Targeting their effectiveness, recent investigations have
attempted to establish polarity scales capable of ranking ILs according to their
chemical behaviors [2]. However, mixtures of ILs can broaden the tailoring
ability of these fluids aiming at tuning their polarity, and thus their effectiveness
as potential solvents for the most diverse applications. Based on this possibility,
this work aims at determining the solvatochromic parameters of mixtures of ILs
and to evaluate the ability of adjusting their polarity. In this work, various
mixtures of ILs, with different proportions of each IL (in the whole composition
range) were investigated by the determination of their Kamlet–Taft
solvatochromic parameters, namely hydrogen-bond acidicity, hydrogen-bond
basicity and dipolarity/polarizability. Since polarity scales only report relative
ranks because they depend on the set of probe dyes used, we additionally
addressed the COSMO-RS (COnductor-like Screening MOdel for Real
Solvents) capability as an alternative tool to estimate the solvatochromic
parameters of mixtures of ILs. This theoretical approach allows to classify
mixtures of ILs according to their chemical behavior and opens the possibility
to pre-screen appropriate mixtures for a given task or application.
References
[1] M. A. Ab Rani, A. Brant, L. Crowhurst, A. Dolan, M. Lui, N. H. Hassan, R.
Wilding, Physical Chemistry Chemical Physics, 2011, 13, 16831-16840.
[2] A. F. M. Cláudio, L. Swift, J. P. Hallett, T. Welton, J. A. Coutinho, M. G.
Freire, Physical Chemistry Chemical Physics, 2014, 16, 6593-6601.
Acknowledgements: This work was developed within the scope of the project
CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT
Ref. UID /CTM /50011/2013), financed by national funds through the FCT/MEC
and when appropriate co-financed by FEDER under the PT2020 Partnership
Agreement. M. G. Freire acknowledges the European Research Council (ERC)
for the Starting Grant ERC-2013-StG-3377.
66
ENHANCED SOLUBILITY OF NATURAL TRITERPENIC ACIDS AND
PHENOLIC COMPOUNDS WITH AQUEOUS SOLUTIONS OF IONIC
LIQUIDS
Emanuelle L. P. de Faria1, Selesa V. Shabudin1, Ana Filipa M. Claúdio1, João
A. P. Coutinho1, Carmen S. Barros1, Fernando M. J. Domingues 2, Armando J.
D. Silvestre1, Mara G. Freire1*
1
of Aveiro, 3810-193 Aveiro, Portugal.
2
Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal.
*E-mail: [email protected]
In the past few years it has been observed an increased interest on the use of aqueous
solutions of ionic liquids (ILs) for the solubilization and extraction of value-added
compounds from biomass [1,2]. The interest on these compounds, and particularly on
triterpenic acids and phenolic compounds, comes from the wide variety of their relevant
properties, namely their antioxidant, anti-inflammatory, radical scavenger and
antimicrobial characteristics [1]. However, these value-added compounds are still
extracted from their natural matrices using volatile and often toxic organic solvents.
Aiming at designing and optimizing more sustainable extraction processes, in this
work, aqueous solutions of ILs were investigated as alternative solvents. In particular,
the solubility of phenolic compounds and triterpenic acids in aqueous solutions of ILs
with different anion/cation combinations, in a wide range of concentrations, was
determined at 303 K. A large number of ILs was studied to infer on the chemical
structure characteristics that better perform for the extraction of these bioactive
compounds. An increase in the solubility of up to 50- and 80-fold was observed for
syringic acid and ursolic acid, respectively, when compared with their solubility in pure
water. The results obtained confirm that aqueous solutions of ILs are improved
solvents for phenolic compounds and triterpenic acids, which thus support their use in
the extraction of value-added components from biomass residues, such as Eucalyptus
globulus bark.
[1] Cláudio, A.F.M., Ferreira, A.M., Freire, C.S.R., Silvestre, A.J.D., Freire, M.G.
and Coutinho, J.A.P., “Optimization of the gallic acid extraction using ionicliquid-based aqueous two-phase systems”, Sep. Purif. Technol., 2012, 97: 142149.
[2] Passos, H., Freire, M.G. and Coutinho, J.A.P., “Ionic liquid solutions as
extractive solvents for value-added compounds from biomass”, Green Chem.,
2014, 16: 4786-4815.
Acknowledgements: This work was developed in the scope of the project CICECOAveiro Institute of Materials (Ref. FCT UID/CTM/50011/2013), financed by national
funds through the FCT/MEC and when applicable co-financed by FEDER under the
PT2020 Partnership Agreement. M.G. Freire acknowledges the European Research
Council (ERC) for the Starting Grant ERC-2013-StG-337753. E. L. P. de Faria
acknowledges the PhD grant (200908/2014-6) and financial support from Conselho
Nacional de Desenvolvimento Científico e Tecnológico – CNPq.
67
MAGNETOELECTRIC EFFECT ENHANCEMENT BY BREAKING THE
GEOMETRIC MAGNETIC FRUSTRATION IN LuMn1+zO3+δ CONTROLLED
OFF-STOICHIOMETRY
F. G. Figueiras1,2, D. V. Karpinsky1, P. Tavares3, J. A. Moreira2, V. S. Amaral1
1
Physics Dep. & CICECO-AIM, Aveiro University, 3810-193 Aveiro, Portugal
2
IFIMUP-IN, Science Faculty; Porto University, 4169-007 Porto, Portugal
3
Chemistry Center, UTAD, 5001-801 Vila Real, Portugal
This study explores controlled off-stoichiometric LuMn1+zO3+δ (|z|<0.1,
|δ|<0.005) compounds, intended to retain the utter LuMnO3 intrinsic hexagonal
symmetry and ferroelectric properties. X-ray powder diffraction measurements
evidenced single phase P63cm structure. Thermo-gravimetric experiments
show a narrow impact of oxygen vacancies while distinguish a gas exchange
at ~700K, surprisingly lower temperature when comparing to perovskite
systems. Comparison of different nominal ceramics revealed pertinent
structural and magnetic properties variations owing to subtle self-doping
effects. Deviations from the archetypal antiferromagnetic state were detected
below ~90K suggesting local rearrangements of the nominal Mn3+ ions matrix,
breaking the ideal geometrical spins frustration, leading to non-compensated
magnetic structure. [1].
A comprehensive insight of the structural and properties effects in the
LuMn0.98O3 coumpound is supported by Neutron Powder Diffraction
measurements confirming single phase hexagonal structure and exposing,
below ~90K, a pertinent ferromagnetic component which breaks the archetypal
geometrical frustrated antiferromagnetic state ascribed for the utter LuMnO3
compound [2]. The evaluated triangular disposition of spins prompts an electric
polarization contribution [3] and a clear enhancement the magnetoelectric
effect [4]. In addition, Raman spectroscopy, dielectric, pyroelectric and
magnetic measurements as function of temperature enabled to recognize
intrinsic interaction between structural, transport and magnetic contributions,
well above Néel transition.
[1] F. G. Figueiras
10.1039/C6CP01562J
et
al.,
Phys.Chem.Chem.Phys.,
[2]
S. Lee, et al., Nature 451, 2008, 805.
[3]
L. N. Bulaevskii et al., Physical Review B 78, 2008, 024402
[4]
I. V. Solovyev, et al., Phis. Review B 86, 2012, 054407.
68
2016,
DOI:
HEAT@UA - THE THERMAL RESEARCH LABORATORY OF THE
UNIVERSITY OF AVEIRO
F. Mohseni1,2, M. J. Pereira1,2, A. Davarpanah1,2, T. Santos1,2, A. BarrosTimmons1,3, V. A. F. Costa4,5, J. S. Amaral1,2, V. S. Amaral1,2
1CICECO
2
3
- Aveiro Institute of Materials, University of Aveiro, Portugal
Department of Physics, University of Aveiro, Portugal
Department of Chemistry, University of Aveiro, Portugal
3
TEMA - Centre for Mechanical Technology and Automation, Aveiro
University, Portugal
4
Department of Mechanical Engineering, Aveiro University, Portugal
The thermal properties of materials affect their performance and applicability in
many fields, particularly in energy applications and conversion. Temperature,
and as a result, other thermal properties can be measured via direct contact
methods between the measuring device and the medium of interest or by
remote observation methods. In the thermal research laboratory of the
University of Aveiro (Heat@UA), the infrastructure exists to investigate different
thermal properties of bulk to nano materials. We aim to face ongoing academic
and industrial challenges on the study and development of new thermal
materials and processes. Our main lines of research employ:
FLIR 5650 Infrared Camera with Microscopy Setup
Infrared (IR) thermometry allows non-contact observation of the dynamic
temperature distribution during processes and cycles, for characterization and
optimization of both materials and thermal processes. IR imaging results can
be compared to numerical simulations, allowing improved model parameters.
Park XE7 AFM with Scanning Thermal Microscopy Module
Standard Atomic Force Microscopy (AFM) topography analysis is widely used
to obtain detailed information on the surface of materials at the nanoscale.
Through our Scanning Thermal Microscopy (SThM) setup, it is possible to
measure temperature, thermal conductivity and study structural phase
transitions at the nano-scale.
HotDisk TPS2500s
The transient plane source (TPS) method allows the measurement of the
thermal conductivity and specific heat of solids, liquids, thin films, coatings and
powders. Our HotDisk setup permits fast and precise measurements, favorable
in both scientific and industrial usages, in a wide temperature range.
For more information, please visit our laboratory webpage: www.heat-ua.pt
69
MULTIPLE EMULSION TEMPLATING OF Ag@SiO2 CAPSULES FOR
ANTIBACTERIAL APPLICATIONS
Filipa L. Sousa1, A. V. Girão1, S. Fateixa1, A. Almeida2, T. Trindade1
1
2
Department of Chemistry-CICECO, University of Aveiro, Campus de
Santiago, 3810-193 Aveiro, Portugal
Department of Biology-CESAM, University of Aveiro, Campus de Santiago
Silver nanoparticles (NPs) encapsulated in amorphous silica shells were synthesized
and evaluated for their antibacterial action using the Gram negative Escherichia coli
bacterium. These inorganic capsules were synthesized using a new approach that
comprises the use of oil-in-water-in-oil O/W/O multiple emulsions to fabricate SiO2
capsules incorporating organically capped Ag NPs. This strategy was explored as a
way to promote the bioadhesion of the microorganisms to the silica rough surfaces
while still keeping the system with a high surface area for the active metal. The results
have shown that the hybrid capsules enable a slow release of cationic silver from the
interior of the silica microsphere to the external medium, probably through the pore
channels in the shell. The antibacterial activity against E. coli is mainly determined by
the Ag+ ion release rate, suggesting that these particulates can be employed as a
robust system for prolonged used as an antimicrobial material [1].
[1] F. L. Sousa, A. Almeida, A. V. Girão, S. Fateixa, T. Trindade, Particle and
Particle Systems Characterization 2015 32, 561.
70
SURFACTANTS AS ALTERNATIVE SOLVENTS IN THE EXTRACTION OF
BIOACTIVE COMPOUNDS FROM BROWN MACROALGAE
Flávia A. Vieira1, Ricardo J. R. Guilherme1, Helena Abreu 2, Márcia C. Neves1, João
A. P Coutinho1, Sónia Ventura 1
1
2
ALGAplus Lda, Travessa Alexandre da Conceição 3830-196 Ílhavo, Portugal
Seaweeds are a marine raw material, rich in a variety of chemicals of economic and
industrial interest. Despite their high potential as source of biofuels, novel materials
and fine chemicals, they are scarcely used and valorized. One of the major limitations
of the use of algae is their large content of water that often compromises the economic
viability of the extraction processes, which explains the limited development of the
marine biorefinery platform. A more effective and appropriate purification method to
extract bioactive chemicals from algae is required. Brown seaweeds are abundant in
Portugal and some of them are being considered as invasive species, namely the
Sargassum muticum [1]. Due to its Japanese origin and the potential problems
associated with some ecosystem alterations and biodiversity loss [2], this species
could be extensively harvested for industrial use. Sargassum muticum will thus be here
adopted as a raw material for the extraction of fucoxanthin, a well-known carotenoid
[1], with important characteristics, namely its antioxidant, anti-inflammatory, and
antitumoral characteristics [1, 2].
Since one of the major limitations of the algae processing is their large water content
that often compromises the economic viability of the extraction processes, in this work
the use of surfactants will be adoted regarding the disruption of the cells and then
extraction of fucoxanthin. The cell disruption will be characterized by scanning electron
microscopy, the micelle morphology by optical microscopy, and the extraction
performance will be quantified by the measurement of the fucoxanthin using HPLC.
Conditions such as, the maceration of the cells, time of exposure, type of surfactants
(non-ionic, anionic, cationic and zwitterionic common surfactants and tensioactive ionic
liquids) and the amount of macroalgae added in the maceration step will be studied.
[1] Nicolantonio, D. O. et al., Marine Drugs, 2012 10, 604.
[2] Peng, J. et al., Marine Drugs, 2011, 9, 1806.
71
AQUEOUS BIPHASIC SYSTEMS FORMED BY COPOLYMERS AND
BIOCOMPATIBLE IONIC LIQUIDS
Francisca A. e Silvaa, Rui M. C. Carmoa, Andreia P. M. Fernandesa, João A.
P. Coutinhoa, Sónia P. M. Venturaa
a
While several fields of industries are increasingly requiring natural compounds
to develop their products, the currently available techniques are not effectively
responding to such a need. Ionic-liquid-based aqueous biphasic systems (ILbased ABS) arise as promising alternatives due to their tunable nature, which
is afforded not only by the designer solvent character of IL itself, but also with
the variety of components which they can be combined with to generate ABS
[1]. Although these systems act outstandingly at extracting several molecules,
when there is the need to selectively purify structurally similar compounds, their
performance is compromised.
Under this scenario, the introduction of copolymers in the IL-based ABS domain
is here envisaged as a way of creating “even more tunable” types of systems.
Once copolymers result from the polymerization of two or more different
monomeric units, their structure and properties can be finely tuned, just like ILs.
Thus, this work is divided into two main parts: one wherein the ternary phase
diagrams for systems composed of copolymer and various cholinium-based ILs
systems were determined and discussed considering ILs’ structural features
and temperature; and another wherein the application of the developed ABS on
the selective extraction of two natural flavonoids was attempted and compared
to more traditional systems. At the end, the novel ABS herein developed not
only possess intermediate properties, but also exhibit a notable selectivity for
structurally similar compounds.
[1] M. G. Freire, A. F. M. Cláudio, J. M. M. Araújo, J. A. P. Coutinho, I. M.
Marrucho, J. N. C. Lopes, L. P. N. Rebelo, Aqueous biphasic systems: a boost
brought about by using ionic liquids, Chem. Soc. Rev. 41 (2012) 4966-4995.
This work was developed in the scope of the project CICECO-Aveiro Institute
of Materials (Ref. FCT UID/CTM/50011/2013), financed by national funds
through the FCT/MEC and when applicable co-financed by FEDER under the
PT2020 Partnership Agreement. F. A. e Silva and S.P.M. Ventura are thankful
to FCT for the financial support on the ambit of their doctoral and postdoctoral
grants (SFRH/BD/94901/2013 and SFRH/BPD/79263/2011), respectively.
72
TEMPERATURE-SWITCHABLE IONIC-LIQUID-BASED AQUEOUS
BIPHASIC SYSTEMS
Helena Passos1, Andreia Luís1, João A. P. Coutinho1 and Mara G. Freire1
1
The ability to induce reversible phase transitions between aqueous
homogeneous solutions and biphasic liquid-liquid systems, at pre-defined and
suitable operating temperatures, is of outstanding relevance in the design of
separation and purification processes for value-added compounds. It was
already demonstrated that phase transitions in mixtures involving ionic liquids
(ILs) and other solvents can be induced by changes in temperature or by
reversible reactions with CO2 [1-3]. Most of binary liquid-liquid systems
comprising ILs typically occur at temperatures far from room temperature and
are confined to mixture compositions imposed by the upper or lower critical
points of the phase diagrams. Moreover, these systems are composed of an
IL-rich phase (typically with hydrophobic characteristics) and a molecularsolvent-rich phase.
In this work, we show that aqueous biphasic systems (ABS), i.e., ternary
systems where the major solvent is water, may have their reversible behavior
triggered by small changes in temperature (as low as 1 ºC). The applicability of
the temperature-induced phase switching is further demonstrated with the
complete extraction for the IL-rich phase, in a single-step, of two value-added
proteins, namely cytochrome c and azocasein. It is shown that the temperature
induced phase switching provided by IL-based ABS is significantly more
versatile than classical liquid-liquid systems which are constrained by their
specific critical temperatures. Instead, this approach allows to combine and to
work in a wide range of temperatures and compositions which can be tailored
to fit the requirements of a given separation process [4].
Acknowledgments: This work was developed within the scope of the project
Agreement. The authors also acknowledge FCT for the doctoral grant
SFRH/BD/85248/2012 of H. Passos. M. G. Freire acknowledges the European
Research Council under the European Union's Seventh Framework
Programme (FP7/2007-2013) / ERC grant agreement n° 337753.
[1]
Y. Kohno, H. Ohno, Chem. Commun. 2012, 48, 7119.
[2]
Y. Kohno, H. Arai, H. Ohno, Chem. Commun. 2011, 47, 4772.
[3]
S. Saita, Y. Kohno, N. Nakamura, H. Ohno, Chem. Commun. 2013, 49,
8988.
[4]
H. Passos, A. Luís, J.A.P. coutinho, M.G. Freire, Sci. Rep. 2016, 6,
20276.
73
IMPROVED EXTRACTION OF FLUOROQUINOLONES WITH
RECYCLABLE IONIC-LIQUID-BASED AQUEOUS BIPHASIC SYSTEMS
Hugo F.D. Almeida1,2, Mara G. Freire2, Isabel M. Marrucho1
1
Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de
Lisboa, 2780-157 Oeiras, Portugal
2
CICECO – Aveiro Institute of Materials, Chemistry Department, University of Aveiro,
In the 21st century, due to the improvement of advanced analytical tools, it was
confirmed the presence of active pharmaceutical ingredients (APIs) in sewage
treatment plants (STPs), wastewater treatment plants (WWTPs) and surface water
effluents, which rose serious concerns since they are present in non-negligible levels
(ng/L – µg/L). The faced increased consumption of pharmaceuticals, although leading
to significant improvements in human living conditions, results in their inevitably
excretion into the environment, and where the continuous humans contact with APIs
also leads to health problems.[1, 2] Aiming at finding cost-effective approaches for
removing APIs from aqueous media, this work shows the feasibility of using ionicliquid-based aqueous biphasic systems (IL-based ABS) in the extraction of a wide
variety of antibiotics, namely fluoroquinolones (FQs) - APIs of particular concern due
to the current increasing number of antibiotic resistant bacteria. In particular, ABS
composed of imidazolium- and phosphonium-based ILs and aluminium-based salts
(already used in water treatement plants) were evaluated in one-step extractions of six
FQs. Foreseeing, the development of more cost-effective and sustainable techniques,
the recyclability/reusability of these systems was also evaluated. The recycling of the
IL and its further reuse without losses in the ABS extractive performance for FQs was
confirmed by consecutive removal/extraction cycles.[3] The results obtained support
the development of IL-based ABS with a lower environmental footprint and economic
impact, while opening perspectives for their implementation in WWTPs.
Acknowledgements: This work was developed in the scope of the project CICECO
(Ref. FCT UID/CTM/50011/2013), financed by national funds through the FCT/MEC
and when applicable co-financed by FEDER under the PT2020 Partnership
Agreement. Hugo F. D. Almeida acknowledge FCT for the doctoral grant
SFRH/BD/88369/2012, M. G. Freire acknowledges the European Research Council
(ERC) for the starting grant ERC-2013-StG-337753 and I. M. Marrucho
acknowledges the 2012 FCT Investigator Program.
1.
T. Heberer, Toxicology Letters, 2002, 131, 5-17.
2.
R. H. Lindberg, M. Östman, U. Olofsson, R. Grabic and J. Fick, Water
Research, 2014, 58, 221-229.
3.
H. F. D. Almeida, M. G. Freire and I. M. Marrucho, Green Chemistry, 2016, doi:
10.1039/C5GC02464A.
74
POTATO INDUSTRY BYPRODUCTS: AN ALTERNATIVE BIOPOLYMERS’
SOURCE FOR RENEWABLE PACKAGING MATERIALS
Idalina Gonçalves1,2, Ana Barra2, Cláudia Nunes1,2, Manuel A. Coimbra1,
Paula Ferreira2
1
2
CICECO - Aveiro Institute of Materials, Department of Materials and Ceramic
Nowadays, the environmental impact and high cost of recycling conventional plastics
are the main motivation to search renewable packaging materials. As a petroleum
substitute, non-reused agrofood industrial byproducts are promising raw materials.
Herein, adding value to potato industry byproducts (washing waters, small potato
fragments removed from slicers, potato peels, and frying oils), through exploitation of
biopolymers for the development of renewable packaging materials, is an opportunity.
Potatoes have a high content of carbohydrates in which starch is the main source of
polysaccharides. Due to its various functional properties such as gelling and thickening
abilities, starch has a high potential for the development of materials [1]. Moreover,
potato peels contain lipids, polyesters constituted by long chain fatty acids (waxes),
and phenolic compounds (such as caffeic and gallic acids) capable to assign
hydrophobic and antioxidant properties to the materials [2, 3].
In this work, starch, oils and waxes were extracted from potato industry byproducts.
Potato starch granule size, morphology (SEM), crystallinity (X-Ray) and
calorimetry (DSC) were evaluated. Moreover, potato starch-based films with suitable
properties for packaging materials were produced. Mechanical and physicochemical
properties of different component ratios were tested to investigate the raw materials
influence on starch-based films characteristics. Commercial potato starch was used
as reference. The unpurified starch from potato washing waters presented a higher
granule size (≈ 89 µm) than commercial starch (≈ 50 µm). In addition, starch from
potato washing waters showed mostly amorphous structure that needed a lower
gelatinization temperature (≈ 58 ºC) than reference (≈ 64 ºC). When applied on films
production, starch from potato washing waters yielded materials with increased tensile
strength and deformation ability, although with less elastic properties than commercial
starch-based films. Besides, oil and waxes incorporation improved potato starchbased films hydrophobicity and elasticity, respectively. Therefore, potato industry
byproducts revealed to be a promising biopolymers’ source for the development of
renewable packaging materials.
Acknowledgements: Thanks are due to FCT through national founds and FEDER, within the
PT2020 Partnership Agreement, for funding QOPNA (FCT UID/QUI/00062/2013) and
CICECO-Aveiro Institute of Materials (FCT UID/CTM/50011/2013; POCI-01-0145-FEDER007679). I.G. (SFRH/BPD/104712/2014), C.N. (SFRH/BPD/100627/2014) and P.F.
(IF/00327/2013) also thank the support of FCT. The authors also acknowledge “A Saloinha,
Lda.” for its interest in the work and providing potato byproducts.
1. K., Alvani, X. Qi, R. F. Tester, C. E. Snape, Food Chemistry 2011, 125, 958-965.
2. Z. G. Wu, H. Y. Xu, Q. Ma, J. N. Ma, C. M. Ma, Food Chemistry 2012, 135, 24252429.
3. B. M. Szafranek, E.E. Synak, Phytochemistry 2006, 67, 80-90.
75
CONTROLLING GABAPENTIN POLYMORPHISM: IONIC LIQUIDS AS
CRYSTALLIZATION MEDIA
Inês C. B. Martins1,2, M. Teresa Duarte1, Luís Mafra2
1
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa,
1049-001, Lisboa, Portugal
2
Department of Chemistry, CICECO – Aveiro Institute of Materials, University of
Up to now pharmaceutical industry has focused its attention on solid dosage form (95%
of marketed drugs), primarily crystalline forms, for the delivery of active pharmaceutical
ingredients (APIs). Most valuable reasons are purity, thermal stability, manufacturing
and ease of handling. However, one of the drawbacks in using APIs as solids is their
propensity to polymorphism. This solid-state phenomenon, characterized by the ability
of an API to crystallize into different packing arrangements, strongly affects its
physicochemical properties, such as solubility, bioavailability and efficacy, causing
severe commercial losses, patent issues and diverse court litigations.
A common approach to tackle API polymorphism issues involves crystallization
screening using a wide range of conventional solvents. In this sense, room
temperature ionic liquids (RTILs) have gained, during the last decade, a new role as
possible and promising crystallization solvents.[2]
Gabapentin (Gaba), an amino acid-based drug used to treat neurodegenerative
diseases, presents itself in three polymorphic forms (II, III and IV) that are easily
interconverted.[3] Gaba Form II is the thermodynamic more stable polymorph, while
Form IV is the kinetic polymorph (less stable at room temperature conditions).
Here we report some challenging results using RTILs in Gaba polymorphic control:[4]
a) RTILs revealed promising capabilities in directing Gaba crystallization; b) for the first
time, pure “bulk” Gaba Form IV was obtained and characterized by X-ray powder and
single crystal diffractions. This polymorph has been to date difficult to isolate.
[1] J. Stoimenovski, D. R. MacFarlane, K. Bica, R. D. Rogers Pharmaceut. Res. 2010,
27, 521-526
[2] R. Ferraz, L. C. Branco, C. Prudêncio, J. P. Noronha, Z. Petrovski, ChemMedChem,
2011, 6, 975-985
[3] D. Braga, F. Grepioni, L. Maini, K. Rubini, M. Polito, R. Brescello, L. Cotarca, M. T.
Duarte, V. André, M. F. M. Piedade, New J. Chem, 2008, 32, 1788-1795
[4] Manuscript submitted
Acknowledgements:The work was financed by FCT, FCT/MEC and cofinanced by
FEDER under the PT2020. The authors acknowledge funding of the FCT projects
UID/QUI/00100/2013 and SFRH/BD/93140/2013.
76
ALD DEPOSITION OF ALUMINA ON UNTREATED CVD GRAPHENE
Inês Oliveira1, Miguel Neto1, Nuno F. Santos2, Bogdan Kulyk2, Alexandre F.
Carvalho2, Filipe J. Oliveira1, António J.S. Fernandes2, Rui F. Silva1, Florinda
M. Costa2
1
2
I3N, Physics Department, University of Aveiro, Campus de Santiago, Aveiro,
Portugal
The integration of graphene with other materials at the nanoscale is required
for a large number of applications, including biosensors, supercapacitors and
field effect transistors (FET). Atomic layer deposition (ALD) is a highly
controllable synthesis technique, enabling ultra-thin films or surface decoration
with individual particles. However, in order to successfully coat graphene by
ALD, the low nucleation yield typical of highly inert intrinsic graphene must be
circumvented.
In this study, we deposited Al2Ox using ALD on graphene grown by microwave
plasma CVD (MPCVD), both in the as grown state (Cu substrate) and after
transferring it into silicon. The explored ALD parameters were temperature,
precursors (H2O, TMA) pulse width, and number of cycles. The resulting films
were characterized by SEM/EDS microscopy, µRaman spectroscopy, X ray
reflectrometry and optical profilometry.
Our results show that alumina nucleated and developed dense films on both
graphene sample types, exceeding 10nm in thickness for runs with 100 cycles.
The MPCVD graphene provided the defective/hydrogenated sites for the
nucleation mechanism. Thus, it was demonstrated that it is possible to directly
coat CVD grown graphene with a dielectric Al2Ox layer by ALD, as required in
graphene FETs, without the need for any pretreatments.
77
VOLUME DEPENDENCE OF MAGNETIC PROPERTIES IN Co2CrGaBASED HEUSLER ALLOYS FOR MAGNETOCALORIC APPLICATIONS: A
FIRST-PRINCIPLES STUDY
J. N. Gonçalves1, N. M. Fortunato1, J. S. Amaral1,2, V. S. Amaral1
1CICECO
- Aveiro Institute of Materials and Departamento de Física,
Universidade de Aveiro, 3810-193 Aveiro, Portugal
2IFIMUP and IN-Institute of Nanoscience and Nanotechnology, Rua do Campo
Alegre, 678, 4169-007 Porto, Portugal
We present a detailed study of quaternary full Heusler alloys with general
formula Co2Cr1−xYxGa (Y=Ti, V, Mn, Fe, Co, Ni), with particular attention given
to the volume and pressure dependence of its magnetic Curie temperatures
(TC) and spin moments. We use the density functional Korringa-Kohn-Rostoker
method as implemented in the SPR-KKR code. We first study some of the
ternary end compounds, and we find that, although the generalized gradient
approximation leads to more accurate equilibrium lattice parameters, the local
density approximation (LDA) leads to better predictions to the change of the
Curie temperature with volume, dTC/dV. We then use the LDA to study the
quaternary alloys, using the coherent potential approximation to treat disorder.
Effective Heisenberg exchange constants are calculated via the magnetic force
approach, and the mean field TC is obtained for changing compositions in steps
of ∆x = 0.1. We present the calculated dTC/dV with a view to find high
performance magnetocaloric materials. These materials display a wide range
of property values suitable for composition tuning. The magnetic moments
range from 0.8 to 4.9 µB, and TC from 130K with Ti to 1250K with Fe. dTC/dV is
negative for the Cr, Mn and Fe rich compounds, but increases with addition of
Ti, V, Ni, and Co becoming positive for high concentrations of these elements.
It ranges from −7 (Co2MnGa) to +6.3 K·Å−3 (Co2Cr0.9Ni0.1Ga). The Ni and V rich
compositions possess TC close to room temperature, and similar magnetic
moments, while clearly higher dTC/dV for Ni should benefit the magnetocaloric
effect, while the Co2CrGa and Co2MnGa compounds possess the largest
negative values. The systematic computational search of optimally
magnetovolume enhanced magnetocaloric materials may be continued with
other materials and more sophisticated calculation approaches.
78
VANADIUM-SUBSTITUTED SrTiO3: FROM OXIDIZED PHASES TO SOFC
ANODES
Javier Macías(1), Aleksey Yaremchenko(1), B.R. Sudireddy (2), S. Veltze (2), P.
Holtappels(2), Jorge Frade(1)
1) Department of Materials and Ceramic Engineering, CICECO,
University of Aveiro, Portugal
2) Department of Energy Conversion and Storage, Technical University of
Denmark, Roskilde, Denmark
Perovskite-type SrTiO3 and SrVO3 and their derivatives were reported to exhibit
substantial sulfur tolerance and resistance to carbon deposition and therefore
attract significant attention as promising ceramic components for anodes of
hydrocarbon-fueled SOFCs. SrVO3 possess high metallic-like electronic
conductivity, but also has a very narrow stability domain limited to reducing
conditions. On the other hand, SrTiO3 demonstrate remarkable thermodynamic
and dimensional stability in a wide range of T-p(O2) conditions, but rather
insufficient electrical conductivity for electrode applications. The present work
was focused on the development of anode materials by vanadium substitution
into SrTiO3 with emphasis on the possibility of in-situ reduction of oxidized
electrode layers, electrical properties and electrochemical behavior.
SrTi1-xVxO3 (x = 0.1-0.3) were prepared by solid state reaction method in air
starting from SrCO3, TiO2 and V2O5. Two routes were employed. In first route,
precursor mixtures were fired with a step-wise increase of temperature (up to
1400°C) and repeated regrindings until formation of impurity-free cubic
perovskite phase. In the second route, the highest firing temperature was
limited to 1100°C yielding multiphase mixtures comprising major SrTiO3-based
perovskite phase, secondary Sr3V2O8 phase, and some other minor impurities.
All prepared materials were ball-milled, compacted and sintered in air at 10001100°C to produce porous ceramic samples emulating electrode layers.
All sintered ceramics demonstrate semiconducting behavior in air with low
conductivity values (< 10-3 S/cm at 1000°C). In-situ reduction in 10%H2-N2 flow
at 900°C was found to result in significant increase of electrical conductivity by
2.5-4 orders of magnitude. Reduced multiphase materials exhibited higher
conductivity (reaching ~5 S/cm at 900°C for x = 0.3) compared to single-phase
counterparts due to transformation of Sr3V2O8 into conducting SrVO3 uniformly
distributed in composite ceramics.
Multiphase oxidized SrTi0.7V0.3O3 was used for fabrication of porous electrodes.
Electrodes were screen-printed onto yttria-stabilized zirconia solid electrolyte,
sintered in air at 1175°C, impregnated with Ni+CGO (gadolinia-doped ceria),
and finally reduced in hydrogen flow at 850°C. Electrochemical activity of
electrode layers was studied by electrochemical impedance spectroscopy
using symmetrical cells in 3%H2O-H2 and 50%H2O-H2 atmospheres at 650850°C.
79
CO-AMORPHOUS γ-CYCLODEXTRIN:MONTELUKAST (1:1) ADDUCT BY
MECHANOCHEMISTRY PROCEDURES, WITH RESOURCE TO
PRE-MILLING OF γ-CYCLODEXTRIN
Jessica Silva Barbosa1,2, Filipe A. Almeida Paz2, Susana Santos Braga1
1
2
Department of Chemistry, QOPNA research unit, University of Aveiro, 3810-193
Aveiro, Portugal
Cyclodextrins are useful molecular capsules to protect guests from degradation. In a
number of situations these molecules were shown to alter pharmacokinetic parameters
of drugs through the formation of inclusion compounds. The current formulations of
Montelukast sodium (MLK) have some instability to light and low bioavailability. In the
present work we propose the formation of inclusion compounds between montelukast
sodium and γ-cyclodextrin (γ-CD), in order to overcome these known issues of this
active pharmaceutical ingredient (API).
To obtain the inclusion compounds a solvent-free method was used:
mechanochemistry. γ-CD was subject to pre-treatment by grinding for 60 minutes.
Then, ground γ-CD was added with an equimolar quantity of montelukast sodium and
this mixture was considered time zero (in minutes). The mixture was ground for 60
minutes and aliquots were collected at 5, 10, 15, 25 and 30 minutes. Samples were
analyzed by solid-state 13C{1H} CP-MAS NMR, Powder X-Ray diffraction, FT-IR ATR
spectroscopy and thermogravimetry. Data from Powder X-Ray diffraction studies show
that the pre-grinding of γ-CD led to its amorphisation, which remain constant during the
co-grinding with MLK. It was also visible in FT-IR ATR a very small shift in the carbonyl
band of MLK. Moreover, thermogravimetry demonstrated a modification in the
degradation temperature of the inclusion compounds with respect to the physical
mixture of MLK and γ-CD. Together, these results suggest the formation of a coamorphous new adduct.
Part of this work was developed within the scope of the project CICECO-Aveiro
Institute
of
Materials,
POCI-01-0145-FEDER-007679
(FCT
Ref.
UID/CTM/50011/2013), financed by national funds through the FCT/MEC and when
appropriate co-financed by FEDER under the PT2020 Partnership Agreement.
Thanks are due to University of Aveiro and FCT/MEC for the financial support to the
QOPNA research project (FCT UID/QUI/00062/2013) through national founds and
where applicable co-financed by the FEDER, within the PT2020 Partnership
Agreement.
80
ASSEMBLY OF METAL COLLOIDS ONTO SURFACE FUNCTIONALIZED
MAGNETITE PARTICLES
Joana L. Lopes1, Karine L. Marques2, Ana V. Girão1, Eduarda Pereira2, Tito
Trindade1
1
Aveiro, 3810-193 Aveiro, Portugal.
2
CESAM – Department of Chemistry, University of Aveiro, 3810-193 Aveiro,
Portugal
In the course of our research on new magnetic sorbents for metal species, we have
recently described the preparation of dithiocarbamate functionalized magnetite
particles that show high efficiency for mercury uptake from water [1] These materials
comprise a ferromagnetic core (magnetite: Fe3O4) coated with silica shells enriched in
dithiocarbamate moieties. Silica coated nanomaterials have been extensively used
because confer robustness to the magnetic phases and offer a convenient platform for
chemical derivatization, thus making easy the grafting of diverse functional groups at
the surface of the nanoparticles. On the other hand, the magnetic cores confer ability
for magnetic separation of the particles from the corresponding suspensions, just by
employing an external magnetic field.
Taking advantage of the above properties of the surface modified magnetite particles,
we have carried a series of experiments in which their sorption behavior for noble metal
colloids (Ag, Au, Pt, Pd) was evaluated. This research demonstrates that the
functionalization of silica coated magnetite particles with dithiocarbamate groups also
confers affinity for such metal nanoparticles, thus allowing their uptake from hydrosols
under a magnetic gradient. En route with these findings, we have varied several
operational parameters in order to investigate this strategy as a new bottom-up
assembly method for producing a range of coupled colloidal nanoparticles. The final
properties of the assemblies will be discussed by taking into account the composition
of the hybrid nanostructures and also their morphological characteristics.
[1] D.S. Tavares, A. L. Daniel-da-Silva, C. B. Lopes, N. J. O. Silva, V.S. Amaral, J.
Rocha, E. Pereira, T. Trindade, J. Mater Chem A 2013, 1, 8134.
81
BIOPLASTICS PRODUCTION THROUGH MIXED MICROBIAL CULTURES
ECO-ENGINEERING
Joana Pereira1, D. Queirós1, P. C. Lemos2, A. Xavier1, L. S. Serafim1
1
CICECO – Aveiro Institute of Materials, University of Aveiro, Chemistry Department,
Aveiro, Portugal
2
LAQV, REQUIMTE, Chemistry Department, Faculty of Science and Technology,
University Nova of Lisbon, Caparica, Portugal
Bioplastics have been the focus of interest as a sustainable alternative to conventional
plastics. Among those, polyhydroxyalkanoates (PHA) can be highlighted, not only for
their biocompatibility and biodegradability, but also because they can be produced by
microbial cultures from agro-industrial wastes, fitting the concept of a biorefinary and
reducing production costs. The Portuguese pulp and paper industry is a sector with
significant impact on the national economy and generates large amounts of byproducts that are usually burned for energy/chemicals recovery, like hardwood sulphite
spent liquors (HSSL) and condensate. Respectively rich in sugars (40–60 g.L-1) and
acetic acid (18 g.L-1) and with potential to be converted into PHA.
In this work, production of PHA by mixed microbial cultures (MMC) was studied in a
three-stage process: acidification of HSSL, selection of a PHA accumulating microbial
culture under aerobic dynamic feeding strategy and PHA accumulation tests. Three
stages were optimized through the manipulation of the operational parameters:
acidogenic fermentation for the conversion sugar into Short-chain Organic Acids
(SCOAs), MMC selection using SCOAs and PHA accumulation. The main objective of
the present work is the optimisation of selection step in order to obtain a stable MMC
able to produce PHA. An aerobic sludge was submitted to different cycle duration and
organic load rates (OLRs). With a 24h cycle and an OLR of 0.5 g/L.d of SCOA, a
Pseudo Stationary State (PSS) was reached in only 7 days, and the maximum SCOA
consumption rate was 0.22 g.L-1. Reducing the cycle for 12h led to the reduction of the
hydraulic retention time (HRT) from 2 days to 1 day and the increase of the OLR to 1
g/L.d, a PSS was reached within 15 days and the maximum SCOA consumption rate
was 0.35 g.L-1. After achieving a new stability stage accumulation tests were
conducted. In order to enhance productivity the OLR was increased again to 1.5 g/L.d
and PSS occurred after 18 days, demonstrating good adaptation from the microbial
culture. The feast and famine ratio after achieving the PSS were, in all conditions ≈
0.18, a clear indication of PHA accumulation. Several accumulation tests were
conducted using the select culture under different conditions of limitations and using
condensate and both streams produced in the HSSL acidification step. The different
composition of SCOA of the substrate feed in the accumulation led to the production
of PHA with distinct monomer composition and, consequentially, different properties.
82
RECOVERY OF PHENOLIC COMPOUNDS FROM SALICORNIA
RAMOSISSIMA USING POLYMER-BASED AQUEOUS BIPHASIC
SYSTEMS
João H. P. M. Santos1, Claúdia R. Martins1, João A. P. Coutinho1, Sónia P.M.
Ventura1,*
1CICECO
- Aveiro Institute of Materials, Department of Chemistry, University of
Salicornia ramosissima is a halophyte plant that grows in the Aveiro lagoon [1].
S. ramosissima contains several compounds with commercial added value with
pharmaceutical properties: antioxidants, antidiabetic and anticancer. Caffeic
acid (CA), ferulic acid (FA) and protocatechuic acid (PA) are the major phenolic
acids present in Salicornia, from 0.5 - 2.1 g of the total amount of phenolic acids
per 100 g of fresh biomass [2]. Such compounds have a great interest in the
pharmaceutical industry, thus justifying the interest by their recovery [3]. Herein,
we pretend to find an optimized and selective platform of extraction and
purification for these phenolic compounds from the S. ramosissima biomass
extract. In this work, polymeric-based aqueous biphasic systems, formed by
two polymers, namely the sodium polyacrylate (NaPA 8000) and the
polyethylene glycol (PEG 8000) in which ionic liquids and inorganic salts are
used as electrolytes in low concentrations (5.0 wt%) were applied [4]. Distinct
proprieties of these polymers and mainly the tailor-made design of ionic liquids
used as electrolytes allowed the manipulation of the phase migration behavior
of the different phenolic acids, in order to find a selective aqueous biphasic
system. The results show that using different electrolytes, e.g. NaCl, Na2SO4
and [C2mim]-based ILs, the phase migration among the phenolic acids (caffeic
acid, ferulic acid and protocatechuic acid) changes, being thus possible to
develop an integrated process of extraction and purification with high selectivity
for similar-structured phenolic acids.
[1] H. Silva, G. Caldeira, H. Freitas, Ecol. Res. 2007, 22, 125-134.
[2] M.R.A. Julião, Dissertação de Mestrado em Tecnologia dos Alimentos 2012 74-76.
[3] H.E. Park, W. Bi, K.H. Row, Anal. Lett., 2013, 46, 2223-2234.
[4] J.H.P.M. Santos, F.A. E Silva, J.A.P. Coutinho, S.P.M. Ventura, A. Pessoa, Process
Biochem. 2015 50, 661-668.
Acknowledgments: This work was developed in the scope of the project CICECOAveiro Institute of Materials (Ref. FCT UID/CTM/50011/2013), financed by national
PT2020 Partnership Agreement. The authors are thankful to FCT for the financial
support on the ambit of the doctoral and post-doctoral grants SFRH/BD/102915/2014
and SFRH/BPD/79263/2011 of J. Santos and S. P. M. Ventura.
83
PURIFICATION AND CHARACTERIZATION OF POLYSACCHARIDES
FROM ISOCHRYSIS GALBANA USING AQUEOUS BIPHASIC SYSTEMS
BASED IN IONIC LIQUIDS
João P. Trigo1,2, João H. P. M. Santos1, Élia Maricato1, Cláudia Nunes1,2,
Manuel A. Coimbra2, Sónia P. M. Ventura1
1CICECO
and 2QOPNA, Department of Chemistry, University of Aveiro, 3810193 Aveiro, Portugal
Isochrysis galbana is a microalgae species rich in biopolymers of high added value,
particularly the sulfated polysaccharides (sPS) [1]. The sPS are structurally similar to
animal origin sulfated glycosaminoglycan’s, making them very useful in food industry
and biomedical/medical field [2].
Nowadays there are a diversity of conventional methodologies used to extract
polysaccharides from biomass [3]. However, efficient methods for their purification,
allowing their separation from proteins are scarce. Thus, the proposal of novel
purification methodologies towards industrial application and commercialization of
these biopolymers is welcome.
Therefore, the purpose of this work is to developed a new technology for sPS
purification. Several ionic liquid-based aqueous biphasic systems (IL-ABS) based on
the imidazolium family ([Cnmim]X) and various inorganic salts were tested. The
polysaccharides and proteins partition was evaluated for each aqueous phase using
the phenol-sulfuric acid method and the Bradford method, respectively. In order to
optimize the selectivity, various studies were made concerning the type of inorganic
phosphate salt and the ionic liquid structure (alkyl side chain length and anion nature).
For the ABS representative of the best results ([C8mim]Cl + K3PO4) the extraction point
composition was also optimized aiming to increase the selectivity of the process,
aiming to maximize the sPS partition to the opposite phase of the proteins (EEproteins =
100 % to the top phase and EEpolysaccharides = 71.21 ± 5.21 % to the bottom phase). The
purified polysaccharides were characterized by gas chromatography and elemental
analysis. The sulfate content was determined by turbidimetry. This proposed
methodology opens up new possibilities in the large-scale separation and purification
of biopolymers produced by microalgae.
[1]
L.-E. Rioux and S. L. Turgeon, Seaweed Sustainability 2015.
[2]
M. F. de J. Raposo, R. M. S. C. de Morais, and A. M. M. Bernardo de Morais,
Mar. Drugs 2013, vol. 11, pp. 233–52.
[3]
Y. Sun, H. Wang, G. Guo, Y. Pu, and B. Yan, Carbohydr. Polym. 2014, vol.
113, pp. 22–31.
Acknowledgements: QOPNA (FCTUID/QUI/00062/2013) and CICECO-Aveiro Institute of
Materials (POCI-01-0145-FEDER-007679; FCTUID/CTM/50011/2013), funded by national
funds through FCT/MEC, FEDER and PT2020. To the financial support given by FCT within a
PhD fellowships SFRH/BD/87245/2012 of Élia Maricato and SFRH/BD/102915/2014 of
J.H.P.M. Santos and postdoctoral fellowship SFRH/BPD/79263/2011 of S.P.M. Ventura and
SFRH/BPD/100627/2014 of Cláudia Nunes. The authors also thank to Necton SA. for providing
the samples.
84
(La,Sr)(Fe,Co)O3-BASED CATHODE CONTACT MATERIALS FOR
INTERMEDIATE-TEMPERATURE SOLID OXIDE FUEL CELLS
Kiryl Zakharchuk1, Szymon Obrębowski2, Eugene Naumovich2,
Aleksey Yaremchenko1
1
CICECO, Department of Materials and Ceramic Engineering, University of Aveiro,
2
Fuel Cell Group, Thermal Processes Department, Institute of Power Engineering,
Augustowka 36, 02-981 Warsaw, Poland
Cathode contact material is usually deposited in a form of thick film between cathode
and interconnect of solid oxide fuel cell (SOFC) in order to provide better electrical
contact and to suppress ohmic losses. Key properties of contact materials include high
electrical conductivity, low temperature of incipient sintering, and chemical inertness
with respect to cathode and interconnect. The operation temperatures of intermediatetemperature SOFCs correspond to 600-700°C, with the highest allowed T ~ 750°C.
Thus, the selection of contact materials is limited due to stiff requirements to incipient
sintering point. The present work was focused on the assessment of (La,Sr)(Fe,Co)O3based complex oxides as prospective cathode contact materials.
La0.6Sr0.35Fe0.8Co0.2O3-δ, La0.55Sr0.4Fe0.8Co0.2O3-δ, La0.6Sr0.4Fe0.8Co0.15Cu0.05O3-δ and
La0.6Sr0.4Fe0.75Co0.15Cu0.10O3-δ ceramics were synthesized by glycine-nitrate
combustion technique. All prepared materials were found to possess rhombohedrallydistorted perovskite structure without impurities detectable by XRD. Average thermal
expansion coefficients were determined by dilatometry to vary in the range (13.814.3)×10-6 K-1 at 40-700°C in air. Electrical measurements revealed slightly higher
electrical conductivity compared to commercial La0.6Sr0.4Fe0.8Co0.2O3-δ and
(La0.6Sr0.4)0.995Fe0.8Co0.2O3-δ materials in the target temperature range.
ASR (area specific resistance) was measured by 4-probe DC technique using model
cells comprising interconnect (Crofer APU steel (0.2 mm thickness) with chromium
barrier (commercial Mn1.5Co1.5O4 spinel, ~10 µm)), applied layer of contact material
(~10 µm), and Pt foil as another electrode. The contact was ensured applying an
external load (constant force of 38.7N). Samples were thermally treated using the
procedure similar to IT-SOFC stack start-up: slow heating until the sealing temperature
(~750°C) followed by step-wise cooling down to 660°C with isothermal steps for 4-5h
before ASR measurements. Application of the contact material layer was found to
result in up to fivefold reduction of ASR values and in substantial improvement in
reproducibility. Studied contact materials demonstrated a moderate advantage over
commercial
materials,
with
best
performance
observed
for
La0.6Sr0.4Fe0.75Co0.15Cu0.10O3 layers. In addition, prepared contact layers were found to
be stable against thermal cycling, although removal of external load resulted in
observable degradation of ASR.
85
TIME-RESOLVED DIFFRACTION STUDY OF THE TRANSFORMATION OF
C60 INTO GRAPHITE-LIKE CARBON
L.Marques1, M. Mezouar2, J-L. Hodeau3
1Departamento
2
de Física and CICECO, Universidade de Aveiro, 3810-193
Aveiro, Portugal.
European Synchrotron Radiation Facility, 38041Grenoble, France.
3
Institut Néel, CNRS, 38042 Grenoble, France.
E-mail: lmarques@ ua.pt
Fullerite C60 collapses irreversibly under high pressure and high temperature
(>800ºC) originating a disordered graphite-like carbon phase. The transformed
phase is considered to be predominantly a sp2-carbon phase exhibiting
semimetallic properties, as in graphite, but displaying higher hardness
(>25GPa) than graphite. Detailed analysis of the quenched partial-transformed
samples has revealed an orientational crystallographic relationship between
the parent C60 phase and the transformed graphite-like structure [1]. The
graphitic planes of the transformed phase are shown to be parallel to the (111)
fcc planes of the C60 parent phase. This relationship is characteristic of
martensitic transformations indicating that the graphitic planes should be
created from the C60 molecules involving limited atomic diffusion. Thus,
detailed kinetic studies are important to confirm this scenario and to provide
insights on the structural mechanism by which graphitic planes grow directly
from the fullerite lattice planes. We have investigated the collapsing of highpressure C60 into disordered graphite-like carbon phase at 5GPa and 827 ºC.
The transformation was followed in situ using time-resolved synchrotron x-ray
diffraction. The 2D diffraction data confirms that the transformation is of
martensitic type (at least, partially). Kinetic data analysis gave an Avrami
exponent consistent with a mixed martensitic and diffusion-limited process.
[1] C. Lepoittevin, M. Álvarez-Murga, L. Marques, M. Mezouar, J-L. Hodeau,
Carbon 2013, 52, 278.
86
THERMOSENSITIVE MICELLAR SYSTEMS AS SELECTIVE PLATFORMS
OF PURIFICATION
Leonor S. Castro3, Inês S. Cardoso3, Filipa A. Vicente1,3, Luciana P.
Malpiedi2,3,
Francisca A. e Silva3, Adalberto Pessoa Jr3, João A.P. Coutinho1 and Sónia
P.M. Ventura1
1CICECO-Instituto
de Materials de Aveiro, Departamento de Química,
Universidade de Aveiro,3810-193 Aveiro, Portugal
2Departamento de Química-Física, Universidad Nacional de Rosario, Rosario,
Argentina
3 Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, São
Paulo, Brasil
Aqueous micellar two-phase systems (AMTPS) using surfactants are advantageous
thermosensitive extraction systems, mostly composed of water, and thus emerging as
an appellative type of liquid-liquid extraction (LLE). AMTPS composed of two
surfactants enhanced the extraction of biomolecules, hence exploiting the advantage
of introducing ionic liquids (ILs) as a new class of co-surfactants came as an attractive
alternative due to their unique properties. Thus, the aim of this work was the
development of new micellar systems with potential to be applied into the extraction
field. Those were firstly studied considering the design of AMTPS, based on Triton X114 as the main surfactant by testing two distinct families of ILs, corresponding to the
imidazolium and phosphonium. In order to evaluate the extractive potential of these
new AMTPS, the partition of different molecules was investigated, considering the
effect of the ILs as cosurfactants in the coexistence curves and their impact upon the
solutes partition. For both molecules under study, cytochrome c (Cyt c) and
Rhodamine 6G (R6G), the partition coefficients (K) and selectivities (SR6G/Cyt c) were
assessed. The obtained results clearly demonstrate that ILs have a major effect on
the Tcloud. The presence of ILs as cosurfactants was able, not only to enhance the KCyt
c (indicated as log KCyt c) from -0.587 ± 0.117 up to -1.510 ± 0.139, but also to improve
the SR6G/Cyt c from 925.25 up to 3418.89
[1] Vicente, F. A. et al. Sep. Purif. Technol. 135, 259–267 (2014).
This work was developed within the scope of the project CICECO-Aveiro Institute of
Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID /CTM /50011/2013),
financed by national funds through the FCT/MEC and when appropriate co-financed
by FEDER under the PT2020
Partnership Agreement. The authors thank financial support from Fundação para a
Ciência e a Tecnologia (FCT) through the doctoral and post-doctoral grants
SFRH/BD/94901/2013 and SFRH/BPD/79263/2011 of F. A. e Silva and S.P.M.
Ventura, respectively. Santander Scholarship granted to Filipa A. Vicente and the
financial support from Fundação de Amparo à Pesquisa do Estado de São Paulo
(FAPESP, Process N° 2011/20521-0) given to Luciana P. Malpiedi. The authors also
thank the financial support from FAPESP through the project FAPESP 2012/120226.
This project was also afford by Coordenação de Aperfeiçoamento de Pessoal de Nível
Superior
(CAPES) and Conselho Nacional de Desenvolvimento Científico e Tecnológico
(CNPq) from Brazil.
87
STUDIES ON CHOLINIUM CHLORIDE-BASED DEEP EUTETIC
SOLVENTS PHASE DIAGRAMS
Liliana P. Silva1,2, Mónia A. R. Martins1, Vanessa Vieira1,2, Olga Ferreira2,
Simão P. Pinho2, João A. P. Coutinho1
1
Aveiro, Aveiro, Portugal.
2
Associate Laboratory LSRE/LCM, Department of Chemical and Biological
Technology, Polytechnic Institute of Bragança, Bragança, Portugal.
E-mail:[email protected]
Find new eco-friendly solvents is one of the goal of green chemistry. Nowadays is
important discover new solvents with equivalent or better performance than
conventional ones. Examples are supercritical CO2 and ionic liquids. Abbott and
coworkers1 proposed another class of solvents, the Deep Eutectic Solvents (DES).
These are mixtures of two or more compounds, for which the eutectic point is far below
that of an ideal liquid mixture2. They are formed by self-association due to the
combination of hydrogen bond donors and hydrogen bond acceptors2.
DES are easily prepared by mixing the constituents at a moderate temperature, without
chemical reaction. Many are prepared using cheap and well-characterized
biodegradable starting materials, making the “synthesis” green and safe, without need
of complex purification steps. They may also be classified as designer solvents since
their structures can be adjusted by selecting the hydrogen-bond donor– acceptor
combinations, and thus, tailoring their phase behavior and physical properties.
Choline chloride is one of the most common components used in DES formulations.
In fact, this quaternary ammonium salt is a very cheap, biodegradable and non-toxic
which can be either extracted from biomass or readily synthesized from fossil reserves
through a very high atom economy process. When combined with urea, carboxylic
acids, or other safe hydrogen bond donors, DES are formed. While much work has
been reported using these novel solvents, data on their phase diagrams are
surprisingly scarce. Yet it may provide very important information on the donoracceptor interactions, and the range of compositions and temperatures of operation of
these systems. The aim of this work is thus to characterize and analyze phase
diagrams of DES composed by choline chloride and mono, di, and tricarboxylic, and
hydroxycarboxylic acids, in the whole composition range. A visual observation method
was used to determine the phase diagrams, and DSC was also employed in order to
check for consistency and identify other phase transitions below the liquidus line.
1
A. P. Abbott, G. Capper, D. L. Davies, R. K. Rasheed, V. Tambyrajah, Chem.
Commun. 2003, 70 – 71.
2 Q. Zhang, K. De Oliveira Vigier, S. Royer, F. Jérôme, Chem. Soc. Rev. 2012,
41, 7108 –7146.
88
DESIGN OF AMINE MODIFIED-PERIODIC MESOPOROUS
ORGANOSILICAS FOR CO2/CH4 SEPARATION: EXPERIMENTAL AND
COMPUTATIONAL STUDIES
M. A. O. Lourenço,1 C. Siquet,2 M. Sardo,1 L. Mafra,1 J. Pires,3 M. Jorge,4 M.
L. Pinto,5 P. Ferreira,1 J. R. B. Gomes1
1
CICECO – Aveiro Institute of Materials, Departments of Chemistry and of Materials
& Ceramics Engineering, University of Aveiro, 3810-193 Aveiro, Portugal
2
LSRE, Faculty of Engineering, University of Porto, 4200-465 Porto, Portugal
3
CCB, Faculty of Sciences, University of Lisbon, 1749-016 Lisboa, Portugal
4
Department of Chemical and Process Engineering, University of Strathclyde,
Glasgow, UK
5
CERENA, Instituto Superior Técnico, University of Lisbon, 1049-001 Lisboa,
Portugal
E-mail: mirtha@ ua.pt
Periodic mesoporous phenylene-silicas (PMO) with controlled pore sizes were
prepared using cationic surfactants of different alkyl chain lengths.[1] Aromatic amine
modification of the resulting Cn-PMOs was made following a procedure described in
the literature.[2] The potential of the resulting materials for CO2/CH4 separation was
determined from the adsorption of pure CO2 and CH4 gases. We did not find a direct
relation between the adsorption of these gases and the textural/physical properties of
the materials. Nevertheless, we observed a clear correlation between the amount of
T2 silanol species and the values of the Henry’s constants of adsorption (KH). The best
parent and amine-functionalized Cn-PMOs were subsequently modified with
aminopropyl groups (APTMS) and their capacities to uptake CO2 and CH4 molecules
were assessed.[3] The PMO with APTMS showed the highest selectivity for CO2 gas,
adsorbing 26 times more CO2 than CH4 at 25 ºC. We also found a good correlation
between the KH values and the interaction energies of the materials with CO2 or CH4
molecules obtained from density functional theory calculations, suggesting that the
latter can be used to guide the experimental synthesis of more effective materials.
This work was developed in the scope of the projects UID/CTM/50011/2013 (POCI01-0145-FEDER-007679), UID/MULTI/00612/2013, UID/ECI/04028/2013, NORTE07-0124-FEDER-000011 | UID/EQU/500230/2013, PTDC/EQU-EQU/099423/2008
(FCOMP-01-0124-FEDER-010345), Investigador FCT, SFRH/BD/80883/2011,
financed by national funds through the FCT/MEC and co-financed by FEDER under
the PT2020 Partnership Agreement.
[1] N. Bion, P. Ferreira, A. Valente, I. S. Gonçalves, J. Rocha, J Mater Chem, 2003,
13, 1910.
[2] M. Ohashi, M. P. Kapoor, S. Inagaki, Chem Comm, 2008, 7, 841.
[3] M. A. O. Lourenço, C. Siquet, M. Sardo, L. Mafra, J. Pires, M. Jorge, M. L. Pinto,
P. Ferreira, J. R. B. Gomes, J Phys Chem C, 2016, 120, 3863.
89
LOCALLY INDUCING AND MAPPING OF STRUCTURAL
TRANSFORMATIONS IN NI-MN-GA THIN FILMS BY SCANNING
THERMAL MICROSCOPY
M. J. Pereira1, J. S. Amaral1, N. J. O. Silva1, V. S. Amaral1, F. Albertini2, F.
Casoli2
1 CICECO – Aveiro Institute of Materials and Physics Department – University
of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal
2 IMEM-CNR, Parco Area delle Scienze 37/A, 43010 Parma, Italy
Ni2MnGa is a ferromagnetic-shape-memory alloy exhibiting two main structural
phases: the austenitic (cubic) phase and the martensitic (tetragonal) phase,
also known as the high and low temperature phases, respectively. The
martensitic deformation characteristic of this structural transformation causes
stress in the material, which can be released by the introduction of twin
boundaries appearing on the sample’s surface as a set of almost parallel waves
[1-4]. The temperature at which the structural transition occurs (TM) is strongly
dependent on sample composition [5]. We present a study of the thermal effect
of locally induced structural transformations by nano-thermal analysis
performed with a Scanning Thermal Microscope on a 400 nm Ni-Mn-Ga thin
film. The Scanning Thermal Microscope thermal tip (radius ~ 100 nm, sensitivity
of ~ 1 Ω/ºC and 50 nm spatial resolution) simultaneously heats and determines
temperature locally, acting respectively as actuator and sensor. As the tip heats
the sample in specific location, the cantilever deflection is measured and
changes in the structure below are signaled in this deflection. The Ni-Mn-Ga
thin film local structural transformation is marked by a discontinuity in the
cantilever deflection curve, which occurs at different temperatures for different
locations in the sample. Mapping of the sample’s TM distribution, ranging from
329 K to 363 K, was performed. The observed accentuated decrease of TM’s
from 344 K to 348 K is consistent with the compositional narrowing observed in
the material’s phase diagram. This work shows how nano-thermal analysis can
be used to map TM inhomogeneity at the nanoscale for systems with structural
transitions such as Ni-Mn-Ga.
[1] P. J. Webster, K. R. A. Ziebeck, S. L. Town, M. S. Peak Phil. Mag. B 1984
49 295.
[2] L. Righi,, F. Albertini, L. Pareti, A. Paoluzi, G. Calestani, Acta Materialia 2007
55 5237.
[3] A. N. Vasil’ev, V. D. Buchel’nikov, T. Takagi, V. V. Khovailo, E. I. Estrin,
Phys. Uspekhi 2003 46 559.
[4] A. Planes, L. Manosa, M. Acet, J. Phys. Condens. Matter 2009 21 233201.
[5] V. V.Khovaylo, V. D. Buchelnikov, R. Kainuma, V. V. Koledov, M. Ohtsuka,
V. G. Shavrov, T. Takagi, S. V. Taskaev, A. N. Vasiliev, Physical Review B
2005 72 224408/1-224408/10
90
ORDERED MICRO/MESOPOROUS Zr,Al-SILICATES FOR INTEGRATED
REDUCTION AND ACID-CATALYSED CONVERSION OF FURFURAL
M. M. Antunes1, S. Lima2, P. Neves1, A. L. Magalhães1, E. Fazio3, F. Neri3,
M.
1
1
T. Pereira , A. F. Silva , C. M. Silva1, S. M. Rocha4, M. Pillinger1, A.
Urakawa2, A. A. Valente1
1 Department
of Chemistry, CICECO - Aveiro Institute of Materials, University
of Aveiro,
2 ICIQ, The Barcelona Institute of Science and Technology, Tarragona, Spain
3
Dipartimento di Fisica e di Scienze Della Terra, Università Degli Studi di
Messina, Italy, 4 Department of Chemistry, QOPNA, University of Aveiro. Email: [email protected]
Multifunctional catalysts possessing zirconium and aluminium sites have been found
to be efficient eco-friendly heterogeneous catalysts for the integrated reduction-acid
conversion of furfural (Fur), a platform chemical industrially produced from
hemicelluloses present in lignocellulosic biomass, obtainable from forest/agricultural
residues, municipal wastes (paper), and as by-products of the pulp and paper industry.
The prepared catalysts were ordered porous silicates of the type TUD-1 and zeolite
Beta with different Al/Zr ratios. Spectroscopic characterisation indicated that the Zrand Alsites were in tetrahedral coordination (framework species) which accounted for
catalyst multifunctionality. The silicates possessed catalytic activity and good stability
for the conversion of Fur in 2-butanol, at 120 ºC, leading to the bio-products furfuryl
alcohol (FA), alkyl furfuryl ethers (FEs), alkyl levulinate esters (LEs), levulinic acid (LA),
angelica lactones (AnLs) and -valerolactone (GVL) with total yields of up to 76% at
85% conversion.
Combining catalytic and kinetic studies with
characterisation details, it was possible to conclude
that Zr sites were essential for the reduction steps
(Fur to FA and 1-BL to GVL), while the Al and Zr-sites
played roles in the intermediate acid catalysed steps
of FA to 2-BMF, 2-BL, AnLs and LA. With (Zr,Al)Beta, yields of GVL were high from a levulinate ester
as substrate, but negligible from Fur, partly attributed
to the limited intermediate formation of 2-BL. When
using catalysts with higher Al/Zr ratios, the levulinate
ester was favoured, although side-reactions were
also promoted. The development of eco-friendly
heterogeneous
multifunctional
catalysts
with
optimum physicochemical properties to obtain the
more end bioproduct (GVL) from Fur is still a major
challenge and the focus of present studies.
[1] M. M. Antunes, S. Lima, P. Neves, A. Magalhães, E. Fazio, F. Neri, M. T. Peri, M.
T. Pereira, A. F. Silva, C. M. Silva, S. M. Rocha, M. Pillinger, A. Urakawa, A. A. Valente,
Appl. Catal. B: Environ. 2016, 182, 485.
91
SUPRAMOLECULAR SYNTHONS IN PHARMACEUTICAL CO-CRYSTALS
STUDIED BY NMR CRYSTALLOGRAPHY
M. Sardo1, I.C.B. Martins2, J.A. Fernandes, D.C. Lazarte3, N. Masciocchi4,
S.M. Santos1, A. Fernandes2, A. Antunes2, V. André2, M.T. Duarte2, L. Mafra1
1
Chemistry Dept., CICECO – Aveiro Institute of Materials, 3810-193 Aveiro, Portugal
2
CQE − Centro de Química Estrutural, IST, Universidade de Lisboa, Portugal
3
Lab. de Estudios Cristalográficos, CSIC-Universidad de Granada, Granada, Spain
4
Dipartimento di Scienza e Alta Tecnologia, Università dell’Insubria, Como, Italy
NMR crystallography is becoming popular in the structure validation of multicomponent
systems [1]. This approach provides complementary structural information by
combining the high sensitivity of solid-state (SS) NMR towards short-range local
structure, with the accuracy of PXRD for long-range ordering. DFT calculations can be
employed for geometry optimization of hydrogen atoms and to obtain theoretical NMR
chemical shifts that can be compared with experimental data for structural validation,
increasing the success rate and confidence level in the obtained final structure [1a].
This multidisciplinary approach was applied to the structural elucidation of two cocrystals of theophylline (TP) [2]: TP:4-aminosalicylic acid and TP:4-aminobenzoic acid;
as well as five new multicomponent crystal forms of azelaic acid (AA) [3]: a co-crystal
with 4,4-bipyridine, an anhydrous and an hydrated molecular salt with piperazine, two
anhydrous molecular salts with morpholine and 1,4-diazobicyclo[2.2.2]octane. All
systems were prepared using the liquid-assisted grinding method and fully
characterized by X-ray diffraction and SSNMR.
SSNMR was particularly decisive in proving the unexpected absence of intermolecular
interactions engaging the amino groups in TP:4-aminobenzoic acid as well as in
determining the co-crystal/salt nature of the systems with AA. Moreover, the X-ray
structure of AA:MORPH exhibits a static disorder in the hydrogen atoms engaged in
an H-bond between two COOH moieties of AA. DFT geometry optimization of the
hydrogen positions followed by GIPAW-DFT calculations of 1H chemical shifts showed
that such disordered atoms refer to O···H···O hydrogens, roughly equidistant from both
proton acceptor and donor atoms. 1H SSNMR combined with DFT geometry
optimization have elucidated the origin of these disordered hydrogens through the
presence of 1H resonances shifted to very high frequencies (up to ca. 20. ppm). The
results show the advantageous use of X-ray diffraction and SSNMR techniques in
tandem with computer simulations for structural elucidation.
The work was financed by FCT, FCT/MEC and cofinanced by FEDER under the
PT2020.
[1] (a) R.K. Harris, R.E. Wasylishen, M.J. Duer, NMR Crystallography; Wiley:
Chichester, UK, 2009 (b) L. Mafra, et al. “Calculation of NMR Chemical Shift:
Application to Small Molecule Pharmaceutical Solids” in Computational Approaches in
Pharmaceutical Solid State Chemistry; Wiley & Sons, Yuriy Abramov (ed.) 2016.
[2] I.C.B. Martins et al., Cryst. Growth Des. 2016, 16, 154.
[3] J.A. Fernandes et al. Cryst. Growth Des. 2015, 15, 3674.
92
1D ZINC NANOSTRUCTURES OBTAINED BY ELECTRODEPOSITION IN
POROUS TITANIA
M. Starykevich1, A.N. Salak1, M.G.S. Ferreira1
1Department
of Materials and Ceramic Engineering, CICECO-Aveiro Institute
of Materials, University of Aveiro, 3810-193 Aveiro, Portugal
The development of one-dimensional nanostructures is currently under serious
investigation for different applications. The areas that would benefit greatly from
advances in the synthesis of well-defined nanostructures include photonics,
nanoelectronics, catalysis and biological diagnosis. Presently, several areas of
nanotechnology are devoted to the preparation of new metal-materials for
applications in energetics. Ionic liquids were investigated in the context of
several applications owing to their unique properties when compared to regular
water- and organic-based solvents: namely, wide electrochemical window, wide
temperature ranges for the liquid phase, negligible vapour pressure and low
pollutant emission. These properties make possible some electrochemical
processes in solution which would be impossible otherwise. Reactive materials
such as Zn, Al, Mg and their alloys can be electrodeposited in ILs.
In the present work the deposition of zinc nanoparticles inside pores of titania
based templates from choline chloride eutectic solution containing ZnCl2 was
performed. Often choline chloride eutectic is named in literature as quasi ionic
liquid since the properties are similar, but in contrast to conventional ionic
liquids the choline based electrolyte is very cheap, non-toxic and thus has
potential for use in industry. Zinc was chosen as a model metal for deposition
due to possibility of subsequent transformation into semiconductor materials
such as zinc oxide and zinc sulphide.
Electrodepostion of zinc in titania porous oxide was performed in one step with
a pulse technique. Parameters of the pulse were tuned to obtain a better fillfactor.
Different template pre-treatments were also studied. Three main templates
types were used. The first is standard template without any treatment. The
second template was annealed after preparation at 450ºC during 5 hours. This
step converts amorphous titania to crystalline and increases conductivity of the
oxide. This procedure increases thickness of the bottom oxide and at the same
time increases its crystallinity and conductivity. All these manipulations have
strong impact on the electrical properties of the matrix which is demonstrated
in the work. Advantages and disadvantages of these templates are presented.
The presence of zinc in the porous system was confirmed by SEM/STEM/EDS
and XRD. Additionally, to control filling of the pores glow discharge optical
emission spectroscopy was used.
93
Ni-Fe LAYERED-DOUBLE-HYDROXIDES AS CATALYSTS FOR OXYGEN
EVOLUTION REACTION
Manon Wilhelm1, Alexandre C. Bastos1, João Tedim1, Mário G.S. Ferreira1
1CICECO,
DEMaC, University of Aveiro E-
mail: [email protected]
The study of the splitting of water into hydrogen and oxygen falls within
the research trend for the production of cleaner fuels. Currently, an important
factor limiting the efficiency of existing water-splitting cells is the slow kinetics
of the Oxygen Evolution Reaction (OER):
4OH− → 2H2O + O2 +4e− (in alkaline medium)
2H2O → 4H+ + O2 + 4e− (in acid)
As reported in the literature, [1] the decrease of the high overpotential of water
oxidation reaction can be achieved with materials such as iridium oxide and
ruthenium oxide. However, iridium and ruthenium are scarce elements and
finding efficient catalysts based on earth-abundant materials is necessary to
produce scalable and sustainable devices with high performance.
During the last decades, some works reported in the literature have highlighted
the importance of defining procedures for the determination of the catalytic
properties of a material [2]. Also, it has been observed that iron-doped nickel
hydroxides present an interesting catalytic behavior towards OER [1]. In this
context, the aim of our work is the development of a relevant strategy to
determine and improve the electrocatalytic efficiency of Ni-Fe Layered Double
Hydroxides (LDH) materials towards OER. The synthesis method, the nature of
the anion intercalated in LDH structure, the crystallinity of the materials are
parameters that can influence on the catalytic properties and that need to be
defined for a better understanding of the water oxidation reaction.
In this work, the synthesis of Ni-Fe LDHs is performed by hydrothermal route
and the material is characterized by XRD, SEM and particle size
measurements. The electrochemical response of the synthesized material is
studied in basic medium by linear sweep voltammetry with a glassy carbon
rotating disk electrode. Iridium and ruthenium oxides are used as references to
evaluate the quality of the synthesized OER catalysts.
[1] M. Gong, H. Dai, Nano Research, 2015, Volume 8, page 23.
[2] L. Trotochaud, S. Boettcher, Scripta Materialia, 2014, Volume 74, page 25.
94
SUPPORTED IONIC LIQUIDS FOR THE PURIFICATION OF
IMMUNOGLOBULIN Y (IGY)
Márcia C. Neves1, Joana Antunes1, Sandra Bernardo1, João A. P. Coutinho1,
Tito S. Trindade1, Mara G. Freire1
1
Aveiro
Due to the actual emergence of antibiotic-resistant pathogens, the application of
antigen-specific antibodies in passive immunotherapy represents an imperative reality
in the near future. In addition to the more investigated mammal antibodies, antibodies
from egg yolk (IgY) can be obtained in higher titres and by non-invasive methodologies
[1]. Up to date, several methods, such as precipitation, dialysis, ultrafiltration and
chromatography are available for IgY purification [1]. Nevertheless, the production cost
of IgY still remains higher than other drug therapies due to the lack of cost-effective
purification techniques. The development of a cost-effective and scalable new strategy
for the purification of IgY is thus in high demand and will have an high impact in
economics and human health. In this work, a new platform for the purification of IgY
using supported ionic liquids (SILs) was investigated. A particular interest has been
given to ILs immobilized in silica materials as sorbents in solid-phase extractions (SPE)
[2]. To this end, silica-functionalized materials were initially synthesized and
characterized, based on a wide array of chemically distinct ILs, and their performance
for purifying IgY from aqueous solutions of egg yolk was investigated.
Acknowledgements:This work was developed in the scope of the project CICECOAveiro Institute of Materials (Ref. FCT UID/CTM/50011/2013), financed by national
PT2020 Partnership Agreement. M. C. Neves acknowledges FCT for a post-doctoral
grant (SFRH/BPD/110423/2015) and M. G. Freire acknowledges the European
Research Council (ERC) for the Starting Grant ERC-2013-StG-337753.
[1] J. Kovacs-Nolan, Y. Mine, Annu. Rev. Food Sci. Technol. 2012, 3, 163.
[2] B. Li, X. Zou , Y. Zhao, L. Sun, S. Li; Mater Sci Eng C Mater Biol Appl. 2013, 33,
2595–2600.
95
CHITOSAN-SILICA HYBRID NANOADSORBENTS FOR THE UPTAKE OF
PHARMACEUTICALS FROM WATER
Margarida I. Rodrigues1, Sofia F. Soares1, Tito Trindade1 and Ana L. Danielda-Silva1
1CICECO
- Aveiro Institute of Materials, Department of Chemistry, University
E-mail: mpenedorodrigues@ ua.pt; [email protected]
Pharmaceutical products have been frequently found in surface waters, since
wastewater treatment plants lack efficient treatment procedures to remove
them1. To overcome this problem alternative treatment methods are needed.
Compared to other methods, adsorption is an attractive process in view of its
simplicity of implementation and low cost.
Nanomaterials, owing to small size and high surface to volume ratio are very
interesting sorbents. Magnetic nanoparticles (MNP) can be easily isolated in
the presence of a magnetic external field, which is convenient for magnetically
assisted removal of pollutants from water. Furthermore, enhanced adsorption
and selectivity of the MNPs toward target pollutants can be achieved by
chemical modification of the MNPs’ surface. In the present study, novel
biosorbents comprising magnetite (Fe3O4) nanoparticles coated with chitosan
hybrid siliceous shells were synthesized and tested for the uptake of three
distinct pharmaceutics from water: diclofenac (DCF), tetracycline (TET) and
metoprolol (MTP).
The method of synthesis comprised the modification of chitosan with an
alkoxysilane containing isocyanate groups and the hydrolysis of a mixture of
the resulting precursor with TEOS.2 For the synthesis of magnetic
nanosorbents the same procedure was used in the presence of Fe3O4 particles.
The materials were characterized using electron microscopy (TEM/SEM), infrared spectroscopy, elemental analysis and zeta potential measurements.
Adsorption experiments with non-magnetic and magnetic sorbents were
performed at different pH and variable initial concentrations of each compound.
The nanosorbents prepared have shown effective sorption affinity for DCF and
TET, and less adsorption capacity for MTP. Higher adsorption values were
obtained for DCF, due to its high affinity to the chemical groups of chitosan
hybrid material.
[1]
T. Deblonde, C. Cossu-Leguille, P. Hartemann, International Journal
of Hygiene and Environmental Health, 2011 214(6), 442–448.
[2] S. F. Soares, T. Trindade, A. L. Daniel-da-Silva, Eur. J. Inorg. Chem. 2015,
27, 4588–4594 .
96
IMPROVEMENT OF R-PHYCOERYTHRIN EXTRACTION FROM RED
MACROALGAE USING AQUEOUS SOLUTIONS OF IONIC LIQUIDS
Margarida Martins1, Flávia A. Vieira1, Helena Abreu2, João A. P. Coutinho1,
Sónia P. M. Ventura1
1CICECO
- Aveiro Institute of Materials, Department of Chemistry, University
2ALGAplus
Lda, Travessa Alexandre da Conceição 3830-196 Ílhavo, Portugal
In the past few years, there has been an increased demand for utilization of cheap and
abundant marine biomass in order to get commercial compounds of added economic
value. Thus, products extracted from natural sources like macroalgae, have gained
significant interest among academia and industries. R-phycoerythrin (R-PE) is a
photosynthetic protein found in red macroalgae and cyanobacteria with recognized
and diversified biological activities, namely its high solubility in water, outstanding
photoluminescence efficiency, high absorption coefficients, and high stability.
Recently, R-PE was point out as a solution to the conventional solar panel cells’ due
to its ability to convert photons into a flow of electrons, being thus applied in production
of energy [1]. However, the major drawback in its large utilization is still associated with
the inexistence of a more effective and as less costly extraction/purification
methodology capable to remove the protein from the marine biomass, while
maintaining its more relevant properties and activities. Therefore, this work focus the
use of ionic liquids (ILs) as alternative solvents, which were applied in the design of a
more efficient solid-liquid extraction methodology [2], for the R-PE extraction from the
red macroalgae Gracilaria sp.. Different ILs (various families, alkyl chain lengths and
anions) were tested considering their capacity to disrupt the macroalgae cells and to
extract as much as possible the R-PE. Other conditions of extraction were tested and
optimized by Surface Response Methodology. The extraction performance was
followed by the measurement of the yields of extraction and purity indexes and then
compared with those of the conventional method. The main results obtained showed
that different ILs are able to extract different compounds from the red macroalgae,
namely chlorophylls and phycobiliproteins, according to the main characteristics of
both the solvent and target biomolecules.
[1]
R. Cubicciotti, U.S. Patent 7,522,162 B2, 2009.
[2] M. G. Freire, A. F. M. Cláudio, J. M. M. Araújo, J. A. P. Coutinho, I. M.
Marrucho, J. N. Canongia Lopes, L. P. N. Rebelo, Chem. Soc. Rev. 2012, 41, 49664995.
Acknowledgements: This work was developed in the scope of the project CICECO-Aveiro
Institute of Materials (Ref. FCT UID/CTM/50011/2013), financed by national funds through the
FCT/MEC and when applicable co-financed by FEDER under the PT2020 Partnership
Agreement. The authors also thank the financial support from CNPq (Ciência sem Fronteiras)
for the supply of the post-doctoral fellowship (249485/2013-3) of F. A. Vieira and to Fundação
para a Ciência e a Tecnologia (FCT) for the post-doctoral grant SFRH/BPD/79263/2011 S.P.M.
Ventura. ALGAplus activities were supported by the project SEACOLORS, LIFE13
ENV/ES/000445.
97
HETEROGENEOUS DOPING OF WEAK ELECTROLYTES
EFFECT OF THE OXIDE COMPOSITION
Maria A. Salvador, F.M. Figueiredo, P. Ferreira
CICECO– Aveiro Institute of Materials, Department of Materials & Ceramic
E-mail: mariasalvador@ ua.pt
Nano-ionics belong to an emerging branch of physics that study specific properties,
phenomena, effects and processes related to the ion transport at the nanoscale, with
a particular focus on understanding and/or manipulation of interfaces or junctions in
solid state ionic materials. [1,2]
The heterogeneous doping is an example of the application of nano-ionics by adding
a second phase to an ionic conducting system, leading to an increase of the
conductivity by means of interfaces.
When oxide particles with a positive surface charge are added to a weak electrolyte,
the negative species are adsorbed to the surface charge inducing a local deviation
from electroneutrality that is compensated by the accumulation of protons, locally
increasing the proton conductivity. The total ionic conductivity of this kind of interfacial
composites (σm) results from the contribution of three different regions in the
composite: i) the bulk of the electrolyte with conductivity (σ∞); ii) the oxide particles with
σp; and iii) the interfacial space charge regions with σL. So σm can be approximated by
the following equation: [3]
where φp is the volume fraction of the oxide particles, βL accounts for the degree of
percolation of the oxide particles, Ω is the ratio of the surface area to the volume of the
oxide, ε0εr is the absolute dielectric permeability, is the mobility of charge in the bulk
and C0 is the concentration of charge carriers in the first layer of the space-charge
zone adjacent to the adsorption layer. This effect was verified by detailed impedance
spectroscopy studies.
This work reports a new kind of protonic conductors obtained by the heterogeneous
doping of triazole and benzimidazole with mesoporous and non mesoporous cerium,
zirconium and titanium oxide nanoparticles. The mesoscopic effect of the
oxide/electrolyte interfaces, apparent by the increase of up to 3 orders of magnitude in
conductivity with respect to the electrolyte, is analyzed by impedance spectroscopy
and correlated to the oxide surface charge.
[1]
[2]
[3]
J. Maier, Phys. Chem. Chem. Phys., 2009, 11, 3011.
C.E. Goodyer, J. S. Fish, J.D. Fehribach, R. O'Hayre, A.L Bunge, Electrochimica
Acta, 2011, 56, 9295.
S. Beyazyildirim, K.D. Kreuer, M. Schuster, A.J. Bhattacharyya, J. Maier, Adv.
Mater., 2008, 20, 1274.
FCT/MEC are aknowlegded for the financial support to CICECO (FCT UID/CTM /50011/2013,
POCI-01-0145-FEDER-007679) through national founds and when applicable co-financed by
FEDER (PT2020 Partnership Agreement); and for PhD (SFRH/BD/60903/2009) and IF grants.
98
DEVELOPMENT OF NEW RENEWABLE AND BIODEGRADABLE
POLY(BUTYLENE FURANDICARBOXYLATE-CO-BUTYLENE
DIGLYCOLATE) COPOLYESTERS
Marina Matos1, Andreia Sousa 1,2, Armando Silvestre
1CICECO
2
and Department of Chemistry, University of Aveiro, 3810-193, Aveiro,
Portugal
CEMUC, Department of Chemical Engineering, University of Coimbra 3030-790,
Coimbra, Portugal
E-mail: marina.matos@ ua.pt
There is a general recognition that the world resources are limited, and sustainability
has become a rallying point for chemical industry. Therefore, bio-based materials, such
as 2,5-furandicarboxylic acid (FDCA)-based polyesters, which may contribute to
reduce the dependence on fossil fuels and the related environmental impacts, are
experiencing a renaissance [1].
FDCA has been successfully used in the synthesis of poly(ethylene 2,5furandicarboxylate) (PEF), which has been announced as the renewable substitute of
poly(ethylene terephthalate) (PET) [1] being already an industrial reality [2]. Moreover,
FDCA has been used in the synthesis of several other polyesters, also homologous to
their terephthalic acid-derived counterpart [1]. Further, a growing interest on
degradable polymers has promoted a growing research activity on polymers that can
be degraded through hydrolytic or/and enzymatic ways [3]. Aliphatic polyesters such
as poly(glycolic acid) (PGA), among others, have been used in the most diverse
applications, since the conventional uses of plastics, to more sophisticated
applications for example among the medical field [4].
Copolymerization of FDCA with aliphatic diacids and/or hydroxy-acids and diols, could
be an elegant way to obtain materials with enhanced thermal and mechanical
properties, and at same time preserving some degree of biodegradability, enlarging
the role for possible applications [5].
Thus, in this study a series of poly(butylene furandicarboxylate-co-butylene
diglycolate) (PBF-co-PBDG) copolyesters were synthesized via a two-step
polyesterification
procedure
(transesterification
followed
by
a
melt
polytransesterification). The ensuing copolyesters were extensively characterized by
SEC, ATR FTIR, 1H and 13C NMR, TGA, DCS, and DMTA.
[1] A. F. Sousa, C. Vilela, A. C. Fonseca, M. Matos, C. S. R. Freire, G. M. Gruter, J.
F. J. Coelho and A. J. D. Silvestre, Polym. Chem., 2015, 6, 5961–5983.
[2] Avantium. 2011. http://avantium.com/news/2011-2/Avantium-and-The-CocaCola-Company-sign-partnership-agreement-to-develop-next-generation-100-plantbased-plastic-PEF.html.
[3] Y. Tokiwa, B. P. Calabia, C. U. Ugwu and S. Aiba, Int. J. Mol. Sci., 2009, 10,
3722–3742.
[4]
L. S. Nair and C. T. Laurencin, Prog. Polym. Sci., 2007, 32, 762–798.
[5]
E. Olewnik and W. Czerwiński, Polym. Degrad. Stab., 2009, 94, 221–226.
99
CELLULAR UPTAKE MONITORING OF HEATER-THERMOMETER
NANOPLATFORMS USING HYPERSPECTRAL IMAGING
Mengistie L. Debasu1,2, Carlos D. S. Brites1, Sangeetha Balabhadra1,2,
Helena Oliveira3, João Rocha2 and Luís D. Carlos1
Universidade de Aveiro, Department of Physics and CICECO, Aveiro,
Portugal
2Universidade de Aveiro, Department of Chemistry and CICECO, Aveiro,
Portugal
3Universidade de Aveiro, Department of Biology, Laboratory of
Biotechnology and Cytomics, CESAM,, Aveiro, Portugal
1
Plasmonic nanostructures concentrate light and heat within a small volume at the
nanoscale, offering potential applications in areas such as biomedicine, e.g.,
hyperthermia. However, the precise quantification of the actual temperature rise in the
vicinity of such nanosystems poses considerable challenges. Here, we present a new
heater-thermometer nanoplatform capable of measuring the plasmon-induced local
temperature increase of Au nanorods via the ratiometric upconversion of
(Gd,Yb,Er)2O3 nanothermometers [1], upon 980 nm laser excitation at a relatively low
power density
(up to 102.0 W cm-2). The local temperature rise, 302–548 K (maximum temperature
sensitivity 1.22% K−1, uncertainty 0.32 K and repeatability >99%), is assessed using
Boltzmann’s distribution of the Er3+ 2H11/2→4I15/2/4S3/2→4I15/2 intensity ratio. Comparing
with similar nanoplatforms that use spherical Au nanoparticles [2], rather than Au
nanorods, the plasmon-induced heating efficiency increases very significantly due to
shifting of the localized surface plasmon resonance of Au nanorods into resonance
with the excitation. Therefore, much lower laser power densities (8.3–24.8 W cm-2) are
used to achieve thermal heating in the physiological temperature range (302–330 K).
The nanoplatforms are biocompatible with MG-63 and A549 cells and were mapped
within the former using hyperspectral imaging, opening up a new avenue to monitor
the cellular uptake of Ln3+-based nanoplatforms [1].
[1]
M. L. Debasu, C. D. S. Brites, S. Balabhadra, H. Oliveira, J. Rocha and L. D.
Carlos, ChemNanoMat 2016, DOI: 10.1002/cnma.201600061.
[2]
M. L. Debasu, D. Ananias, I. Pastoriza-Santos, L. M. Liz-Marzán, J. Rocha and
L. D. Carlos, Adv. Mater. 2013, 25, 4868.
100
ENHANCED CATALYTIC ACTIVITY OF MESOPOROUS ZERO-VALENT IRON
NANOPARTICLES PREPARED UNDER SONOCHEMICAL IRRADIATION
Mohammadreza Kamali1,2, Maria Elisabete V. Costa2, Isabel Capela1
1
Department of Environment and Planning, Center for Environmental and Marine
Studies, CESAM, University of Aveiro, 3810-193 Aveiro, Portugal
2
Department of Materials and Ceramics Engineering, CICECO-Aveiro Institute of
Materials, University of Aveiro, 3810-193 Aveiro, Portugal
E-mail: Kamali@ ua.pt
Ultrasonic irradiation (UI) is drawing a particular interest in the field of functional
materials synthesis from solution. The extremely high temperatures and pressures that
develop during the acoustic cavitation induced by UI account for unique solution
conditions which allow obtaining nanoscale metals and metal oxides with controlled
morphology [1]. This study addresses the effects of the ultrasonic cavitation on the
improvement of the properties of nanoscale zero valent iron (nZVI) which is a catalyst
for systems designed for the production of energy from wastes (such as anaerobic
digestion [2]). Under selected synthesis conditions of the liquid-phase reduction
process, including the reagent injection rate, the metal cation [Fe+3] concentration, and
the reductant [NaBH4] to cation ratio, nZVI samples were prepared without, and with
UI using an ultrasonic probe. Transmission electron microscopy (TEM), X-ray
diffraction (XRD), particle size distribution (PSD) analysis, Brunauer-Emmett-Teller
(BET) surface area and porosity analysis, and TG-DTA combined thermoanalytical
techniques were utilized to characterize the chemical and physical properties of the
prepared nanoparticles. Also, the catalytic performance of the prepared nanomaterials
towards the reduction reaction of nitrate to nitrite was examined while using ion
chromatography to follow the concentrations of nitrate and nitrite in the reaction media.
The ultrasonic irradiation resulted in nanomaterials with lower particle size and higher
specific surface area (21 m2/g to 26 m2/g), improved dispersion and higher synthesis
yield as compared to the materials synthesized from non-irradiated solutions. Such
improvements coupled with the higher catalytic activity of the UI products towards
nitrate (~71% after 2 hrs, considerably higher than previous reported values [3]),
clearly demonstrate the efficiency of the proposed method for the preparation of nZVI
particles in terms of technical and economic considerations.
[1]
H. Xu, B. W. Zeiger, and K. S. Suslick, Sonochemical synthesis of
nanomaterials, Chem. Soc. Rev., 2013, vol. 42, 2555–2567.
[2]
M. Kamali, T. Gameiro, M. E. Costa, and I. Capela, Anaerobic Digestion of Pulp
and Paper Mill Wastes - An Overview of the Developments and Improvement
Opportunities, Chem. Eng. J., 2016 vol. 298, 162–182.
[3]
Y.-H. Hwang, D.-G. Kim, and H.-S. Shin, Effects of synthesis conditions on the
characteristics and reactivity of nano scale zero valent iron, Appl. Catal. B Environ.,
2011, vol. 105, 144–150.
101
TOWARDS FAST COMPUTATIONAL DESIGN OF MAGNETOCALORIC
MATERIALS
N. M. Fortunato1, J. N. Gonçalves1 , J. S. Amaral1,2, V. S Amaral1
1.
2.
Departamento de Física and CICECO, Universidade de Aveiro, Aveiro 3810-093,
Portugal
Instituto de Física dos Materiais da Universidade do Porto, Institute of Nanoscience
and Nanotechnology, Porto 4169-007, Portugal
The Magnetocaloric Effect (MCE) has attracted interest as a promising path for
more energetically efficient refrigeration systems [1]. By exploiting the relation
between magnetism, entropy and temperature it is possible to design a
refrigeration cycle based on the application and removal of a magnetic field. Of
especial importance is the Giant Magnetocaloric Effect, where structural or
volume transitions enhance the change of entropy. The search for such
materials remains largely experimental, with exhaustive experimental studies
of stoichiometric families of compounds.
We show that it is possible to perform a fast computational calculation of the
thermodynamics of materials with magnetic, volume and structural degrees of
freedom. By using the density of states of spin systems obtained from the
Random Path Sampling method [2], it is possible to describe the system in a
field and temperature independent fashion, while Density Functional theory can
give volume dependent exchange interactions and the energies of the
structures.
We apply this methodology to Gadolinium a well-known magnetocaloric
material and describe accurately both magnetostriction (change of lattice
parameter with field) and entropy variation which is a figure of merit for MCE.
This opens up the possibility of replacing the extensive experimental effort
employed in the search for better magnetocaloric materials with computational
material design.
[1]
K .A. Gschneidner Jr et al, Rep. Prog- Phys. 2005, 68, 1479
[2]
J. S. Amaral et al, IEEE Transactions on Magnetics 2014 , 50, 11
102
IN SITU FUNCTIONALIZATION OF CELLULAR ALUMINOSILICATES
N. Vitorino 1, A. Kovalevsky 1, J.R. Frade 1
1
Department of Materials and Ceramic Engineering, (CICECO), University of
Aveiro, 3810 Aveiro, Portugal
Natural clays are often studied for different applications such as adsorbents,
filter materials, catalytic supports, etc., due to their abundance, low cost and
optimal absorption capabilities for a variety of organic and inorganic
compounds. Nevertheless, these functionalities are usually lost on sintering at
high temperatures, and even on calcining at intermediate temperatures if one
seeks strong agglomerates; this is caused mainly by elimination of hydrated
groups from the aluminosilicates. Thus, the actual work proposes an alternative
strategy based on processing of highly porous clay ceramic monoliths, using
kaolin and other natural clays as raw materials, and subsequent in situ
functionalization with zeolites by hydrothermal synthesis using Al and Si
removed by leaching from the aluminosilicate network. Different hydrothermal
conditions was assessed with consequent different zeolite phases (sodalite,
fajausite and cancrinite) as a resulting product.
103
FUNCTIONAL CELLULAR CERAMICS FOR SUSTAINABLE ENERGY
SYSTEMS
N. Vitorino, S.G. Patrício, J. R. Frade, F.M.B. Marques
Department of Materials and Ceramic Engineering/CICECO, University of Aveiro,
Aveiro, 3810-193, Portugal
Porous ceramics with engineered microstructures have been highlighted in a
myriad of applications, including catalysis, biomedicine, energy conversion and
environmental technologies. Among advanced porous ceramics, special
attention has been devoted to cellular ceramics due to their outstanding
properties such as high permeability, low relative density, high specific area,
low thermal conductivity and high thermal shock resistance [1]. The ability to
tailor their microstructural features, namely porosity, shape, average cell size
and size distribution, wall thickness and also connectivity between the cells is
a key parameter that allows engineering their properties en route to the target
application [2].
Among the diversity of processing methods, emulsification of ceramic
suspensions in melted paraffin shown to be one of the most suitable strategy
of providing more homogeneous, highly porous cellular ceramics, easily
scalable with constant cross-section for industrial applications [2,3].
In this work, porous cellular ceramics based on Gd-doped ceria were for the
first time processed by the emulsification method of CGO suspensions in
melted paraffin and subsequently consolidated at 1500 ºC for 2 h after a burnout
stage of the organic phase. The potential use of this cellular preforms is to
support molten carbonates as functional composites for application in either
low-temperature solid oxide fuel cells or carbon dioxide separation membranes
[4].
Dual ionic conduction model (trough CGO matrix and molten carbonate) based
on composite microstructural features was also developed to predict their
electrical properties.
[1] F.S. Ortega, A.E.M. Paiva, J.A. Rodrigues, V.C. Pandolfelli, Cerâmica
2003, 49, 1.
[2] N. Vitorino, J.C.C. Abrantes, J.R. Frade, Mater. Lett. 2013, 98, 120.
[3] N. Vitorino, C. Freitas, M.J. Ribeiro, J.C.C. Abrantes, J.R. Frade, Appl.
Clay Sci. 2014, 101, 315.
[4] Y. Li, Z. Rui, C. Xia, M. Anderson, Y.S. Lin, Catal. Today 2009, 148, 303.
104
ELECTROCATALYSTS FOR SOLID ALKALINE FUEL CELLS
Nuno Sousa1, Biljana Šljukić2, David Cardoso2, Diogo Santos1,2,
Filipe L. Figueiredo1
1
2
CICECO, Dep. of Materials and Ceramic Engineering, University of Aveiro,
Materials Electrochemistry Group, Dep. of Chemical Engineering, Technical
University of Lisbon
In Solid Alkaline Fuel Cells (SAFC), the improved electrode kinetics
(characteristic of the alkaline media) may allow the use of low cost materials in
replacement of the expensive platinum based ones. Oxides with the layeredperovskite structure La2MO4, where M is a transition metal have attracted much
attention due to the oxygen mobility and the possible substitution of trivalent
La3+ for divalent Sr2+ (Sr’La), which stimulates the creation of electron holes.
However, when tested in alkaline environments La2NiO4 presented poor
stability.[1]
La2M1-xDxO4±δ materials, where M is Ni or Cu and D is Ce, Sr and Pr, were
prepared by reactive milling combined with a high temperature annealing, and
characterized by XRD, SEM and EDS. Dense ceramic electrodes were
assembled in order to assess their electronic conductivity and intrinsic
electrochemical activity for the reduction of hydrogen peroxide in alkaline media
(2 M NaOH aqueous solution), using 4-probe dc and cyclic voltammetry as the
instrumental techniques, respectively. The ceramic samples were immersed for
48h in 2M NaOH and the filtered supernatant was analyzed by ICP-MS.
Single phase lanthanum cuprates and nickelates (with the exception of the Ce
doped materials) could be obtained by a combination of high energy milling of
the precursors and subsequent treatment at 1000 °C for 10 min. The pure
lanthanum nickelate does not show intrinsic electrocatalytic activity for H2O2
reduction, either due to mass transport or ohmic limitations, or possibly also
due to competing mechanisms associated to the initial H2O2 decomposition. In
fact, among all materials analysed, only La2CuO4, La1.8Ce0.2NiO4 and
La1.9Sr0.1NiO4 showed increased current densities when using H2O2 solution,
and therefore catalytic activity for its reduction. However, the promising
electrochemical may be compromised by the limited chemical stability of these
materials in strong alkaline media (pH>14). Ex-situ stability tests in 2M NaOH
indicate that Sr and Cu cations tend to leach out of the surface, which may
compromise the long term stability of these catalysts. Post mortem SEM
analysis of the ceramic electrodes used in the electrochemical measurements
revealed a heterogeneous surface that may be the face of the degradation,
probably enhanced by the cathodic bias applied in those tests.
[1]
S. K. Poznyak, V. V. Kharton, J. R. Frade, A. A. Yaremchenko, E. V.
Tsipis, S. O. Yakovlev, and I. P. Marozau J. Solid State Electrochem. 2007 12:
15–30.
105
A BACTERIAL CELLULOSE NANOCOMPOSITE MEMBRANE
WITH OH- CONDUCTIVITY
Nuno Sousa1, Carla Vilela2, Carmen S. R. Freire2, Armando J. D. Silvestre2,
Filipe L. Figueiredo1
1
CICECO, Dep. of Materials and Ceramic Engineering, University of Aveiro
2
CICECO, Dep. of Chemistry, University of Aveiro
In Solid Alkaline Fuel Cells (SAFC), the lower OH- conductivity when compared
to H+ in Proton Exchange Membrane Fuel Cells (PEMFC) is a drawback that
could be overcome by increasing the ionic exchange capacity (IEC) of the
SAFC membranes. However, this usually lowers their mechanical properties.
Solutions to overcome this drawback include cross-linking of polymeric chains
or casting the polymer on a supporting mesh [1]. This work aims at showing the
use of bacterial cellulose (BC) as a support matrix for SAFC OH- conducting
membrane. BC is a biopolymer stable in alkaline media with high tensile
strength due to a nanofibrilar 3D-network. Polymers containing quaternary
ammonium groups are stable in alkaline media, namely those derived from
aminoalkylacrylates such as poly(3-Acrylamidopropyl) trimethylammonium
chloride (PAPTACl), selected for this work.
BC:PAPTAClcomposite membranes were prepared with different PAPTACl
content by in situ free radical polymerization and simultaneous cross-linking
with N,N methylene-Bis-acryalmide: BIS). Exchange for OH- originated the
desired PAPTAOH:Bis hydroxyl conductor. Extensive characterization was by
FTIR-ATR, solid state NMR, SEM and XRD. The in-plane anionic conductivity
was determined by impedance spectroscopy under variable temperature (3094 °C) and relative humidity (RH, 20-98%). The materials were also
characterized by Dynamic Mechanical Analysis (DMA) and Thermogravimetric
Analysis (TGA). The IEC and water retention capacities were measured by
back-titration and the difference between wet and dry weights, respectively.
All membranes were crack-free and with thickness between 80 and 400 µm.
The DMA revealed a viscoelastic behavior typical of the BC, with all materials
stable up to at least 160 °C. All the membranes showed to be stable under the
temperature and pH conditions typical of a SAFC in which they were tested.
The best nanocomposites have water uptake around 160%, close to pure BC,
and IEC increasing from 0.3 to 1.7 mmol[OH-]g-1 with increasing PAPTAOH:Bis
content. Finally, the best materials achieved conductivity in excess of 0.03
S.cm-1 at 94 °C/98% RH.
[1]
Tiago D. O. Gadim, Andrea G. P. R. Figueiredo, Nataly C. RoseroNavarro, Carla Vilela, José A. F. Gamelas, Ana Barros-Timmons, Carlos
Pascoal Neto, Armando J. D. Silvestre, Carmen S. R. Freire, and Filipe M. L.
Figueiredo ACS Applied Materials & Interfaces 2014 6: 7864-7875
106
THIN FILM VERSUS PAPER-LIKE REDUCED GRAPHENE OXIDE:
COMPARATIVE STUDY OF STRUCTURAL, ELECTRICAL, AND
THERMOELECTRICAL PROPERTIES
Olena Okhay1,2, Gil Gonçalves1, Catarina Dias3, Joao Ventura3,
Manuel Fernando Ribeiro da Silva4, Luís Miguel Valente Gonçalves4,
Elby Titus1, Alexander Tkach2
1
Nanotechnology Research Division, Center for Mechanical Technology and
Automation (TEMA), Department of Mechanical Engineering, University of Aveiro,
3810-193 Aveiro
2
Engineering, University of Aveiro, 3810-193 Aveiro
3
Institute of Physics of Materials of the University of Porto (IFIMUP), 4169-007 Porto
4
Industrial Electronics Department, University of Minho, Azurem, 4800-058
Guimaraes
Graphene, a two-dimensional nanocarbon material, has attracted significant
attention in recent years due to its extraordinary physical and chemical
properties, although it is extremely difficult to synthetize defect free graphene
at macroscopic scale. Being also graphite-derived, reduced graphene oxide
(rGO) appears as an efficient and low-cost solution for the development of large
area graphene-based materials. Thanks to the combination of its excellent
mechanical properties and chemical tunability, rGO films as well as freestanding rGO paper-like materials are exciting systems for potential
applications such as membranes with controlled permeability, anisotropic ionic
conductors, mechanically reinforced composites or transparent, electrically
conductive films.
We report fabrication of reduced graphene oxide (rGO) films using chemical
reduction by hydrazine hydrate and rGO paper-like samples using low
temperature treatment reduction. Structural analysis confirms formation of the
rGO structure for both samples. Current-voltage (I-V) measurements of the rGO
film reveal semiconductor behavior with the maximum current value of ~3×10-4
A. The current for the rGO paper sample is found to be, at least, one order of
magnitude higher. Moreover, bipolar resistance switching, corresponding to
memristive behavior of type II, is observed in the I-V data of the rGO paper.
Although precise values of the rGO film conductivity and Seebeck coefficient
could not be measured, rGO paper shows an electrical conductivity of 6.7×102
S/m and Seebeck coefficient of -6 µV/°C. Thus, we demonstrate a simplified
way for the fabrication of rGO paper that possesses better and easier
measurable macroscopic electrical properties than that of rGO thin film [1].
[1] O. Okhay, G. Gonçalves, A. Tkach, C. Dias, J. Ventura, M. F. Ribeiro da
Silva, L. M. Valente Gonçalves, E. Titus, J. Appl. Phys. 2016, accepted.
107
SYSTEMATIC STUDY OF GALVANIC CORROSION MITIGATION ON
Zn+Fe AND AA2024+CFRP JOINTS
Oliveira M. P.1, Kallip S.1,2, Bastos A.C.1, Hack T.3, Nixon S.3, Ferreira
M.G.S.1, Zheludkevich M.L.1,4
1CICECO
– Aveiro Institute of Materials, Department of Materials and
Ceramics Engineering, 3810-193 Aveiro, Portugal
2Institute of Chemistry, University of Tartu, Ravila 14a, 50411 Tartu, Estonia
3Airbus Group Innovations, 82024 Munich, Germany
4Institute of Materials Research, Helmholtz-Zentrum Geesthacht, Centre for
Materials and Coastal Research GmbH, Max-Planck-Str. 1, 21502
Geesthacht, Germany
Galvanic joints of different materials such as Zn+Fe, AA2024+CFRP are widely
used nowadays industrial constructions, especially in aeronautical industry due
to high demands on weight reduction and high mechanical properties. It is clear
that corrosion problems arise when these materials are galvanically coupled
and the corrosion of the less noble structural material occurs. Current measures
for the protection are inefficient or expensive. Therefore, novel protection
strategies are under development with a significant industrial demand.
The main objective of this work was to try to understand the inhibition
mechanisms present in previously studied synergistic mixtures[1].
It has found that the corrosion impact on specific galvanic systems can be
successfully inhibited by using specially designed and dedicated combinations
of corrosion inhibitors based on the synergistic cooperation of their different
corrosion inhibition mechanisms.
Different electrochemical techniques such as EIS, DC-polarization and ZRA
together with a full analysis and modelling of data were systematically applied.
As the galvanic system is electrochemically demanding and dynamic system,
the new aspects analyze and data interpretation will be discussed.
[1]
S. Kallip, A. C. Bastos, K. a. Yasakau, M. L. Zheludkevich, and M. G. S.
Ferreira, Electrochem. commun., 2012, vol. 20, no. 1, pp. 101–104.
108
HIGH IONIC CONDUCTIVITY IN ZEOLITIC IMIDAZOLATE FRAMEWORK 8
P. C. Barbosa1, M.R. Soares2, M. Pinto3, F. A. Almeida Paz4, F. M.
Figueiredo1
1
CICECO - Aveiro Institute of Materials, Dep. Materials & Ceramic Eng, U. of Aveiro,
Portugal;
2
CICECO - Aveiro Institute of Materials, LCA, U. of Aveiro, Portugal;
3
CERENA, Dep. Chemistry Engineering, IST, U. Lisboa, Portugal;
4
CICECO – Aveiro Institute of Materials, Chemistry Dep., U. of Aveiro, Portugal
The variety of crystalline architectures of metal organic frameworks (MOFs) with
significant porosity and thus high surface area allow the design of novel protonic
conductors based on these versatile scaffolding materials [1]. Zeolitic Imidazolate
Frameworks (ZIFs), a subfamiliy of MOFs, are a class of porous crystals with extended
3D frameworks and great potential for many applications such as separation and
storage of gases [2]. ZIF8 is one of the most studied prototypical ZIF compounds and
is composed of Zn and 2-methylimidazole ligands, forming the sodalite (SOD) zeolite
structure with large cavities (11.6 Å) and small pore apertures (3.4 Å) [3]. ZIF8 has
high thermal stability and remarkable chemical resistance in the presence of water and
organic solvents, mostly due to its hydrophobic framework [3].Recently the synthesis
of ZIF8 with different amounts and types of porosity and the study of their influence on
the protonic conductivity of this type of MOFs have been reported [4]. The specific
surface area of the powders varies between 800 and 2251 m2g-1, with the highest
values obtained for the pure ZIF8. The most conducting samples corresponded to
those with highest surface area, attaining a maximum of 4.6x10-4 Scm-1 at 94 ºC and
98% RH. Here we present the synthesis under controlled pH conditions of a modified
ZIF8 framework with the pores filled with hydrofilic domains that greatly enhance the
water absortion capacity in comparison with the highly hydrofobic unmodified material,
while maintaining their stability under humid conditions. These nanocrystals present
an ionic conductivity of 7.39x10-2 Scm-1 at 94ºC and 98% RH, which is up to 2 orders
of magnitude higher than for pure ZIF8 and represents one of the highest values
reported for a MOF-based ionic conductor [1]. At 1:8 Zn/Hmim molar ratios, surface
areas are estimated in the range of ~450-1660 m2g2 (SBET) and the material is
structurally stable up to 400ºC.
[1] P. Ramaswamy, N. E. Wong, G. K. H. Shimizu, Chem. Soc. Rev., 2014,43, 5913
[2] B. Chen, Z. Yang, Y. Zhu, Y. Xia, J. Mater. Chem. A, 2014, 2, 16811
[3] K.S. Park, Z. Ni, A.P. Cote, J.Y. Choi, R. Huang, F.J. Uribe-Romo, H.K. Chae, M.
O'Keeffe, O.M. Yaghi, Proc Natl Acad Sci U S A, 2006, 103, 10186.
[4] P. Barbosa, N. C. Rosero-Navarro, F.-N. Shi, F. M.L. Figueiredo, Electrochem.
Acta, 2015, 153, 19.
Akowledgements
Work funded by FCT through grants FCOMP-01-0124-FEDER-014605 (Ref.
PTDC/CTM-NAN/110776/2009), CICECO - FCOMP-01-0124-FEDER-037271 (Ref.
FCT PEst-C/CTM/LA0011/2013), IF/01174/2013 and SFRH/BPD/96665/2013.
109
THICKNESS DEPENDENCY OF STRUCTURE AND MAGNETIC
PROPERTIES OF La1-xSrxMnO3 THIN FILMS ON SrTiO3 SUBSTRATE
P. Mirzadeh Vaghefi1, A. Baghizadeh2, M. J. Pereira1, M. Willinger2, V. S.
Amaral1
1Department
2Department
of Physics & CICECO, University of Aveiro, Portugal.
of Ceramics and Materials Engineering, CICECO, University of
Aveiro, Portugal.
3Department
of Inorganic Chemistry, F.-H.-Inst. Max-Planck-Gesellschaft,
Faradayweg, Berlin, Germany.
The crystal structure, magnetization and microstructure of the La0.67Sr0.33MnO3
(LSMO) thin films, epitaxially grown on (1 0 0) SrTiO3 (STO) substrate have
been investigated. It is found that the as-processed films show an abnormal
behaviour in temperature dependent magnetization below antiferrodistortive
SrTiO3 phase transition, below 105 K [1]. Films with thicknesses above 100 nm
show an in-defect magnetization, where below 100 nm, the magnetization
behaviour of the samples show an in-excess magnetization, in the same
temperature region. We have analysed the crystal and microstructure of the
films, using high resolution XRD (HRXRD) and high resolution cross-section
transmission electron microscopy (HR-XTEM). The samples are showing a
rhombohedral pseudocubic structure in bulk form; where X-ray diffraction θ/2θ
scans at room temperature indicates that the 200 nm film can be considered as
a mixture of two phases, rhombohedral (La0. 7Sr0.28Mn0.99O3) and orthorhombic
(La0.98Sr0.02MnO3), also proved by STEM analysis. The Sr-deficient phase is
observed near the interface with the substrate. Using HRTEM and STEM
analysis, it is possible to observe a transition in structure of thin film, from
epitaxial polycrystalline in 13.5 nm film, to a branched structure in 320 nm film.
In the middle thicknesses, the film is arranges into tilted columns, with 67.2°
growth direction, in respect to the substrate.
It is obvious that the in-defect magnetization observed for thicker films can be
understood by the formation of randomly oriented magnetic domain
reconstructions associated with film relaxations, confirmed by both XRD and
HRTEM. This shows a close relation between the structural unit cells of both
SrTiO3 and LSMO film [1], where the structural coupling between the film and
substrate, through the SrTiO3/LSMO interface is the driving force of the
structure of the film and magnetic properties of the film, consequently. The
interface-mediated magneto-elastic coupling is playing the main role in the
magnetization behaviour of the thin film [1].
[1] D. A. Mota et al., Journal of Physics D: Applied Physics 47, 435002 (2014).
110
GROWTH OF FUNCTIONAL PROTEIN FIBRILS FROM EGG WHITE
PROTEOME: EFFECT OF PROTEIN CROWDING
Pankaj Bharmoria,1Dibyendu Mondal,1 Matheus M. Pereira,1 Márcia C.
Neves,1 Mafalda R. Almeida,1 João A. P. Coutinho,1 Mara G. Freire1
1CICECO
- Aveiro Institute of Materials, Department of Chemistry,
University of Aveiro, 3810-193 Aveiro, Portugal
Protein fibrils, which are typically affiliated to amyloidogenic diseases,1 have
attracted attention in recent years as smart materials in nano/biotechnology on
account of their functional nature, mechanical strength and stiffness.2 However,
scalability and synthesis kinetics are the major hurdles of their broad scale
application.3 The fibrillation propensity of a protein is governed by features viz.
hydrophobicity, secondary structure variations, charge/aromatic/hydrogen
bonding interactions and physiological environment. In the present work, we
have played both with the physiological environment of proteins and fibrillating
agent (containing sites for aromatic, coulombic and hydrogen bonding
interactions) for bulk scale incipient fibrillation of functional fibrils from egg white
proteome (EWP). The fibrillating agent used is a bio-based ionic liquid (IL),
customized to attain the desired physico-chemical properties, while favouring
incipient fibrillation on the basis of protein crowding phenomena. Insights into
protein-protein and protein-IL interactions were obtained from computational
studies and spectroscopic analyses. The synthesized fibrils show an excellent
capacity to adsorb Cytochrome c with a large enhancement of its peroxidase
activity compared to aqueous media. Finally, the prepared fibrils have tendency
to form functional membranes with excellent pH stability in the acidic region,
which could be explored to elute biomolecules based on their charge when
envisaging the development of separation processes for proteins.
[1] M. Dobson, Nature, 2003, 426, 884.
[2] T. P. J. Knowles, T. W. Oppenheim, A. K. Buell, D. Y. Chirgadze, M. E.
Welland, Nat. Nanotech., 2010, 5, 204
[3] O. G. Jonesa, R. Mezzenga, Soft Matter, 2012, 8, 876
Ref. UID /CTM /50011/2013), financed by national funds through the
FCT/MEC and when appropriate co-financed by FEDER under the PT2020
Partnership Agreement. M. G. Freire acknowledges the European Research
Council under the European Union's Seventh Framework Programme
(FP7/2007-2013) / ERC grant agreement n° 337753.
111
ONE-POT CONVERSION OF FURFURAL IN THE PRESENCE OF A Sn,AlCONTAINING ZEOLITE BETA CATALYST
Patrícia Neves1, Margarida M. Antunes1, Sérgio Lima2,1, Ana L. Magalhães1,
Enza Fazio3, Auguste Fernandes4, Fortunato Neri3, Carlos M. Silva1, Sílvia M.
Rocha5, Maria F. Ribeiro4, Martyn Pillinger1, Atsushi Urakawa2, Anabela A.
Valente1
1
CICECO, Department of Chemistry, University of Aveiro, Aveiro, Portugal
2
3
ICIQ, Av. Països Catalans, Tarragona, Spain
Dipartimento di Fisica e di Scienze della Terra, Università degli Studi di Messina,
Viale F. Stagno d’Alcontres, Messina, Italy
4
5
Institute for Biotechnology and Bioengineering, IST, Lisboa, Portugal
Department of Chemistry, QOPNA, University of Aveiro, Aveiro, Portugal
E-mail: pneves@ ua.pt
The one-pot conversion of Furfural (Fur) to useful bio-products (furfuryl alkyl
ethers, levulinate esters, levulinic acid, angelica lactones, γ-valerolactone) was
investigated using a single heterogeneous catalyst, in 2-butanol, at 120 ºC
(Scheme 1) [1]. Modified versions of zeolite beta containing Al, Sn sites,
prepared from commercially available nanocrystalline zeolite beta via postsynthesis
partial
dealumination
followed by solid-state ion-exchange,
were explored. The best-performing
catalyst had Si/(Al + Sn) = 19 (Sn/Al
= 27): total yield of bio-products of
83% at 86% Fur conversion and
steady catalytic performance for six
consecutive runs. This was related to
the dealumination degree, dispersion
and amount of Sn-sites, and acid
properties. A systematic catalytic
Scheme 1. Conversion of Fur in alcohol media
study using the prepared catalysts to give useful bio-products via acid/reduction
with different bio-products as chemical routes.
substrates, together with the
characterisation of the materials, helped understand the effects of material
properties on the specific reaction pathways in the overall system.
Acknowledgements:
CICECO
(POCI-01-0145-FEDER-007679;
FCT
ref.
UID/CTM/50011/2013) and QOPNA (FCT ref. UID/QUI/00062/2013), financed by
national funds through the FCT/MEC and by FEDER under the PT2020 Agreement;
the FCT and the EU for BPD grants to MMA, PN (SFRH/BPD/73540/2010), ALM and
AF, co-funded by MCTES and the ESF through the program POPH of QREN. SL and
AU thank MINECO for support through Severo Ochoa Excellence Accreditation 20142018 (SEC-2013-0319).
[1] M. Antunes, S. Lima, P. Neves, A.L. Magalhães, E. Fazio, A. Fernandes, F.
Neri, C. M. Silva, S. M. Rocha, M. F. Ribeiro, M. Pillinger, A. Urakawa, A. A.
Valente, Journal of Catalysis 2015, 329, 522.
112
SERS-ACTIVE MAGNETIC SORBENTS FOR REMOVAL AND OPTICAL
DETECTION OF PENICILLIN G
Paula C. Pinheiro1, Tito Trindade1,2
1Department
of Chemistry-CICECO, University of Aveiro, 3810-193 Aveiro,
Portugal
Serious concerns have been raised about the occurrence of antibiotics in the
environment due to their potential risk to human health and aquatic ecosystem.1
Particularly, such water contaminants contribute to the increased resistance of
some pathogenic microorganisms to conventional antibiotics. In this context,
recent developments in nanomaterials science and environmental
nanotechnology have provided new methods for purification of trace pollutants
in water. Our own interest in this field, led us to develop new colloidal sorbents
for the removal of water contaminants via magnetic separation.2,3 The upgrade
of such sorbents for simultaneous use in water purification and contaminant
detection is a challenging task but of great practical interest.
The present work aims the developing of SERS-active magnetic sorbents, as
innovative platforms for magnetic removal and Raman analysis of penicillin G
dissolved in water. Multifunctional nanomaterials combining magnetic and
plasmonic components have been prepared by surface-modification of colloidal
magnetite nanoparticles with siliceous shells enriched in dithiocarbamate
groups2, followed by adsorption of gold nanoparticles onto the nanoparticles
surfaces.3 The ability of such multifunctional sorbents to act as SERS platforms
for the detection of penicillin G removal was then evaluated. Several analytical
conditions have been investigated in order to optimize the SERS detection of
penicillin G. Additionally, microscopic methods, including Raman confocal
microscopy, have been employed to characterize the SERS substrates and
respective monitoring process. These results will be discussed on a perspective
of potential use of these materials for laboratory monitoring and water treatment
units.
[1] C. Xi, Y. Zhang, C. F. Marrs, Applied Environmental Microbiology, 2009, 75, 5714.
[2] D. S. Tavares, A. L. Daniel-da-Silva, C. B. Lopes, N. J. O. Silva, V. S. Amaral, J.
Rocha, E. Pereira, T. Trindade, Journal of Materials Chemistry A, 2013, 1, 8134.
[3] J. L. Lopes, K. L. Marques, A. V. Girão, E. Pereira, T. Trindade, Journal of Colloid
and Interface Science, 2016, 475, 96.
Acknowledgements P. C. Pinheiro thanks FCT for the grant SFRH/BD/96731/2013.
This work was financed by national funding from FCT (Fundação para a Ciência e a
Tecnologia) by FEDER through program COMPETE and by national funding through
FCT in the frame of project CICECO - FCOMP-01-0124-FEDER- 037271 (Ref. FCT
Pest-C/CTM/LA0011/2013).
113
PROMISING CALCIUM PHOSPHATE CEMENTS FOR VERTEBROPLASTY
APPLICATION
Paula M. C. Torres1, Ana Marote2, Ana R. Cerqueira 2, António J. Calado3,
João C. C. Abrantes1,4, Susana Olhero1, Odete A. B. da Cruz e Silva2,
Sandra I. Vieira2, José M. F. Ferreira1
1
Department of Materials and Ceramic Engineering, CICECO, University of Aveiro,
2
Department of Medical Sciences, Institute for Biomedicine (iBiMED), University of
3
Department of Biology, GeoBioTec, University of Aveiro, 3810-193 Aveiro, Portugal
4
UIDM, ESTG, Polytechnic Institute of Viana do Castelo, 4900 Viana do Castelo,
Portugal
E-mail: ptorres@ ua.pt
Calcium phosphate bioceramics are among the most suitable bone graft
materials due to their close chemical similarity with mineral bone composition.
These biocompatible, bioresorbable, bioactive and osteoconductive materials
are commercially available in various forms, i.e. granules, blocks, nonhardening pastes and hydraulic cements. The injectable forms of calcium
phosphate cements (CPCs) combine the optimal bone defect filling capacity,
via minimally invasive surgeries with the ability to harden in vivo at body
temperature, and low exothermicity setting reactions [1]. However, the poor
mechanical properties and low injectability are the major drawbacks hampering
the widespread application of these cements in osteoregeneration.
The main target of this work is the enhancing of both handling (setting time,
injectability) and mechanical strength properties of brushite CPCs, maintaining
or even improving their biological performance. The cements were prepared by
mixing monocalcium phosphate monohydrate with doped β-TCP powders heat
treated at 800ºC with different liquids, using citric acid and sugars (sucrose and
fructose) as setting retarders, and polyethylene glycol, hydroxypropyl
methylcellulose as gelling agents. The combination of: (1) co-doping with Mn
and Sr; (2) adding sucrose to the setting liquid, and (3) using powders with a
suitable particle size distribution, greatly enhanced the overall properties of
cements in terms of handling, microstructure, mechanical and biological
behaviours. This combined use not only greatly improved osteogenic
performance such as adhesion and growth of osteoblastic cells on the cement’s
surface, but also extended the cements’ working time and conferred them an
excellent injectability and an improvement of mechanical properties making
them very promising for bone regeneration and tissue engineering.
[1] S.V. Dorozhkin, J. Funct. Biomater. 2013, 4, 209-311.
114
DISPELLING SOME MYTHS ABOUT THE CO2 SOLUBILITY IN IONIC
LIQUIDS
Pedro J. Carvalho1, João A. P. Coutinho2
1CICECO
– Aveiro Institute of Materials , Department of Chemistry, University
of Aveiro, 3810-193 Aveiro, Portugal.
Ionic liquids are undeniably interesting compounds, with a wide range of
potential applications and the ability to be designed to meet a specific set of
requirements. This does not mean however that their application can be
successful in all fields. ILs have been object of extensive research for physical
sorption of CO2 and a number of myths have been perpetuating in the literature,
for lack of a critical analysis, concerning their potential for CO2 capture.
This work carries a critical analysis of a number of widely accepted ideas, and
others not so well accepted, that have been repeatedly expressed in the
literature concerning the CO2 physical sorption in ionic liquids. Using the CO2
solubility in eicosane as benchmark, it will be shown that there is no evidence
that ionic liquids display a physical sorption of CO2 larger than n-alkanes when
analyzed in adequate concentration units; the fluorination of the ions has no
impact on the CO2 solubility and the oxygenation will marginally contribute to a
decrease of the solubility. Ionic liquid-based deep eutectic systems are also
shown to have a poor CO2 solubility.
eicosane
Although these widely used approaches, to physically enhance the CO2
solubility in ionic liquids, do not seem to have any positive influence, this does
not mean that other type of interactions, cannot provide enhanced CO2
solubility as is the case of the anion [B(CN)4]. The mechanism of the CO2
physical sorption on ionic liquids is discussed based on the results analyzed,
supported by spectroscopic measurements and molecular simulations
previously reported, and further suggestions of possibilities for enhanced
physical sorption based on fluorinated aromatic rings, other cyano-based
anions, mixtures with other ionic liquids or solvents or the use of porous liquids
are proposed.
Figure 1. pTmCO2 phase diagram of ILs
with hydroxyl, ether and ester
functionalization, at 333 K. The black
line represent the estimated pressure
values for the eicosane and the dashed
red line the [C6C1im][NTf2] + CO2
experimental equilibrium pressure
values.
115
NANOSCALE ELECTROMECHANICAL PROPERTIES OF GRAPHENE
R. Vidyasagar1, K. Romanyuk1, G. da Cunha Rodrigues1, S. Luchkin2, Ya.
Kopelevich2, A. Kholkin1
1Dept.
of Physics & CICECO – Aveiro Institute of Materials, University of
2Instituto
de Física, UNICAMP, Campinas, Sâo Paulo 13083-859, Brasil
Recent discovery of piezoelectricity in two-dimensional (2D) materials [1] opens
up new opportunities for stretchable electronics [2], sensors, actuators and
other electronic components based on the direct and converse piezoelectric
effects. Being a 2D monoatomic material with many unique properties,
graphene is one of the favorable candidates for these applications. It exhibits a
variety of emergent properties such as high thermal conductivity, superior
mechanical strength and extremely high flexibility. Although pristine graphene
does not possess any piezoelectric activity due to its intrinsically
centrosymmetric crystal structure, piezoelectricity can be induced by breaking
the inversion symmetry, by adsorption of foreign atoms, by introducing specific
in-plane defects or by non-uniform deformation of graphene layers in which
strain gradients can create internal polarization in a material.
In this work, we observed a strong piezoelectric activity of a single-layer
graphene (SLG) deposited on Si/SiO2 calibration grating substrates [3].
Mapping the strain distribution in graphene was performed via confocal Raman
measurements and converse piezoelectric effect was measured locally by
Piezoresponse Force Microscopy (PFM). The piezoelectric activity of graphene
layers was mainly attributed to the chemical interaction of carbon atoms with
underlying oxygen from SiO2 substrates. Piezoelectric effect is sufficiently high
(d33≈1.4 nm/V, that is, more than twice of the best piezoelectric ceramics such
as modified lead zirconate titanate - PZT). The effect was linear in the range of
applied voltages up to 2 V and strongly amplified by the cantilever resonance.
In addition, we found that that the work function of graphene layer is becoming
smaller while its thickness decreases. This response could be attributed to the
variation of the Fermi energy with respect to the Dirac point energy of graphene
band structure and the electrostatic interlayer screening effects between the
graphene and SiO2. Our findings will provide an understanding on how the
Fermi level can be controlled by thickness of single-layer graphene, thus
enabling to develop next-generation quantum transport device.
[1] K.A.N. Duerloo, M.T Ong, J. T. J. Reed, Phys. Chem. Lett. 2012, 3, 2871.
[2] J. A. Rogers, T. Someya, Y. Huang, Science 2010, 327, 1603.
[3] G. da Cunha, P. Zelenovskiy, K. Romanyuk, S. Luchkin, Ya. Kopelevich, A.
Kholkin, Nat. Commun. 2015, 6, 7572.
116
BUILDING LIGHT-EMITTING METAL-ORGANIC FRAMEWORKS BY
POST-SYNTHETIC MODIFICATION
Reda M. Abdelhameed,1,2 Artur M. S. Silva,2 João Rocha,1 Luis D. Carlos,3
1
Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro,
Portugal.
2
Department of Chemistry, QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal.
3
Department of Physics, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal.
E-mail: reda.abdelhameed@ ua.pt
Metal-organic frameworks (MOFs) are crystalline materials consisting of metal
ions and organic linkers. MOFs have a potential application in gas storage, gas
separations, chemical sensing, ion exchange, drug delivery, removal of heavy
metals from aqueous solutions, catalysis, and as photoactive and luminescent
materials [1]. One of the most attractive features of MOF materials is the
possibility of their post-synthetic modification (PSM) [2], particularly by the
functionalisation of linkers to produce materials with new functionalities.
Lanthanide-organic frameworks (Ln-MOFs) have promising applications due to
their unique luminescence properties. However, it is still very challenging to
develop suitable Ln-MOF materials capable of producing color tunable and
white-light emission. Moreover, a higher coordination number and more flexible
coordination geometry of lanthanide ions make it even harder to obtain stable
porous lanthanide MOFs [3].
Our main research interest focuses on PSM as a route to introduce active sites
for light-emitting devices into MOFs. [4] Isoreticular metal-organic framework-3
(IRMOF-3) was chosen due to its highly porous, crystalline structure and the
presence of non-coordinating amino groups on the benzenedicarboxylate (bdc)
linker, which can be easily modified. IRMOF-3 was modified with organic
reagents such as methyl 3-chloro-3-oxopropanoate and pyridine-2,6-dicarbonyl
dichloride. 1H NMR of the digested post-synthetic modified samples showed
that the conversion of the amino group was 100%. The pendant groups of
modified IRMOF-3 were used to coordinate the light-emitter lanthanide (Ln+3)
and the luminescent properties of the materials were studied. The samples
were characterised by powder XRD, EDS elemental analysis and solid-state
NMR.
[1] R.J. Kuppler, D.J. Timmons, Q. Fang, J. Li, T.A. Makal, M.D. Young, D.
Yuan, D. Zhao, W. Zhuang, H. Zhou, Coord. Chem. Rev., 2009, 253, 3042–
3066.
[2] R.M. Abdelhameed, L.D. Carlos, A.M.S. Silva and J. Rocha, Chem.
Commun., 2013, 49, 5019.
[3] J. Rocha, L.D. Carlos, F.A.A. Paz, D. Ananias, Chem. Soc. Rev., 2011, 40,
926-940.
[4] R.M. Abdelhameed, L.D. Carlos, A.M.S. Silva, J. Rocha, New J. Chem.,
2015, 39, 4249-4258.
117
LAMELLAR COORDINATION POLYMER WITH A REMARKABLE
CATALYTIC ACTIVITY
Ricardo F. Mendes,1 Margarida M. Antunes,1 Patrícia Silva,1Paula
Barbosa,2Filipe Figueiredo,2 Anthony Linden,3João Rocha,1 Anabela A.
Valente,1 Filipe A. Almeida Paz1
1Department
of Chemistry, CICECO– Aveiro Institute of Materials, University
2Department of Materials & Ceramic Engineering, CICECO – Aveiro Institute
of Materials, University of Aveiro, 3810-193 Aveiro, Portugal
3Department of Chemistry, University of Zürich, CH-8057 Zürich, Switzerland
E-mail: rfmendes@ ua.pt
Metal-Organic Frameworks (MOFs) and/or Coordination Polymers (CPs) are
highly ordered crystalline compounds based on the self-assembly of metal
centers (transitional transition metal cations or lanthanides) with a variety of
organic linkers. This research area is currently driven by the need to employ
these materials in important technological areas for society by taking advantage
of the high versatility of these networks.[1,2]
In this work a typical one-pot approach using water as a “green” solvent allowed
the preparation of the first reported phosphonate-based MOF having positively
charged 2D layers, [Gd(H4nmp)(H2O)2]Cl·2H2O (1), counterbalanced by forcing
the inclusion of additional acid sites by employing HCl in the synthesis.
Compound 1performs as a heterogeneous, versatile acid catalyst, with
outstanding activity in different organic reactions, namely, the alcoholysis of
styrene oxide, acetalisation of benzaldehyde and ofcyclohexanaldehyde, and
ketalisation of cyclohexanone. For all reaction systems, very high conversions
were reached (92-97%) in only 15-30 min, under mild conditions (35 ºC,
atmospheric pressure)[3].
[1] H.-C. Zhou, S. Kitagawa, Chemical Society Reviews 2014, 43, 5415
[2] P. Silva, S. Vilela, J. P. C. Tomé, F. A. A. Paz, Chemical Society Reviews
2015, 44, 6774
[3] R. F. Mendes, M. M. Antunes, P.Silva, P. Barbosa, F. Figueiredo,A.
Linden,J. Rocha,A. A. Valente, F. A. A. Paz, Chemistry – A European
Journal 2016, Submitted
118
VERTICALLY ALIGNED CARBON NANOTUBES-SUPPORTED
MANGANESE OXIDE NANOCOMPOSITES AS BINDER-FREE
ELECTRODES FOR ELECTROCHEMICAL CAPACITORS
Ricardo M. Silva1,2, Nicola Pinna2, Rui F. Silva1
1
2
Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2,
12489 Berlin, Germany
Carbon nanotubes (CNTs) present a high surface area and exceptional
physical properties. As matter of fact, they are ideally suited as support for a
secondary material that can be deposited onto their surface either as particles
or as a thin film. CNTs can be synthesized by various methods but only catalytic
thermal chemical vapor deposition (TCVD) has been shown to directly grow
dense aligned CNTs (VACNTs) on metallic current collectors. This strategy
enables the elaboration of binder-free electrodes and the formation of robust
CNT-metal contacts during the growth [1]. In this particular case, the internal
resistance is reduced enough because both ion and electron conductive paths
are simplified due to the vertical alignment of the nanotubes on the current
collector.
Atomic layer deposition (ALD) technique emerges as a powerful and versatile
technique for the coating or decoration of the CNTs with metal oxides [2]. In the
present work, it is highlighted the versatility of ALD approach for the precise
coating of carbon nanotubes. The process was successfully applied to the
conformal and homogeneous coating of VACNTs surface with thin films of ALD
manganese oxide, preserving the support geometry. As a proof of concept, the
capacitive behavior of the coated VACNTs arrays coupled to the metallic
substrate as the active electrode material and the current collector,
respectively, in supercapacitors is demonstrated.
[1] R.M. Silva, A.C. Bastos, F.J. Oliveira, D.E. Conte, Y. Fan, N. Pinna, R.F.
Silva, J. Mater. Chem. A 2015, 3, 17804-10.
[2] C. Marichy, N. Pinna, Coord. Chem. Rev. 2013, 257, 121301-57.
119
ZIRCONIA BASED CERMETS: ELECTRICAL, MAGNETIC AND THERMAL
CHARACTERIZATION
Ricardo Serrazina1 , Nuno Neves2, Rosa Calinas2 , Venkata Ramana E.2, Ana
Senos1, Paula M. Vilarinho1
1Department
of Materials and Ceramics Engineering, CICECO – Aveiro
Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal
2INNOVNANO,
3
Coimbra, Portugal
I3N-Aveiro, Department of Physics, University of Aveiro, Aveiro 3810-193,
Portugal.
In this work the electrical, magnetic and thermal characteristics of yttria
stabilized zirconia (YSZ) powders and of YSZ-metal cermet powders were
investigated.
Composites using the dispersion of nano-scaled second phase particles in a
ceramic based matrix show improved mechanical properties. [1] Additionally,
they offer the possibility to engineer other functional properties, such as
thermal, electrical and magnetic response, requested for the development of
new multifunctional materials. [2], [3]
Within a collaboration between the Company INNOVNANO and the University
of Aveiro, composite powders of YSZ and a metallic alloy up to 20 mol% have
been prepared by Mechanosynthesis. [4], [5] The milling was performed in a
high energy planetary mill, using a steel bowl and YSZ balls under controlled
atmosphere (Argon, 2 bar), at 350 rpm, for 2h. Sintered bodies were also
produced in a vacuum furnace (approximately at 20 Pa) at 1400 ˚C.
The structure and the microstructure of the powders were characterized by Xray diffraction (XRD), Raman spectroscopy and Scanning electron microscopy
(SEM). The magnetic response of the produced powders and ceramics was
studied by Vibrating sample magnetometer (VSM) technique. Impedance
spectroscopy and a thermal conductance tester (transient mode) were used to
assess the electrical and thermal behavior of the composites. The relations
between the amount of alloy, phase structure and physical properties of the
cermets are established.
[1]
H. Kondo, T. Sekino, N. Tanaka, T. Nakayama, T. Kusunose, and K. Niihara,
J. Am. Ceram. Soc., 2005, vol. 88, no. 6, pp. 1468–1473.
[2]
J. T. Abiade, G. X. Miao, A. Gupta, A. A. Gapud, and D. Kumar,Thin Solid
Films, 2008 vol. 516, no. 8, pp. 2082–2086.
[3]
A. Morrissey, J. Tong, B. P. Gorman, and I. E. Reimanis, J. Am. Ceram. Soc.,
2014, vol. 97, no. 4, pp. 1041–1047.
[4]
[5]
J. B. Puga, University of Aveiro, 2014.
K. Wieczorek-Ciurowa, D. Oleszak, and K. Gamrat, J. Alloys Compd., 2007
vol. 434–435, no. SPEC. ISS., pp. 501–504.
120
SHORT CHAIN FATTY ACIDS PRODUCTION THROUGH MIXED
MICROBIAL CULTURES ECO-ENGINEERING
Rita Sousa1, D. Queirós1, J. Pereira1, A. Xavier1, L. S. Serafim1
1CICECO
– Aveiro Institute of Materials, University of Aveiro, Chemistry
The excessively use of non-renewable resources causes the rise of
costs of energy and commodities and also the release of high amounts of
carbon dioxide. The introduction of more sustainable processes using
renewable resources, such as biomass, is of major interest. Due to its
abundance, low cost and broad availability, lignocellulosic biomass is a
promising substrate for the production of chemicals and energy, among others.
Biorefineries are industries analogous to the conventional refineries that aspire
to replace them in the near future, using biomass as raw material and also
microbial processes for the conversion of substrates into value-added products.
The Portuguese pulp and paper industry is a sector that experienced
rapid expansion and growth in the past decades and nowadays present a
significant impact on the national economy. It integrates the sulphite pulping
process which generates large amounts of hardwood sulphite spent liquors
(HSSL) as byproducts that are usually burned for energy/chemicals recovery.
However, due to its large amounts of sugars (40 – 60 g.L-1), HSSL can
constitute a base for many value-added products, such as short-chain organic
acids (SCOAs), the main objective of this work. SCOAs present a great
potential not only due to their wide applicability, with a special focus on
biopolymers, but also due to the fact that they can be produced biologically
through acidogenic fermentation from renewable resources, such as
lignocellulosic biomass. The optimization and control of this process is crucial
and comprises the monitoring of parameters such as temperature, pH, organic
loading rate and sludge and hydraulic retention times. Furthermore, the origin
of the inoculum and the choice of reactor type are also critical parameters to
consider. In this work two complete stirred tank reactors (CSTR), with and
without pH control, were operated in order to evaluate the effect of this
parameter not only on the concentration of SCOA but also in the SCOA profiles
obtained.
121
HIGH BUFFER CAPACITY WASTE-CONTAINING GEOPOLYMERS TO
ENHANCE BIOGAS PRODUCTION
Rui M. Novais1, L.H. Buruberri1, M.P. Seabra1, D. Bajare2, J.A. Labrincha1
1Departement
of Materials and Ceramic Engineering/CICECO – Aveiro
Institute of Materials, University of Aveiro, Campus Universitário de Santiago,
2
Institute of Materials and Structures, Riga Technical University, Latvia
Keywords: lightweight geopolymer; biomass fly ash; buffer capacity
The production of energy using biogas technology has attracted increased
attention being an alternative to conventional fossil fuels [1]. The anaerobic
digestion in bioreactors is highly dependent of the pH value [2] which needs to
be strictly controlled. pH adjustment is often required to enhance the methane
gas yield. For this purpose commercial alkaline materials, such as lime and
sodium hydroxide, have been employed. Geopolymers with high buffer capacity
could provide prolonged pH adjustment and may be an effective alternative to
commercial alkaline materials.
In this work, innovative porous waste-containing geopolymers were developed
[3] by using hydrogen peroxide as blowing agent. Afterwards the potential of
these geopolymers as pH buffering materials was studied. The influence of
porosity and solid/liquid ratio on the geopolymers leaching rate and on the
geopolymer physical properties was evaluated. The high buffer capacity and
tailored alkalis leaching [4] shown by these innovative materials demonstrates
their potential as pH buffering material in several applications such as in
bioreactors.
[1] G. Bumanis, D. Bajare. 2014. The effect of porous alkali activated material
composition on buffer capacity in bioreactors. International Journal of
Chemical, Nuclear, Metallurgical and Materials Engineering, 2014, 8, 10401046.
[2] G. Bumanis, D. Bajare, K. Rugele. The effect of alkaline material particle
size on adjustment ability of buffer capacity. Medziagotyra, 2015, 21, 405-409.
[3] R.M. Novais, L.H. Buruberri, G. Ascensão, M.P. Seabra, J.A. Labrincha.
Porous biomass fly ash-based geopolymers with tailored thermal conductivity.
Journal of Cleaner Production, 2016, 119, 99-107.
[4] R.M. Novais, L.H. Buruberri, M.P. Seabra, D. Bajare, J.A. Labrincha.
Novel porous fly ash-containing geopolymers for pH buffering applications.
Journal of Cleaner Production, 2016, 124, 395-404.
122
HYBRID CONJUGATES OF CORROLE AND Fe3O4@SiO2
NANOPARTICLES FOR PHOTODYNAMIC THERAPY
Rute A. Pereira1, Joana F. B. Barata1,2, Tito Trindade1
1
Department of Chemistry & CICECO – Aveiro Institute of Materials, University of
Aveiro, Aveiro, Portugal
2
Department of Chemistry & QOPNA, University of Aveiro, Aveiro, Portugal
Photodynamic Therapy (PDT) is a cancer treatment that has been extensively
studied and used, due to its proved efficiency in several tumors, namely of the
skin and esophageal. This method involves three main agents – a
photosensitizer, light and oxygen – where the photosensitizing molecules after
light irradiation are the generating agents of reactive oxygen species, such as
singlet oxygen – which causes oxidative damage, leading to the death of cancer
cells [1]. Tetrapyrrolic macrocycles, such as porphyrinoids, have been top
choices to be used as photosensitizers due to their intrinsic photochemical
properties, although less investigated, as compared to porphyrins. The use of
corroles (tetrapyrrolic macrocycles) as photosensitizers, have been recently
evaluated towards cancer cells [2]. Considering the huge interest to develop
new photosensitizers conjugates with intrinsic advantages, the combination of
corroles with magnetic nanoparticles opens the way to explore new
functionalities in PDT. For instance, the magnetic guiding of the photosensitizer
hybrid to cancer cell targets, hence enhancing locally the photodynamic effect,
or the possibility to complement with other therapeutic strategies such as
hyperthermia [3].
In this communication, we report the synthesis and characterization of the first
example of a hybrid conjugate composed of corrole molecules and
Fe3O4@SiO2 nanoparticles. These nanoparticles have been obtained by
chemical grafting og Ga(III) 5,10,15-tris(pentafluorophenyl)corrole complex
onto the surfaces of previously prepared Fe3O4@SiO2 colloidal nanoparticles.
Finally, the optical properties of the new materials will be presented and the
results will be discussed in the context of their application as photosensitizers
in PDT.
Acknowledgements: The authors wish to thank to FCT and POPH/FSE for the
postdoctoral grants to J. F.B. Barata (SFRH/BPD/63237/2009), This work was
developed within the scope of the project CICECO – Aveiro Institute of Materials,
POCI-01-0145-FEDER-007679 (FCT Ref. UID /CTM /50011/2013), and QOPNA
research Unit (FCT UID/QUI/00062/2013), financed by national funds through the
FCT/MEC and when appropriate co-financed by FEDER under the PT2020
Partnership Agreement
[1] M. Thandu, V. Rapozzi, L. Xodo, F. Albericio, C. Comuzzi, and S. Cavalli,
Chempluschem 2014, vol. 79, pp. 90-98.
[2] J. F. B. Barata, A. Zamarrón, M. G. P. M. S. Neves, M. A. F. Faustino, A.
C. Tomé, J. a S. Cavaleiro, B. Röder, Á. Juarranz, F. Sanz-Rodríguez, Eur. J.
Med. Chem. 2015, vol. 92, pp. 135-44.
[3] T. Nann, Nano Biomed. Eng. 2011, vol. 3, pp. 137-143.
123
CORK-POLYMER COMPOSITES FOR INJECTION MOULDING
APPLICATIONS
S. P. Magalhães da Silva1,2, P. S. Lima1, J. M. Oliveira1,2
1 Escola
2 Aveiro
Superior Aveiro Norte, Universidade de Aveiro
Institute of Materials (CICECO), Universidade de Aveiro Email: sarapms@ ua.pt
The demanding of new materials derived from renewable resources has been
increasing, mostly due to environmental concerns and waste accumulation
driven by the restrictive measures imposed by the European Commission.
Nowadays, there is a need for more innovative, sustainable and recyclable
materials, combined with an increase market demand for products with lower
ecological footprint.
Lignocellulosic materials’ incorporation in synthetic polymers has become an
effective approach to develop new sustainable materials [1]. Cork is a wellrecognized Portuguese raw material and product. Cork is the outer bark of oak
tree Quercus suber
L., which regenerates in every 9-10 years. The main chemically component is
suberin (33-50%), followed by lignin (20-25%); the carbohydrate fraction is
composed by cellulose and hemicelluloses (12-20%); extractives represent
nearly 14-18% and ≈1% are ashes [2]. Cork possesses an unique combination
of properties, more specifically, low density, elasticity and compressibility
(without lateral expansion), high recovery capacity after impact, impermeability
to liquids and gases, excellent thermal and acoustic insulation and, microbial
and fire resistance [2].
The present study is part of a larger project that focuses on the research of
corkpolymer composites (CPC) for injection moulding applications. One of the
problems on CPC formulation is the lack of compatibility between cork (polar
material) and the polymeric matrix (non-polar material). In this particular study,
it will be analysed the adhesion of cork particles on a polypropylene (PP) matrix
through the employment of a coupling agent based on maleic anhydride –
polypropylene grafted maleic anhydride (PPgMA). Cork particles used present
an average size distribution of 70 µm and 15% wt were added to the PP matrix.
For the formulation of the compatibilized CPC 5% of PPgMA was added.
Mechanical, thermal and morphological analyses were performed to assess the
compatibility between cork particles and PP.
All the different analyses revealed that the addition of PPgMA resulted in the
interfacial adhesion of cork particles to PP matrix. This study showed that
industrial cork residues with low ganulometry can be considered for the
sustainable development of CPC.
[1]
M. N. Belgacem, A. Gandini, Amsterdam, Elsevier. 2008;
[2]
H. Pereira, Amsterdam, Elsevier. 2007;
124
ELECTROCHEMICAL PERFORMANCE OF CERIA-BASED
(NANO)COMPOSITE ELECTROLYTES
S.G. Patrício, A.I.B. Rondão, F.M.B. Marques
Department of Materials and Ceramic Engineering/CICECO, University of Aveiro,
Aveiro, 3810-193, Portugal
Composite electrolytes based on doped-ceria oxide-ion conductors and
alkaline carbonates (typically sodium and lithium) are currently in the forefront
of sustainable energy conversion and environmental applications because of
their multi-ionic conducting behavior [1]. As such, the underlying dual-ionic
transport makes these composite materials potential candidates for CO2
separation membranes, while proton conduction can be targeted for ammonia
synthesis or low-intermediate temperature fuel cells [2,3].
Previous works pointed out that the interface between ceramic oxide and
carbonate phase improves the interaction of both constituents and also provide
a highway channel for ionic conductivity. This is specially expected for protons
since the conduction mechanism presumably occurs along the oxide particle
surfaces and interfaces between constituent phases [4].
In this sense, the design of nanocomposite electrolytes should increase the role
of protons on the fuel cell electrochemical performance, but this so called
“nanocomposite effect” is still controversial.
In this work, ceria-based composite electrolytes were prepared from powders
with ceramic particle size varying from the micrometric (< 5µm) to the
nanometric (< 25 nm) scale. Sintering conditions were optimized in order to
produce dense composite electrolytes with similar phase content.
The influence of the total interfacial area contribution to the conductivity was
firstly evaluated by impedance spectroscopy in dry and wet diluted hydrogen,
within the 250 to 650 ºC temperature range. Afterwards, fuel cell standard V
(voltage) versus I (current) curves were obtained over the temperature range
of 550 to 650 ºC, with diluted hydrogen and air supplied to the cell anode and
cathode sides, respectively. These results provided further insights of the
ceramic particle size effect on the fuel cell performance.
[1]
L. Fan, C. Wang, M. Chen,B. Zhu, J. Power Sources 2013, 234, 154.
[2]
J. Wang, Z. Mao, L. Yang, R. Pen, Electrochem. St. 2005, 8, A437.
[3]
S.G. Patrício, E. Papaioannou, G. Zhang, I. S.Metcalfe, F.M.B. Marques,
J. Membr. Sci. 2014, 471, 211.
[4]
Q.Liu, B. Zhu, Appl. Phys. Lett. 2010, 97, 183115.
125
ORGANIC-INORGANIC HYBRIDS FOR LUMINESCENT SOLAR
CONCENTRATORS
Sandra F. H. Correia1,2, A. R. Frias1,2, R. Rondão1, V. T. Freitas1,3, P. S.
André4, R. A. S. Ferreira1, L. D. Carlos1
1
Department of Physics and CICECO - Aveiro Institute of Materials, University of
Aveiro, 3810-193 Aveiro, Portugal;
2
Instituto de Telecomunicações, University of Aveiro, 3810-193, Aveiro, Portugal;
3
Laboratoire Charles Coulomb (L2C), UMR 5521 CNRS-Université de Montpellier,
34095 Montpellier, France
4
Department of Electric and Computer Engineering and Instituto de
Telecomunicações, Instituto Superior Técnico, Universidade de Lisboa, Lisbon,
Portugal.
E-mail: [email protected]; [email protected]; [email protected]; [email protected];
Nowadays, despite the recent developments of PV systems, the conversion of solar
energy into electricity through PV cells is still not efficient enough and market
competitive, remaining an obstacle for their large-scale dissemination. One of the
major factors limiting the efficiency of the Si-based cells is the mismatch between the
solar spectrum and the Si response curve.
The concept of luminescent solar concentrator (LSC) appeared as an effective
approach towards economically collecting sunlight without additional sun trackers with
potential to overcome the limiting factors of PV conversion efficiency. LSCs consist of
a layer containing optically active centers deposited on a transparent substrate, that,
when exposed to light, converts part of the absorbing radiation into a specific emitting
wavelength that is guided through total internal reflection to PV cells located at the
edges of the substrate.
The geometry of the LSCs is an important parameter, since it will account for the
geometrical gain and, consequently, for its overall performance. During the last few
years, our group produced planar [1] and cylindrical [2,3] LSCs, whose optically active
layers are based on organic-inorganic hybrids doped with Eu3+ complexes and organic
dyes (Rhodamine 6G, Rhodamine 800 and silicon 2,3-naphthalocyanine
bis(trihexylsilyloxide)) with distinct absorption and emission ranges, from UV to NIR.
Concerning cylindrical LSCs, short (centimeters) [2] and long length [3] (meters)
devices based on plastic optical fibers (POFs) were produced, in order to test the
possibility of increasing the LSC concentration factor. These ones were produced in
bulk-coated and hollow-core configurations, in which the optically active layer is,
respectively, on the outside of the POF, as a coating, or inserted in the hollow-core of
the POF, for an enhanced mechanical and atmospheric protection, with
unprecedented optical conversion efficiency values. Our optimized device showed an
optical conversion efficiency of 72.4% and a concentration factor of F=12.3, larger than
the higher value reported so far for large-area LSCs (F=4.4) [4].
[1]
V. T. Freitas, et al., ACS Appl. Mater. Inter. 2015, 7, 8770.
[2]
S. F. H. Correia, et al., Sol. Energ. Mat. Sol. C. 2015, 138, 51.
[3]
S. F. H. Correia, et al., Prog. Photovolt.: Res. Appl. 2016.
DOI:10.1002/pip.2772
[4]
F. Meinardi, et al., Nat. Photonics 2014, 8, 392.
126
ALKALI NIOBATE AND TANTALATE PEROVSKITES. ESTABLISHING
PHOTOCATALYTIC ACTIVITY
Sebastian Zlotnik, David M. Tobaldi, M. Paula Seabra, João A. Labrincha and
Paula M. Vilarinho
CICECO–Aveiro Institute of Materials, Department of Materials and Ceramic
E-mail: sebastian.zlotnik@ ua.pt
Lead-free ternary oxides with perovskite structure are functional materials with
versatile properties, such as piezoelectricity, ferroelectricity, ferromagnetism,
etc. Therefore, they can be used in numerous applications, e.g.
microelectronics (dielectrics, ferroelectrics and electro-optic waveguides),
energy harvesting (piezoelectrics and thermoelectrics), and photocatalysis in
water splitting or pollutant degradation [1]. Lately, heterogeneous
photocatalysis based on semiconductor oxides has been considered as an
emerging green technology for environmental remediation using photochemical
processes to eliminate organic compounds. Among those compounds, the
alkali tantalates and niobates are listed as important photocatalysts for the
development of renewable energy technologies and environmental
remediation. Their good photo-physical properties originate from crystal
structure, a three dimensional framework made up of TaO6 or NbO6 octahedra,
and band structure, with the bottom level of conduction bands consisting of Ta
5d or Nb 4d orbitals located at a more negative state of redox potential of H+/H2
than TiO2 (Ti 3d). These features ensure to promote the separation of charge
carriers due to proper light irradiation, and allow an easy migration and
separation of the photogenerated electron-holes [2].
Within this context, a comparative study of the photocatalytic degradation of
methylene blue dye in an aqueous solution using well-crystalline particles with
perovskite-like structures, LiTaO3, LiNbO3, NaTaO3, NaNbO3, KNbO3 and
KTaO3 was investigated. It is demonstrated that ferroelectric KNbO3 is the most
efficient photocatalyst among the tested ones (>50 %), because it combines an
electronic band structure, which can respond successfully to the UVA-light with
a relatively high surface energy that enhances catalytic properties. Additionally,
the build-in electric field due to internal polarisation of a ferroelectric may
contribute to the unique properties of this functional photocatalyst. This work
provides an ideal platform for a rational design of more efficient ferroelectric
based photocatalytic devices [3].
[1]
A. Kudo, Y. Miseki, Cem. Soc. Rev. 2009, 38, 253.
[2]
P. Zhang, J. Zhang, J. Gong, Chem. Soc. Rev. 2014, 43, 4395.
[3]
S. Zlotnik, D. M. Tobaldi, M. P. Seabra, J. A. Labrincha, P. M. Vilarinho,
ChemPhysChem 2016 (submitted).
127
ROLE OF STRAINS ON THE STRUCTURAL, MICROSTRUCTURAL AND
ELECTRICAL BEHAVIOUR OF LEAD-FREE SODIUM POTASSIUM
NIOBATE THIN-FILMS
Siriny Laumier1,2, Sebastian Zlotnik1, Pedro L. Marques1, André Santos1,
Jean-René Duclere2, M. Elisabete Costa1, Paula M. Vilarinho1
1CICECO–Aveiro
Institute of Materials, Department of Materials and Ceramic
2SPCTS,
Centre Européen de la Céramique, 12 rue Atlantis, 87068 Limoges
Cedex, France
E-Mail: [email protected]
Materials that respond in a controlled manner to external stimulus are currently very
important. There are different types of Smart Materials that include thermoelectrics,
magnetocaloric, shape memory alloys and piezoelectrics, among others.
Piezoelectrics with the ability to transform electrical signals into a mechanical response
and vice versa are the basis of important products as sensors, actuators, motors,
transducers, for industrial and manufacturing, automotive, medical, information and
communication applications. The market for piezoelectric devices is expected to reach
USD 27.24 Billion by 2020, growing 6.01% between 2015 and 2020
(marketsandmarkets.com). High precision micro-positioning, medical and high-speed
communication devices are the main drivers for this market growth.
In terms of piezoelectric materials, the leading compositions are lead based
perovskites, as Pb(Zr, Ti)O3 (PZT), due to their excellent electromechanical properties
[1]. However, the presence of lead is currently a limitation related to the high toxicity of
lead [2]. In the search for alternative lead free piezoelectrics sodium potassium
niobate, (K, Na)NbO3 (KNN) because of its high Curie temperature (420°C) and high
piezoelectric coefficient is a promising candidate [3]. For miniaturised microelectronic
applications KNN thin films might be needed and efforts have been made to fabricate
KNN thin films, through various techniques. Among them RF magnetron sputtering
through the control of the deposition parameters, e.g. atmosphere, pressure, substrate
temperature, among others, permits the growth of epitaxial and columnar films with a
reasonable control of the composition stoichiometry. It is also well known for different
ferroelectrics based perovskites that strains caused by the substrate underneath thin
films may affect markedly the structure, microstructure and properties.
Within this context, we are conducting a systematic study about the effect of strain on
the structural, microstructural and electromechanical behaviour of lead-free
K0,5Na0,5NbO3 (KNN) thin films. Distinct substrates have been selected, such as silicon,
stainless steel and alumina to control the strain level. The films are being deposited by
RF magnetron sputtering using a stoichiometric ceramic target, and then crystallized
via Rapid Thermal Processing (RTP) at 700°C for 10 min in O2. Subsequently,
structure, electrical, and strain analysis are conducted to understand and improve
piezoelectric properties of KNN thin films.
[1] Y. Feng, W. L. Li, D. Xu, W. P. Cao, Y. Yu, W. D. Fei, RSC Adv. 2016, 6, 36118.
[2] Directive 2002/95/EC of the European Parliament and of the Council of 27 January
2003 on the restriction of the use of certain hazardous substances in electrical and
electronic equipment. EC, 2003.
[3] G. Shirane, PHYSICAL REVIEW, 1954, 96, 581
128
BIOPOLYMER-SILICA HYBRID PARTICLES PREPARED BY A NONEMULSION METHOD FOR ENVIRONMENTAL APPLICATIONS
Sofia F. Soares1, Tito Trindade1, Ana L. Daniel-da-Silva1
1
Silica based hybrid materials merge the properties of organic and inorganic
components to provide improved properties such as better mechanical
properties and higher thermal decomposition temperatures. The development
of silica hybrid materials derived of polysaccharides has experienced
remarkable growth due to attractive properties of polysaccharides such as
biocompatibility, biodegradability, low cost and availability [1].
This research aimed to develop novel organic-inorganic hybrid nanomaterials
derived from polysaccharides extracted from renewal resources. The method
developed allows preparing biopolymer-silica hybrids in the form of uniform
spherical particles with submicrometer size, without using surfactants. Herein,
we report a non-emulsion method for preparing biopolymer-silica hybrid
particles from a number of polysaccharides. The biopolymer was reacted with
the alkoxysilane 3-isocyanatopropyltriethoxysilane (ICPTES) and the resulting
compound was mixed with a silica precursor (tetraethyl orthosilicate, TEOS) to
yield uniform spherical hybrid particles via a sol-gel method (Figure 1) [2]. This
method also allows to coat magnetic nanoparticles with a thin shell with hybrid
composition comprising a biopolymer covalently bonded to the silica network,
imparting new properties to hybrid materials. The resulting materials were
extensively characterized using electron microscopy (TEM, SEM), solid state
NMR, FTIR spectroscopy and elemental analysis. Results on the application of
these materials as nano-adsorbents for the efficient removal of emerging
chemical pollutants from water will be also presented.
Figure 1 Scheme of the reactions involved in the synthesis of biopolymer-siliceous
hybrid particles.
[1]
[2]
E. Ruiz-Hitzky, P. Aranda, M. Darder, M. Ogawa, Chemical Society
Reviews 2011, 40, 801–28.
S. F. Soares, T. Trindade, A. L. Daniel-da-Silva, European Journal of
Inorganic Chemistry 2015, 27, 4588–4594.
129
CATALYTIC ALCOHOLYSIS OF EPOXIDES USING METAL-FREE
CUCURBITURIL-BASED SOLIDS
Sofia M. Bruno1, Ana C. Gomes1, Tânia S. M. Oliveira2, Margarida M.
Antunes1, André D. Lopes2, Anabela A. Valente1, Isabel S. Gonçalves1,
Martyn Pillinger1
1Department
of Chemistry, CICECO – Aveiro Institute of Materials, University
of Aveiro. 2 Faculty of Science and Technology, CIQA, University of the
Algarve.
Cucurbit[n]urils (CBn, n = 5–8, 10, 14) are a family of macrocyclic compounds,
that can be readily prepared on a large scale by one-pot synthesis from cheap
starting materials, glycoluril and formaldehyde [1]. The unique properties of
CBs, notably their rigid structure, two highly polar carbonyl-lined portals, a
hydrophobic non-polarisable inner cavity, and high binding affinities, have
prompted numerous studies within the fields of host–guest chemistry,
supramolecular catalysis, drug delivery, molecular machines and electronics,
amongst others. Catalytic applications are still waiting to be extensively
explored [2].
We report the use of cucurbit[7]uril (CB7) in the alcoholysis of aliphatic and
aromatic epoxides under mild conditions to give β-alkoxy alcohols, which are
important intermediates for the synthesis of a vast range of compounds such
as bioactive pharmaceuticals [2]. The catalytic process is heterogeneous and
the catalyst can be reused in consecutive runs without any reactivation
treatment. To date, only a few examples of metal-free heterogeneous acid
catalysts have been investigated for the alcoholysis of epoxides, e.g. graphene
oxide, mesoporous carbon, and the commercial ion-exchange resin
Amberlyst™-15 [3].
[1]
K. I. Assaf, W. M. Nau, Chem. Soc. Rev. 2015, 44, 394.
[2] S. M. Bruno, A. C. Gomes, T. S. M. Oliveira, M. M. Antunes, A. D. Lopes, A. A.
Valente, I, S. Gonçalves, M. Pillinger, Org. Biomol. Chem. 2016, 14, 3873.
[3] (a) A. Dhakshinamoorthy, M. Alvaro, P. Concepción, V. Fornésand, H. Garcia,
Chem. Commun. 2012, 48, 5443. (b) I. Matos, P. D. Neves, J. E. Castanheiro, E.
Perez- Mayoral, R. Martin-Aranda, C. Duran-Valle, J. Vital, A. M. Botelho do Rego, I.
M. Fonseca, Appl. Catal., A 2012, 439–440, 24.
(c) Y.-H. Liu, Q.-S. Liu, Z.-H.
Zhang, J. Mol. Catal. A: Chem. 2008, 296, 42.
130
CHOLINIUM SALTS WITH INCREASED WATER-SOLUBILITY AND
ANTIOXIDANT PROPERTIES
Tânia E. Sintra1, Samuel N. Rocha1, Andreia Luís1, Ana I.M.C. Lobo Ferreira2,
Fernando Gonçalves3, Luis M. N. B. F. Santos2, Bruno Miguel Neves4,5, Sónia
P. M. Ventura1, Mara G. Freire1, João A. P. Coutinho1
1
2
Chemical Research Center, Department of Chemistry and Biochemistry, Faculty of
Science, University of Porto, 4169-007 Porto, Portugal
3
4
Department of Biology, CESAM, University of Aveiro, 3810-193 Aveiro, Portugal
5
CNC, University of Coimbra, 3004-504 Coimbra, Portugal
Although there is an increasing interest on antioxidants, some of them present a
solubility limitation in aqueous media and related pharmaceutical/cosmetic
formulations [1-2]. In this context, cholinium-based salts appear as promising
candidates if based in compounds with antioxidant characteristics aiming at enhancing
their water solubility. In this work, five new cholinium-based salts with antioxidant
nature were synthetized. Their antioxidant activity was investigated using the 2,2diphenyl-2-picrylhydrazyl hydrate (DPPH) radical scavenging assay. Moreover, their
physicochemical properties, namely melting point, temperature of decomposition and
water solubility were experimentally assessed, as well as their ecotoxicological impact
toward the luminescent marine bacteria Vibrio fischeri. Finally, the impact of the
synthesized salts on mammalian cells was addressed, in which their cytotoxicity and
pro/anti-inflammatory activity were analyzed in relevant human cell lines. The data
obtained reveal that these new cholinium-based salts present not only similar or even
higher antioxidant and anti-inflammatory activities, as well as comparable cytotoxicity
and lower ecotoxicity profiles than their respective acidic precursors. Furthermore, the
synthesized compounds are significantly more soluble in water (on average, 3 orders
of magnitude higher) than the corresponding acids [3]. Since all synthesized
compounds are based on the cholinium cation, they can also be foreseen as essential
nutrients for use in dermatological formulations and oral drugs.
[1] S. Briganti, M. Picardo, J. Eur. Acad. Dermatol. Venereol. 2003, 17, 663.
[2] J. Dai, R.J. Mumper, Molecules 2010, 15, 7313.
[3] T.E. Sintra, A. Luís, S.N. Rocha, A.I.M.C. Lobo Ferreira, F. Gonçalves, L.M.N.B.F.
Santos, B.M. Neves, S.P.M. Ventura, M.G. Freire, J.A.P. Coutinho, ACS Sustainable
Chem. Eng. 2015, 3, 2558.
Acknowledgements: This work was developed within the scope of the project CICECO - Aveiro
Institute of Materials POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM/50011/2013),
financed by national funds through the FCT/MEC and when appropriate, co-financed by FEDER
under the PT2020 Partnership Agreement. Thanks are due, for the financial support, to CESAM
(UID/AMB/50017), to FCT/MEC through national funds, and the co-funding by the FEDER,
within the PT2020 Partnership Agreement and Compete 2020. The authors are grateful for
financial support through FCT for the doctoral and post-doctoral grants SFRH/BD/85871/2012
and SFRH/BPD/79263/2011 of T.E. Sintra and S. P. M. Ventura, respectively. M. G. Freire
acknowledges the European Research Council (ERC) for the Starting Grant ERC 2013-StG337753.
131
METAL OXIDE-TRIAZOLE HYBRIDS AS HETEROGENEOUS OR
REACTION-INDUCED SELF-SEPARATING CATALYSTS
Tatiana R. Amarante1, Patrícia Neves1, Anabela A. Valente1, Filipe A.
Almeida Paz1, Martyn Pillinger1, Isabel S. Gonçalves1
1
Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal
An important goal in transition metal catalysis science is the development of
systems that combine the advantages of homogeneous catalysts with those of
heterogeneous catalysts [1]. The principal approach to solving this problem has been
the immobilization of molecular catalysts onto organic, inorganic or hybrid organicinorganic supports [2]. In the period 2001-2003 two papers reported on a new
approach involving catalyst self-separation or self-precipitation. The first report, by Xi
et al., described reaction-controlled phase-transfer catalysis for propylene oxidation to
propylene oxide [3]. Exhaustion of the oxidant led to spontaneous precipitation of the
catalyst that could be recovered and used again. The second approach, developed by
Dioumaev and Bullock, consisted of alternative solid-liquid-solid phase separation that
relied on the differences in solubility of the catalyst in the liquid substrate and
product [4]. Since the publication of these two landmark papers, progress on selfprecipitating transition metal catalysts has been slow.
In the present work, we describe a new type of self-separating catalyst based
on a molybdenum oxide hybrid material. The material [MoO3(trz)0.5] (trz = 1,2,4triazole), which was first reported by Zubieta and co-workers [5], was chosen for study
as part of our ongoing investigations into the catalytic properties of Mo(VI) and W(VI)
oxide-organonitrogen hybrid materials [6]. We know that depending on the structure
and composition of these hybrids, as well as the catalytic reaction conditions, the
materials typically act either as sources of soluble active species or (more rarely) as
heterogeneous catalysts. In a manner similar to that reported with a polyoxometalate
salt in ref. 3, a solid-liquid-solid phase transfer takes place, with spontaneous
reassembly and self-precipitation of the original molybdenum oxide-triazole solid upon
completion of the reaction. Results with Mo(VI) hybrid are compared with those for the
corresponding W(VI) compound, and the catalytic performances of both materials have
been further examined for the oxidation of benzyl alcohol and benzaldehyde.
[1] J. A. Gladysz, Chem. Rev. 2002, 102, 3215; [2] S. Shylesh, et al., Eur. J.
Inorg. Chem. 2010, 4395. [3] Z. Xi, et al., Science, 2001, 292, 1139. [4] V. K.
Dioumaev, et al., Nature 2003, 424, 530. [5] P. J. Hagrman, et al., Inorg. Chem.
2000, 39, 4311. [6] T.R. Amarante, et al., Inorg. Chem, 2015, 54, 9690.
Acknowledgements to FEDER through COMPETE. To FCT through the projects:
FCOMP-01-0124-FEDER-029779 (ref. PTDC/QEQ-SUP/1906/2012) and FCOMP-010124-FEDER-041282 (ref. EXPL/CTM-NAN/0013/2013). To CICECO (FCT ref. UID/
CTM/50011/2013) financed by national funds through the FCT/MEC and co-financed
by FEDER under the PT2020. Thanks to FCT and the EU for the postdoc grants to
P.N. (SFRH/BPD/73540/2010) and T.R.A. (SFRH/BPD/97660/2013) co-funded by
MCTES and the European Social Fund through the program POPH of QREN. Thanks
to the ESRF (Grenoble, France) for approving the experiment CH-4254 (ID22).
132
AN ALTERNATIVE EXTRACTION/CONCENTRATION APPROACH FOR
AN IMPROVED DETECTION OF WATER POLLUTION TRACERS
Teresa B. V. Dinis1, Helena Passos1, Diana L. D. Lima2,3, Valdemar I.
Esteves2, João A. P. Coutinho1, Mara G. Freire1
1
2
Chemistry Department, CESAM, University of Aveiro, 3810-193 Aveiro, Portugal
3
Instituto Politécnico de Coimbra, ESTESC-Coimbra Health School, Complementary
Sciences, Rua 5 de Outubro, S. Martinho do Bispo, 3046-854 Coimbra, Portugal
The synthetic hormone 17α-ethinylestradiol (EE2) is classified as a priority
substance with a significant risk to or via aquatic environments [1]. EE2 displays
the most potent estrogenic activity amongst the estrogens currently existent,
being thus a prominent endocrine disruptor in water cycles. However, due to
the low content of EE2 in wastewaters (usually in ng·L-1), its
identification/quantification is not accurately carried out and a complete
assessment of its persistence and environmental impact is far from being
established [1].
Aqueous biphasic systems (ABS) composed of ionic liquids (ILs) are here
proposed for the one-step extraction/concentration of EE2 from wastewater
matrices [1]. ABS composed of various hydrophilic ILs and KNaC4H4O6 were
initially tested and optimized, reaching extraction efficiencies of EE2 from 92 to
100% for the IL-rich phase. The improved systems that led to the complete
extraction of EE2 were further investigated by a proper manipulation of the
concentration of the phase forming-components, while controlling the
concentration factor achievable. An outstanding concentration of EE2 up to
1000-fold (from ng·L-1 to µg·L-1) in a single extraction and concentration step
was achieved [1]. Therefore, IL-based ABS are novel and promising strategies
to improve the performance of conventional analytical equipment for the
accurate analysis of water pollution tracers.
[1] T. B. V. Dinis, H. Passos, D. L. D. Lima, V. I. Esteves, J. A. P. Coutinho,
M. G. Freire, Green Chem. 2015, 17, 2570.
Agreement. D. L. D. Lima and H. Passos acknowledge FCT for grants
SFRH/BDP/80315/2011 and SFRH/BD/85248/2012, respectively. M. G. Freire
acknowledges the European Research Council under the European Union's
Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement n°
337753.
133
MIXTURES OF IONIC LIQUIDS IN AQUEOUS BIPHASIC SYSTEMS:
TAILORING THEIR FORMATION ABILITY AND EXTRACTION
EFFICIENCY
Teresa B. V. Dinis1, Helena Passos1, Mara G. Freire1, João A. P. Coutinho1
1
E-mail: tbdinis@ ua.pt
Aqueous biphasic systems (ABS) are commonly used as liquid-liquid
separation strategies. Due to the aqueous nature of their phases, ABS are ideal
media for the separation of biologically active molecules. In the past decade,
ionic liquids (IL) were introduced as phase-forming components and as
promising replacements of polymers in ABS [1]. These systems offer additional
advantages, such as low viscosity, quick phase separation and high and
tailored extraction efficiencies [2]. As a result, the phase diagrams and possible
applications of ABS composed of ILs and salts were widely investigated in the
past decade [3], and it is now accepted that the phases’ demixing ability and
polarities of the coexisting phases are largely dependent on the IL anion
hydrogen-bond basicity [3].
In this work, mixtures of two ILs with a common cation and different anions were
investigated aiming a more controlled manipulation of the phases’ polarities and
ABS ability to undergo liquid-liquid demixing. Novel ABS phase diagrams were
determined for systems composed of K2CO3, water and mixtures of
[C4C1im][CF3SO3] and [C4C1im]Cl in different molar fractions. The relative
polarity of the coexisting phases was additionally evaluated by partitioning
experiments of a series of dinitrophenylated (DNP) amino acids. Moreover,
extraction efficiencies of tryptophan and tyrosine (two model aminoacids widely
produced at an industrial scale) were also evaluated. It was found that the
selective partitioning of aminoacids is mainly dependent on the IL ratio in each
mixture. Therefore, more tailored separation processes can be developed if an
adequate control of the IL proportion in ILs mixtures is carried out.
[1] K. E. Gutowski, G. A. Broker, H. D. Willauer, J. G. Huddleston, R. P.
Swatloski, J. D. Holbrey, R. D. Rogers, Journal of the American Chemical
Society 2003, 125, 6632.
[2] M. G. Freire, A. F. M. Claudio, J. M. M. Araújo, J. A. P. Coutinho, I. M.
Marrucho, J. N. C. Lopes, L. P. N. Rebelo, Chemical Society Reviews 2012,
14, 4996.
[3] A. F. M. Cláudio, A. M. Ferreira, S. Shahriari, M. G. Freire, J. A. P.
Coutinho, Journal of Physical Chemistry B 2011, 115, 11145.
and FEDER under the PT2020 Partnership Agreement. H. Passos
acknowledges FCT for the grant SFRH/BD/85248/2012. M. G. Freire
acknowledges the European Research Council under the European Union's
Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement n°
337753.
134
AN INVITATION TO MAGNETISM
V. S. Amaral1 and the MagLab team1,2
1Departamento
2
de Física e CICECO
Departamento de Engenharia de Materiais e Cerâmica e CICECO
Magnetic properties and phenomena encompass a very large range of scales,
from sub-atomic particles to large scale objects. In modern experimental
studies for magnetic materials development, high resolution properties
characterization are crucial to understand the behavior of thin films,
heterostructures or nanoparticles, and assess their performance for device or
bio-medical applications. On the other hand, molecular and low dimensional
system magnets are a challenging field for new and versatile multifunctional
applications.
The installation in 2015 of the new Quantum Design MPMS3 SQUID-VSM
Magnetometer brought the capability of performing studies with resolution more
than 3 orders of magnitude increased in comparison with the already available
instruments, in the temperature range from 1.8K up to 400K and magnetic fields
up to 7 Tesla, with noise level below 10-8 e.m.u (equivalent to 10-10 g or 20 (µm)3
of magnetite). The cryogenic system allows fast and stable studies of small,
weak signal samples.
This presentation reports in general some of the recent work, emphasizing the
demanding situations, which in some cases are also requiring the use of more
complex data analysis and modelling to account for finer details (and impurities)
detected. Its aim is to invite to add some magnetic spice to your research.
The SQUID magnetometer was financed by Programa MaisCentro – Sistema
de Apoio a Infra-estruturas Científicas e Tecnológicas, Centro-01-CT62FEDER-002003, under the operation “capacitar o CICECO para
internacionalizar a I&DT em materiais e incrementar a competitividade
nacional”.
135
NOVEL BIOMEMBRANES BASED ON A PLA/CHOLINE BLEND SYSTEM
P. Barbosa1, J. M. Campos2, A. Turygin3, V. Shur3, A. Kholkin4
A. Barros-Timmons2, F.M. Figueiredo1
1
CICECO - Aveiro Institute of Materials, Department of Materials & Ceramic
Engineering, U. of Aveiro, Portugal
2
CICECO – Aveiro Institute of Materials, Department of Chemistry, U. of Aveiro,
Portugal
3
Institute of Natural Sciences, Ural Federal University, 620000 Ekaterinburg, Russia
4
CICECO – Aveiro Institute of Materials, Department of Physics, U. of Aveiro,
Portugal
E-mail: paula.barbosa@ ua.pt
Over the last years, many attempts have been made to reduce solid waste disposal
problems related with petrochemical products. Biodegradable polymers bring a
significant contribution to the sustainable development in view of the available
attractive methods for disposal with minor environmental impact. Aliphatic polyesters
represent a large part of biodegradable polymers and among these, poly(lactic acid)
(PLA) appear to be one of the most attractive because of its availability and
biodegradability [1]. PLA has extensive applications in packaging [2], biomedical fields
[3], including suture, bone fixation material, drug delivery microsphere, and tissue
engineering. A great variety of techniques and additives have been evaluated to
improve the physicochemical properties of PLA and enlarge its range of application
fields. Ionic liquids (ILs) have emerged as a new class of materials with unique
combination of negligible vapor pressure, low flammability, high ionic conductivity, and
high electrochemical stability [4].
In this study we report the preparation and characterization of PLA/choline-based
blend systems. The morphology of membranes with 10% wt. [Ch][DHP] consists of
PLA microspheres with enhanced crystallinity and ca. 50-60 µm in diameter, which are
formed due to the PLA/ [Ch][DHP] immiscibility. These membranes are stable up to
200ºC, and show negligible humidity dependence and overall low values of the ionic
conductivity (5x10-7– 4x10-6 Scm-1), which confirm the dominant hydrophobic character
of PLA. On the other hand, piezoelectric force microscopy revealed enhanced
piezoelectric properties at the microsphere interfaces, thus reinforcing the potential of
the new morphology to produce soft piezoelectric mats [5].
[1] R. Mehta, V. Kumar, H. Bhunia, S. N. Upadhyay, J. Macromol. Sci. C 2005, 45, 325.
[2] R. Auras, B. Harte, S. Selke, Macromol. Biosci. 2004, 4, 835.
[3] K. Hamad, M. Kaseem, H.W. Yang, F. Deri, Y. G. Ko, Express Polym. Lett. 2015,
9, 435.
[4] Y. Fukaya, Y., K. Sekikawa, H. Ohno, Green Chem. 2007, 9, 1155.
[5] C. S. Lovell, J. M. Fitz-Gerald, C. Park, J Polym Sci B Polym Phys 2011, 49, 1555.
Akowledgements
Work funded by FCT through grants FCOMP-01-0124-FEDER-014605 (Ref.
PTDC/CTM-NAN/110776/2009), CICECO - FCOMP-01-0124-FEDER-037271 (Ref.
FCT PEst-C/CTM/LA0011/2013), IF/01174/2013, SFRH/BPD/96665/2013 and
SFRH/BPD/85811/2012.
136

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