ENERGYTrends and Future Challenges

Book of Abstracts

JORNADAS CICECO 2016

1

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

2

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

3

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

4

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

5

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 PLASMON-ENHANCED 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 MIL-103(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

6

F. Mohseni, M. J. Pereira, A. Davarpanah, T. Santos, A. Barros-Timmons, 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

7

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

8

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. Andre, M.T. Duarte, L. Mafra SUPRAMOLECULAR SYNTHONS IN PHARMACEUTICAL CO-CRYSTALS 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

97

9

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 HEATER-THERMOMETER NANOPLATFORMS USING HYPERSPECTRAL IMAGING

100

Mohammadreza Kamali, Maria Elisabete V. Costa, Isabel Capela ENHANCED CATALYTIC ACTIVITY OF MESOPOROUS ZERO-VALENT 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 ELECTROCATALYSTS FOR SOLID ALKALINE FUEL CELLS

105

Nuno Sousa, Carla Vilela, Carmen S. R. Freire, Armando J. D. Silvestre, Filipe L. Figueiredo A BACTERIAL CELLULOSE NANOCOMPOSITE MEMBRANE WITH OH- CONDUCTIVITY

106

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

107

10

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

11

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

127

12

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 LEAD-FREE 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

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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

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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

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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

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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.

15

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

16

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

17

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

14:40

Discussion panel Funding Opportunities: Structural Funds and the H2020

Moderator: Paula Pais (CICECO's Technology Transfer Interface, Universidade de Aveiro)

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

16:00

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

- 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

18

ORAL ABSTRACTS

19

TOWARDS NEARLY ZERO ENERGY BUILDINGS

Adélio Mendes

E-mail: mendes@fe.up.pt

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.

20

PROTEIN FIBRILS AS FUNCTIONAL NANOSTRUCTURES FOR TH E DEVELOPMENT OF INNOVATIVE BIOMATERIALS

Carmen Freire

CICECO - Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal

E-mail: cfreire@ua.pt

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.

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GRAPHENE-COATED TRANSPARENT CONDUCTING FIBERS FOR SMART TEXTILES

Helena Alves1, Daniela Rodrigues1, Isabel de Schrijver2, Ana I. S. Neves3, Monica Craciun3

1CICECO, Portugal

2Centexbel, Belgium 3University of Exeter, UK

E-mail: alves.helena@ua.pt

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 fault-tolerance 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.

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REPROGRAMMING OF ENERGY METABOLISM IN MACROPHAGES EXPOSED TO DIFFERENT NANOPARTICLES

Iola F. Duarte1, Raquel Saborano1, Thidarat Wongpinyochit2, F. Philipp Seib2,3

1 CICECO - Aveiro Institute of Materials, Department of Chemistry, University of

Aveiro, 3810-193 Aveiro, Portugal. 2 Strathclyde Institute of Pharmacy and Biomedical Sciences, University of

Strathclyde, 161 Cathedral Street, Glasgow, G4 0RE, UK. 3 Leibniz-Institut für Polymerforschung Dresden e.V., Max Bergmann Centre for

Biomaterials Dresden, Hohe Strasse 6, 01069 Dresden, Germany.

E-mail: ioladuarte@ua.pt

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.

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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 de Física and CICECO, Universidade de Aveiro, Portugal

2IFIMUP and IN-Institute of Nanoscience and Nanotechnology, Universidade do Porto, Portugal

3Departamento de Engenharia de Materiais e Cerâmica and CICECO, Universidade de Aveiro, Portugal

4Departamento de Engenharia Mecânica and TEMA, Universidade de Aveiro, Portugal

E-mail: jamaral@ua.pt

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 fuel-based, 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 heat-pumps. 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.

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SOFT NATURAL-BASED BIOMATERIALS FOR HUMAN TISSUE ENGINEERING

João F. Mano

Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal.

E-mail: jmano@ua.pt

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 regenerative-based 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.

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BIOECONOMY AND SMART REGIONS: THE BIOREFINA-TER PRO JECT

João Nunes1, Susana Pereira1, Rita Pontes1

1BLC3 Association - Technology and Innovation Campus, Rua Nossa

Senhora da Conceição, 2 Lagares, 3405-155 Oliveira do Hospital

E-mail: joao.nunes@blc3.pt

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.

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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

E-mail: jfrade@ua.pt

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.

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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 E-

mail: 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.

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RECENT ADVANCES, PRESENT CHALLENGES AND FUTURE TREN DS 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 teo.rojo@ehu.es

CIC energiGUNE, Parque Tecnológico de Álava, Albert Einstein 48, 01510, Miñano, Spain.

E-mail: trojo@cicenergigune.com 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 Li-ion 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 CIC- Energigune on these technologies.

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USING COMPUTATIONAL TOOLS TO UNDERSTAND THE FORMATI ON 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

Aveiro, 3810-193 Aveiro, Portugal

E-mail: tlpgalvao@ua.pt

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.

30

HIERARCHICAL AND NANO ZEOLITES: PROSPECTS

Valentin Valtchev,1,2 Svetlana Mintova2

1 Department of Chemistry, Jilin University, Changchun, China

2 Normandie Univ, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, 6 boulevard Maréchal Juin, 14000 Caen, France

E -mail: valentin.valtchev@enscaen.fr

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.

31

POSTER ABSTRACTS

32

CHALLENGES AND OPPORTUNITIES FOR MAGNETIC REFRIGERA TION 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.

250 270 290 310 330 350 370 390

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Mn1.3

Fe0.65

P0.4

Si0.6

The

rmal

con

duct

ivity

W/m

/K

Temperature (K)

Mn1.25

Fe0.7

P0.45

Si0.55

La2/3

(Ca1-x

Srx)1/3

MnO3

X=0.00 X=0.06 X=0.15 X=0.30 X=1.00

-------------------------------------

Figure 1. Thermal conductivity of Mn1.25Fe0.7P0.45Si0.55 and Mn1.3Fe0.65P0.4Si0.6 and La2/3(Ca1-

xSrx)1/3MnO3, x= 0, 0.06, 0.15, 0.3, and 1

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 field-dependence of thermal conductivity is needed and should be adequately considered.

[1] Brück et al, J. Magn. Magn. Mater. 2007, 310, 2793. [2] Turcaud et al, Scr. Mater. 2013, 68, 510.

33

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 Coimbra Chemistry Centre, University of Coimbra

2 CICECO – Aveiro Institute of Materials, University of Aveiro

E-mail: anacosta@qui.uc.pt

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).

34

PORCELAIN FORMULATIONS FOR ROBOCASTING 3D

A.F.V. Carvalho1, J.Luís1, L.S.O. Pires1,2,3, J.M. Oliveira1,2

1School of Design, Management & Production Technologies Northern Aveiro, University of Aveiro, Oliveira de Azeméis, PT

2 CICECO-Aveiro Institute of Materials, University of Aveiro, PT

3 Dept. Materials & Ceramic Engineering, University of Aveiro, PT

E-mail: andreiac@ua.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.

[1] 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.

35

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

E-mail: atkach@ua.pt

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 off-central displacement of small Y3+ ions on large Sr sites, whereas the giant low-temperature 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 low-temperature 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.

36

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 Department of Physics and CICECO − Aveiro Institute of Materials,

University of Aveiro, 3810–193 Aveiro, Portugal 2 Department of Physics and I3N, University of Aveiro, 3810−193 Aveiro,

Portugal 3 Department of Mechanical Engineering, University of Minnesota

Minneapolis, MN 55455, USA 4 Walter Schottky Institut and Physik − Department, Technische Universität

München, Am Coulombwall 4, Garching 85748, Germany

E-mail: a.botas@ua.pt

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 1-dodecene (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 SiNPs-C12 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 SiNPs-H. 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 oxide-related 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.

37

STRUCTURAL, CHEMICAL, OPTICAL AND ELECTRICAL PROPER TIES 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

E-mail: alicemarciel@ua.pt

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.

38

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 Ceramic Engineering, University of Aveiro, 3810-193 Aveiro, Portugal

E-mail: alyne@eq.uc.pt

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.

39

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

1Physics Department and CICECO − Aveiro Institute of Materials, University of Aveiro, Portugal

2Instituto de Telecomunicações, University of Aveiro, Portugal 3Department of Electronics, Telecommunications and Informatics and Instituto de

Telecomunicações, University of Aveiro, Portugal 4Department of Electrical and Computer Engineering and Instituto de

Telecomunicações, Instituto Superior Técnico, University of Lisboa, Portugal E-mail: rita.bastos@ua.pt

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 organic-inorganic hybrids for low cost photonic integrated circuits. The organic-inorganic 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.

40

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

E-mail: ana.estrada@ua.pt

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 visible-light 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 co-financed 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.

41

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

E-mail: agomes1@ua.pt

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.

42

PURIFICATION OF PHYCOBILIPROTEINS USING AQUEOUS BIP HASIC 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

Aveiro, 3810-193 Aveiro, Portugal 2ALGAplus Lda, Travessa Alexandre da Conceição 3830-196 Ílhavo, Portugal

E-mail: spventura@ua.pt

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 cholinium-based 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: R-phycoerythrin 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.

43

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,

3810-193 Aveiro, Portugal 2 Department of Chemistry, QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal

3 Department of Physics, CICECO – Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal

4 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal

E-mail: danielafirmino1@ua.pt 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).

44

MICELLE-MEDIATED EXTRACTION OF CHLOROPHYLLS FROM SPINACH LEAVES USING AQUEOUS SOLUTIONS OF IONIC LIQ UIDS

Ana M. Ferreira1, Ana Cláudia Leite1, Imran Khan1, Mara G. Freire1 and João

A. P. Coutinho1

1CICECO - Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, Aveiro, Portugal

E-mail: ana.conceicao@ua.pt

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” cost-effective 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.

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LACCASE PARTITION IN IONIC-LIQUID-BASED AQUEOUS BIP HASIC SYSTEMS

Ana P.M. Tavares1, Oscar Rodriguez2, João A. P. Coutinho1, Ana Soto2, Mara G. Freire1

1CICECO-Aveiro Institute of Materials, Chemistry Department, University of Aveiro,

3810-193 Aveiro, Portugal 2Department of Chemical Engineering, Universidade de Santiago de Compostela,

Santiago de Compostela, Spain

E-mail: aptavares@ua.pt

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 CICECO-Aveiro 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.

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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

E-mail: ritateles@ua.pt

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.

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Mg-PARTIALLY STABILIZED ZIRCONIA, ELECTRICAL AND STRUCTURAL CHARACTERIZATION

Ana Rondão1, M.F. Évora1, F.M.B. Marques1

1Dept. of Materials and Ceramic Eng./CICECO, University of Aveiro, 3810-193

Aveiro, Portugal

E-mail: ines.rondao@ua.pt

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 needle-type 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.

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POROUS BIPHASIC CALCIUM PHOSPHATE SCAFFOLDS DERIVED FROM CUTTLEFISH BONE

Ana S. Neto, José M.F. Ferreira

Department of Materials and Ceramics Engineering, CICECO E-

mail: E-mail: sofia.neto@ua.pt

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.

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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, Patrick-Kurt Dannecker3, M. A. R. Meier3, Armando J. D. Silvestre1

1CICECO and Department of Chemistry, University of Aveiro, 3810-193 Aveiro,

Portugal 2CEMUC, 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

E-mail: mariajsoares@ua.pt

Polymers are everywhere in the everyday life, however they are still mainly produced from fossil resources raising several sustainability issues. In this vein, 2,5-furandicarboxylic 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 2,5-furandicarboxylate) (PEF) [3], due to its resemblance to the well-known poly(ethylene terephthalate) (PET),however, PEF lacks ofbiodegradability.Indeed turning furan-based 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.

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PURIFICATION OF CRUDE GLYCEROL, BY-PRODUCT OF BIODI ESEL 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 2Sapec-Química SA, Ovar, Portugal

3 CICECO-Aveiro Institute of Materials, Escola Superior de Tecnologia e Gestão de Águeda, Águeda, Portugal

E-mail: brunogodinho@ua.pt

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

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UTILIZATION OF PAC OF RADIOISOTOPE TRACKERS AND DFT CALCULATIONS TO DETERMINE LOCAL ENVIRONMENT OF Hg(I I) IN DITHIOCARBAMATE FUNCTIONALIZED PARTICLES FOR MAGNET IC

REMOVAL OF Hg 2+ 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

E-mail: amorim5@ua.pt

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)

52

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 1140-1147

[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).

53

PECULIAR HIGH TEMPERATURE MAGNETOELECTRIC COUPLING IN BaTiO 3: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

E-mail: amorim5@ua.pt

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

54

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.

55

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

1CICECO – Aveiro Institute of Materials, Department of Chemistry, University of

Aveiro, 3810-193 Aveiro, Portugal 2CICECO – Aveiro Institute of Materials, Department of Materials and Ceramic

Engineering, University of Aveiro, 3810-193 Aveiro, Portugal

E-mail: cvilela@ua.pt

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 nano-fibrils 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 H2-air 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.

56

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 co-financed 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.

57

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

E-mail: acmarques@ua.pt

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.

58

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 2CIIMAR - Interdisciplinary Centre of Marine and Environmental Research, Rua dos

Bragas 289, 4050-123 Porto, Portugal 3University of Aveiro and CESAM/Chemistry Department, Aveiro, Portugal

E-mail: claudia.b.lopes@ua.pt

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.

59

CHITOSAN-GENIPIN/REDUCED GRAPHENE OXIDE BIOCOMPOSIT E FILM FOR ACTIVE FOOD PACKAGING

Cláudia Nunes1,2, Ana Barra1, M.A. Martins1, Manuel A. Coimbra2, Paula Ferreira1

1CICECO - Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro,

Portugal 2QOPNA, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal

E-mail: claudianunes@ua.pt

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).

60

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

1Department of Materials and Ceramic Engineering, CICECO – Aveiro Institute of

Materials, University of Aveiro, Aveiro 3810-193, Portugal 2Institute of Physics, Faculty of Science, P.J. Šafárik University in Košice, 9 Park

Angelinum, 04154 Košice, Slovakia 3B.Verkin Institute for Low Temperature Physics and Engineering of NAS of Ukraine,

Prospekt Nauky, 47, 61103 Kharkiv, Ukraine

E-mail: danielevieira@ua.pt

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 face-linked 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.

61

Ag-TiO 2 NANO-HETEROSTRUCTURES EXHIBITING GAS SENSING PROPERTIES, VISIBLE-LIGHT ACTIVATED PHOTOCHROMISM W ITH

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

E-mail: david.tobaldi@ua.pt

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].

62

[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.

63

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

Department, Aveiro, Portugal 2 CIIMAR - Interdisciplinary Centre of Marine and Environmental Research, Rua dos

Bragas 289, 4050-123 Porto, Portugal

E-mail: danielatavares@ua.pt

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.

64

HETEROGENEOUS OXOMOLYBDENUM(VI)@IONIC LIQUID SYSTEMS AS EFFECTIVE CATALYSTS FOR OXIDATIVE DESULFURIZATIO N

Diana Julião1,2, Ana C. Gomes1, Martyn Pillinger1, Rita Valença3, Jorge C. Ribeiro3, Isabel S. Gonçalves1, Salete S. Balula2

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 3 Galp Energia, Refinaria de Matosinhos, 4452-852 Leça da Palmeira, Matosinhos,

Portugal

E-mail: diananetojuliao@ua.pt

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.

65

CRYOGENIC NANOTHERMOMETER BASED ON THE MIL-103(TB,E U) METAL ORGANIC FRAMEWORK

Duarte Ananias1, Carlos D. S. Brites2, Luís D. Carlos2, João Rocha1

1 Department of Chemistry, CICECO – Aveiro Institute of Materials, University

of Aveiro, 3810-193 Aveiro, Portugal

2 Department of Physics, CICECO – Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal

E-mail: dananias@ua.pt

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.

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.

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66

HYDROGEN-BOND ACIDITY AND BASICITY OF MIXTURES OF I ONIC 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 CICECO - Aveiro Institute of Materials, Department of Chemistry, University

of Aveiro, 3810-193 Aveiro, Portugal 2 Center of Research in Ionic Liquids, Department of Chemical Engineering,

Universiti Teknologi PETRONAS, Tronoh 31750, Perak, Malaysia

E-mail: emanuelcapela@ua.pt

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.

67

ENHANCED SOLUBILITY OF NATURAL TRITERPENIC ACIDS AN D 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*

1CICECO - Aveiro Institute of Materials, Department of Chemistry, University

of Aveiro, 3810-193 Aveiro, Portugal. 2Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal.

*E-mail: maragfreire@ua.pt

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 ionic-liquid-based aqueous two-phase systems”, Sep. Purif. Technol., 2012, 97: 142-149.

[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 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. 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.

68

MAGNETOELECTRIC EFFECT ENHANCEMENT BY BREAKING THE GEOMETRIC MAGNETIC FRUSTRATION IN LuMn 1+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

E-mail: ffigueiras@ua.pt

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 et al., Phys.Chem.Chem.Phys., 2016, DOI: 10.1039/C6CP01562J

[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.

69

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. Barros-Timmons1,3, V. A. F. Costa4,5, J. S. Amaral1,2, V. S. Amaral1,2

1CICECO - Aveiro Institute of Materials, University of Aveiro, Portugal

2 Department of Physics, University of Aveiro, Portugal 3 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

E-mail: f.mohseni@ua.pt

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

70

MULTIPLE EMULSION TEMPLATING OF Ag@SiO 2 CAPSULES FOR

ANTIBACTERIAL APPLICATIONS

Filipa L. Sousa1, A. V. Girão1, S. Fateixa1, A. Almeida2, T. Trindade1

1 Department of Chemistry-CICECO, University of Aveiro, Campus de

Santiago, 3810-193 Aveiro, Portugal 2 Department of Biology-CESAM, University of Aveiro, Campus de Santiago

3810-193 Aveiro, Portugal

E-mail: filipalsousa@ua.pt

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.

71

SURFACTANTS AS ALTERNATIVE SOLVENTS IN THE EXTRACTI ON 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

1CICECO - Aveiro Institute of Materials, Department of Chemistry, University of

Aveiro, 3810-193 Aveiro, Portugal 2ALGAplus Lda, Travessa Alexandre da Conceição 3830-196 Ílhavo, Portugal

E-mail: flavia.vieira@ua.pt

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.

72

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 CICECO - Aveiro Institute of Materials, Department of Chemistry, University

of Aveiro, 3810-193 Aveiro, Portugal

E-mail: francisca.silva@ua.pt

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 (IL-based 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.

73

TEMPERATURE-SWITCHABLE IONIC-LIQUID-BASED AQUEOUS BIPHASIC SYSTEMS

Helena Passos1, Andreia Luís1, João A. P. Coutinho1 and Mara G. Freire1

1 CICECO - Aveiro Institute of Materials, Department of Chemistry, University

of Aveiro, 3810-193 Aveiro, Portugal

E-mail: hpassos@ua.pt

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 molecular-solvent-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 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 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.

74

IMPROVED EXTRACTION OF FLUOROQUINOLONES WITH RECYCLABLE IONIC-LIQUID-BASED AQUEOUS BIPHASIC SYST EMS

Hugo F.D. Almeida1,2, Mara G. Freire2, Isabel M. Marrucho1

1Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de

Lisboa, 2780-157 Oeiras, Portugal 2CICECO – Aveiro Institute of Materials, Chemistry Department, University of Aveiro,

3810-193 Aveiro, Portugal

E-mail: hugo.f.d.almeida@itqb.unl.pt

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 ionic-liquid-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.

75

POTATO INDUSTRY BYPRODUCTS: AN ALTERNATIVE BIOPOLYM ERS’ SOURCE FOR RENEWABLE PACKAGING MATERIALS

Idalina Gonçalves1,2, Ana Barra2, Cláudia Nunes1,2, Manuel A. Coimbra1, Paula Ferreira2

1 QOPNA, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal

2 CICECO - Aveiro Institute of Materials, Department of Materials and Ceramic Engineering, University of Aveiro, 3810-193 Aveiro, Portugal

E-mail: idalina@ua.pt

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 starch-based 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-FEDER-007679). 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, 2425-2429.

3. B. M. Szafranek, E.E. Synak, Phytochemistry 2006, 67, 80-90.

76

CONTROLLING GABAPENTIN POLYMORPHISM: IONIC LIQUIDS AS CRYSTALLIZATION MEDIA

Inês C. B. Martins1,2, M. Teresa Duarte1, Luís Mafra2

1Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa,

1049-001, Lisboa, Portugal 2Department of Chemistry, CICECO – Aveiro Institute of Materials, University of

Aveiro, 3810-193 Aveiro, Portugal

E-mail: inesbmartins@tecnico.ulisboa.pt

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.

77

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 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

E-mail: nfsantos@ua.pt

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.

78

VOLUME DEPENDENCE OF MAGNETIC PROPERTIES IN Co 2CrGa-BASED HEUSLER ALLOYS FOR MAGNETOCALORIC APPLICATION S: 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

E-mail: joaonsg@ua.pt

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.

79

VANADIUM-SUBSTITUTED SrTiO 3: 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

E-mail: jmacias@ua.pt

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 1000-1100°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 650-850°C.

80

CO-AMORPHOUS γγγγ-CYCLODEXTRIN:MONTELUKAST (1:1) ADDUCT BY MECHANOCHEMISTRY PROCEDURES, WITH RESOURCE TO

PRE-MILLING OF γγγγ-CYCLODEXTRIN

Jessica Silva Barbosa1,2, Filipe A. Almeida Paz2, Susana Santos Braga1

1 Department of Chemistry, QOPNA research unit, University of Aveiro, 3810-193

Aveiro, Portugal 2 Department of Chemistry, CICECO – Aveiro Institute of Materials, University of

Aveiro, 3810-193 Aveiro, Portugal

E-mail: jessicambarbosa@ua.pt

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 13C1H 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 co-amorphous 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.

81

ASSEMBLY OF METAL COLLOIDS ONTO SURFACE FUNCTIONALI ZED MAGNETITE PARTICLES

Joana L. Lopes1, Karine L. Marques2, Ana V. Girão1, Eduarda Pereira2, Tito Trindade1

1CICECO – Aveiro Institute of Materials, Department of Chemistry, University of

Aveiro, 3810-193 Aveiro, Portugal. 2 CESAM – Department of Chemistry, University of Aveiro, 3810-193 Aveiro,

Portugal

E-mail: jllopes@ua.pt

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.

82

BIOPLASTICS PRODUCTION THROUGH MIXED MICROBIAL CULT URES ECO-ENGINEERING

Joana Pereira1, D. Queirós1, P. C. Lemos2, A. Xavier1, L. S. Serafim1

1CICECO – Aveiro Institute of Materials, University of Aveiro, Chemistry Department,

Aveiro, Portugal 2LAQV, REQUIMTE, Chemistry Department, Faculty of Science and Technology,

University Nova of Lisbon, Caparica, Portugal

E-mail: joanasofiapereira@ua.pt

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 by-products 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.

83

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

Aveiro, 3810-193 Aveiro, Portugal E-mail: spventura@ua.pt

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 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 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.

84

PURIFICATION AND CHARACTERIZATION OF POLYSACCHARIDE S 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, 3810-

193 Aveiro, Portugal E-mail: joao.trigo@ua.pt

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.

85

(La,Sr)(Fe,Co)O 3-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,

3810-193 Aveiro, Portugal 2 Fuel Cell Group, Thermal Processes Department, Institute of Power Engineering,

Augustowka 36, 02-981 Warsaw, Poland

E-mail: k.zakharchuk@ua.pt

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 intermediate-temperature 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)O3-based 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 rhombohedrally-distorted perovskite structure without impurities detectable by XRD. Average thermal expansion coefficients were determined by dilatometry to vary in the range (13.8-14.3)×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.

86

TIME-RESOLVED DIFFRACTION STUDY OF THE TRANSFORMATI ON OF C60 INTO GRAPHITE-LIKE CARBON

L.Marques1, M. Mezouar2, J-L. Hodeau3

1Departamento de Física and CICECO, Universidade de Aveiro, 3810-193

Aveiro, Portugal. 2 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 high-pressure 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.

87

THERMOSENSITIVE MICELLAR SYSTEMS AS SELECTIVE PLATF ORMS 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 E-mail: l.castro@ua.pt

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 X-114 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.

88

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

1CICECO - Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, Aveiro, Portugal.

2Associate Laboratory LSRE/LCM, Department of Chemical and Biological Technology, Polytechnic Institute of Bragança, Bragança, Portugal.

E-mail:lilianasilva306@hotmail.com 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 donor-acceptor 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.

89

DESIGN OF AMINE MODIFIED-PERIODIC MESOPOROUS ORGANOSILICAS FOR CO 2/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

1CICECO – Aveiro Institute of Materials, Departments of Chemistry and of Materials

& Ceramics Engineering, University of Aveiro, 3810-193 Aveiro, Portugal 2LSRE, Faculty of Engineering, University of Porto, 4200-465 Porto, Portugal 3CCB, Faculty of Sciences, University of Lisbon, 1749-016 Lisboa, Portugal

4Department of Chemical and Process Engineering, University of Strathclyde, Glasgow, UK

5CERENA, 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 (POCI-01-0145-FEDER-007679), UID/MULTI/00612/2013, UID/ECI/04028/2013, NORTE-07-0124-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.

90

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

E-mail: mariasapereira@ua.pt

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

91

ORDERED MICRO/MESOPOROUS Zr,Al-SILICATES FOR INTEGR ATED REDUCTION AND ACID-CATALYSED CONVERSION OF FURFURAL

M. M. Antunes1, S. Lima2, P. Neves1, A. L. Magalhães1, E. Fazio3, F. Neri3,

M. T. Pereira1, A. F. Silva1, 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. E-mail: margarida.antunes@ua.pt

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 Zr- and 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.

92

SUPRAMOLECULAR SYNTHONS IN PHARMACEUTICAL CO-CRYSTA LS 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

1Chemistry Dept., CICECO – Aveiro Institute of Materials, 3810-193 Aveiro, Portugal

2CQE − Centro de Química Estrutural, IST, Universidade de Lisboa, Portugal 3Lab. de Estudios Cristalográficos, CSIC-Universidad de Granada, Granada, Spain

4Dipartimento di Scienza e Alta Tecnologia, Università dell’Insubria, Como, Italy

E-mail: msardo@ua.pt

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 co-crystals 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.

93

1D ZINC NANOSTRUCTURES OBTAINED BY ELECTRODEPOSITIO N 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

E-mail: mstarykevich@ua.pt

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 fill-factor. 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.

94

Ni-Fe LAYERED-DOUBLE-HYDROXIDES AS CATALYSTS FOR OX YGEN EVOLUTION REACTION

Manon Wilhelm1, Alexandre C. Bastos1, João Tedim1, Mário G.S. Ferreira1

1CICECO, DEMaC, University of Aveiro E-

mail: manon.wilhelm@ua.pt

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.

95

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

1CICECO – Aveiro Institute of Materials, Department of Chemistry, University of Aveiro

E-mail: mcneves@ua.pt

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 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. 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.

96

CHITOSAN-SILICA HYBRID NANOADSORBENTS FOR THE UPTAK E OF PHARMACEUTICALS FROM WATER

Margarida I. Rodrigues1, Sofia F. Soares1, Tito Trindade1 and Ana L. Daniel-da-Silva1

1CICECO - Aveiro Institute of Materials, Department of Chemistry, University

of Aveiro, 3810-193 Aveiro, Portugal

E-mail: mpenedorodrigues@ ua.pt; ana.luisa@ua.pt

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), infra-red 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 .

97

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

of Aveiro, 3810-193 Aveiro, Portugal 2ALGAplus Lda, Travessa Alexandre da Conceição 3830-196 Ílhavo, Portugal

E-mail: margaridamartins@ua.pt

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, 4966-4995.

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.

98

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 Engineering, University of Aveiro, 3810-193 Aveiro, Portugal

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] J. Maier, Phys. Chem. Chem. Phys., 2009, 11, 3011. [2] C.E. Goodyer, J. S. Fish, J.D. Fehribach, R. O'Hayre, A.L Bunge, Electrochimica

Acta, 2011, 56, 9295. [3] 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.

99

DEVELOPMENT OF NEW RENEWABLE AND BIODEGRADABLE

POLY(BUTYLENE FURANDICARBOXYLATE-CO-BUTYLENE

DIGLYCOLATE) COPOLYESTERS

Marina Matos1, Andreia Sousa 1,2, Armando Silvestre 1CICECO and Department of Chemistry, University of Aveiro, 3810-193, Aveiro,

Portugal 2 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 2,5-furandicarboxylate) (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-Coca-Cola-Company-sign-partnership-agreement-to-develop-next-generation-100-plant-based-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.

100

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

1Universidade 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

E-mail: debasu@ua.pt

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.

101

ENHANCED CATALYTIC ACTIVITY OF MESOPOROUS ZERO-VALE NT IRON NANOPARTICLES PREPARED UNDER SONOCHEMICAL IRRADIATI ON

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.

102

TOWARDS FAST COMPUTATIONAL DESIGN OF MAGNETOCALORIC MATERIALS

N. M. Fortunato1, J. N. Gonçalves1 , J. S. Amaral1,2, V. S Amaral1

1. Departamento de Física and CICECO, Universidade de Aveiro, Aveiro 3810-093,

Portugal 2. Instituto de Física dos Materiais da Universidade do Porto, Institute of Nanoscience

and Nanotechnology, Porto 4169-007, Portugal

E-mail: fortunato@ua.pt

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

103

IN SITU FUNCTIONALIZATION OF CELLULAR ALUMINOSILICA TES

N. Vitorino 1, A. Kovalevsky 1, J.R. Frade 1

1 Department of Materials and Ceramic Engineering, (CICECO), University of

Aveiro, 3810 Aveiro, Portugal

E-mail: nuno.vitorino@ua.pt

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.

104

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

E-mail: nuno.vitorino@ua.pt

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.

105

ELECTROCATALYSTS FOR SOLID ALKALINE FUEL CELLS

Nuno Sousa1, Biljana Šljukić2, David Cardoso2, Diogo Santos1,2, Filipe L. Figueiredo1

1 CICECO, Dep. of Materials and Ceramic Engineering, University of Aveiro,

2 Materials Electrochemistry Group, Dep. of Chemical Engineering, Technical University of Lisbon

E-mail: nunoasousa@ua.pt

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 layered-perovskite 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.

106

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

E-mail: nunoasousa@ua.pt

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 (30-94 °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. Rosero-Navarro, 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

107

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 CICECO – Aveiro Institute of Materials, Department of Materials and Ceramic Engineering, University of Aveiro, 3810-193 Aveiro

3Institute of Physics of Materials of the University of Porto (IFIMUP), 4169-007 Porto 4Industrial Electronics Department, University of Minho, Azurem, 4800-058

Guimaraes

E-mail: olena@ua.pt

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 free-standing 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.

108

SYSTEMATIC STUDY OF GALVANIC CORROSION MITIGATION O N 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

E-mail: mpo@ua.pt

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.

109

HIGH IONIC CONDUCTIVITY IN ZEOLITIC IMIDAZOLATE FRA MEWORK 8

P. C. Barbosa1, M.R. Soares2, M. Pinto3, F. A. Almeida Paz4, F. M. Figueiredo1

1CICECO - Aveiro Institute of Materials, Dep. Materials & Ceramic Eng, U. of Aveiro,

Portugal; 2CICECO - Aveiro Institute of Materials, LCA, U. of Aveiro, Portugal;

3CERENA, Dep. Chemistry Engineering, IST, U. Lisboa, Portugal; 4CICECO – Aveiro Institute of Materials, Chemistry Dep., U. of Aveiro, Portugal

E-mail: paula.barbosa@ua.pt

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.

110

THICKNESS DEPENDENCY OF STRUCTURE AND MAGNETIC PROPERTIES OF La1-xSrxMnO3 THIN FILMS ON SrTiO 3 SUBSTRATE

P. Mirzadeh Vaghefi1, A. Baghizadeh2, M. J. Pereira1, M. Willinger2, V. S. Amaral1

1Department of Physics & CICECO, University of Aveiro, Portugal.

2Department of Ceramics and Materials Engineering, CICECO, University of Aveiro, Portugal.

3Department of Inorganic Chemistry, F.-H.-Inst. Max-Planck-Gesellschaft, Faradayweg, Berlin, Germany.

E-mail: pegah.mirzadeh@ua.pt

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).

111

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

E-mail: pankaj@ua.pt

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

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 under the European Union's Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement n° 337753.

112

ONE-POT CONVERSION OF FURFURAL IN THE PRESENCE OF A Sn,Al-CONTAINING 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 ICIQ, Av. Països Catalans, Tarragona, Spain 3 Dipartimento di Fisica e di Scienze della Terra, Università degli Studi di Messina,

Viale F. Stagno d’Alcontres, Messina, Italy 4 Institute for Biotechnology and Bioengineering, IST, Lisboa, Portugal

5 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 post-synthesis 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 study using the prepared catalysts with different bio-products as 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 2014-2018 (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.

Scheme 1. Conversion of Fur in alcohol media to give useful bio-products via acid/reduction chemical routes.

113

SERS-ACTIVE MAGNETIC SORBENTS FOR REMOVAL AND OPTIC AL DETECTION OF PENICILLIN G

Paula C. Pinheiro1, Tito Trindade1,2

1Department of Chemistry-CICECO, University of Aveiro, 3810-193 Aveiro,

Portugal

E-mail: pcpinheiro@ua.pt

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).

114

PROMISING CALCIUM PHOSPHATE CEMENTS FOR VERTEBROPLA STY 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

1Department of Materials and Ceramic Engineering, CICECO, University of Aveiro,

3810-193 Aveiro, Portugal 2Department of Medical Sciences, Institute for Biomedicine (iBiMED), University of

Aveiro, 3810-193 Aveiro, Portugal 3Department of Biology, GeoBioTec, University of Aveiro, 3810-193 Aveiro, Portugal

4UIDM, 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, non-hardening 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.

115

DISPELLING SOME MYTHS ABOUT THE CO 2 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.

E-mail: quijorge@ua.pt

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.

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.

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116

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

Aveiro, 3810-193 Aveiro, Portugal 2Instituto de Física, UNICAMP, Campinas, Sâo Paulo 13083-859, Brasil

E-mail: vidyasagar@ua.pt

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.

117

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.

118

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

of Aveiro, 3810-193 Aveiro, Portugal 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

119

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 CICECO - Aveiro Institute of Materials, Department of Materials and Ceramic Engineering, University of Aveiro, 3810-193 Aveiro, Portugal

2 Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany

E-mail: rmsilva@ua.pt

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.

120

ZIRCONIA BASED CERMETS: ELECTRICAL, MAGNETIC AND TH ERMAL 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, Coimbra, Portugal

3 I3N-Aveiro, Department of Physics, University of Aveiro, Aveiro 3810-193, Portugal.

E-mail: serrazina@ua.pt

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 X-ray 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] J. B. Puga, University of Aveiro, 2014.

[5] K. Wieczorek-Ciurowa, D. Oleszak, and K. Gamrat, J. Alloys Compd., 2007 vol. 434–435, no. SPEC. ISS., pp. 501–504.

121

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

Department, Aveiro, Portugal

E-mail: sousa.rita@ua.pt

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.

122

HIGH BUFFER CAPACITY WASTE-CONTAINING GEOPOLYMERS T O 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, 3810-193 Aveiro, Portugal

2 Institute of Materials and Structures, Riga Technical University, Latvia

E-mail: ruimnovais@ua.pt

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, 1040-1046.

[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.

123

HYBRID CONJUGATES OF CORROLE AND Fe 3O4@SiO2 NANOPARTICLES FOR PHOTODYNAMIC THERAPY

Rute A. Pereira1, Joana F. B. Barata1,2, Tito Trindade1

1Department of Chemistry & CICECO – Aveiro Institute of Materials, University of

Aveiro, Aveiro, Portugal 2 Department of Chemistry & QOPNA, University of Aveiro, Aveiro, Portugal

E-mail: rute.pereira@ua.pt

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.

124

CORK-POLYMER COMPOSITES FOR INJECTION MOULDING APPLICATIONS

S. P. Magalhães da Silva1,2, P. S. Lima1, J. M. Oliveira1,2

1 Escola Superior Aveiro Norte, Universidade de Aveiro

2 Aveiro Institute of Materials (CICECO), Universidade de Aveiro E-

mail: 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 well-recognized 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;

125

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

E-mail: sgpatricio@ua.pt

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.

126

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

1Department of Physics and CICECO - Aveiro Institute of Materials, University of

Aveiro, 3810-193 Aveiro, Portugal; 2Instituto de Telecomunicações, University of Aveiro, 3810-193, Aveiro, Portugal;

3Laboratoire Charles Coulomb (L2C), UMR 5521 CNRS-Université de Montpellier, 34095 Montpellier, France

4Department of Electric and Computer Engineering and Instituto de Telecomunicações, Instituto Superior Técnico, Universidade de Lisboa, Lisbon,

Portugal.

E-mail: sandracorreia@ua.pt; ritafrias@ua.pt; rrondao@ua.pt; vania.freitas@ua.pt;

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.

127

ALKALI NIOBATE AND TANTALATE PEROVSKITES. ESTABLISH ING 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 Engineering, University of Aveiro, 3810-193 Aveiro, Portugal

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).

128

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

Engineering, University of Aveiro, 3810-193 Aveiro, Portugal 2SPCTS, Centre Européen de la Céramique, 12 rue Atlantis, 87068 Limoges Cedex, France

E-Mail: siriny.laumier@etu.unilim.fr

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

129

BIOPOLYMER-SILICA HYBRID PARTICLES PREPARED BY A NO N-EMULSION METHOD FOR ENVIRONMENTAL APPLICATIONS

Sofia F. Soares1, Tito Trindade1, Ana L. Daniel-da-Silva1

1 CICECO - Aveiro Institute of Materials, Department of Chemistry, University of

Aveiro, 3810-193 Aveiro, Portugal

E-mail: sofiafsoares@ua.pt

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] E. Ruiz-Hitzky, P. Aranda, M. Darder, M. Ogawa, Chemical Society Reviews 2011, 40, 801–28.

[2] S. F. Soares, T. Trindade, A. L. Daniel-da-Silva, European Journal of Inorganic Chemistry 2015, 27, 4588–4594.

130

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.

E-mail: sbruno@ua.pt

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.

131

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 CICECO - Aveiro Institute of Materials, Department of Chemistry, University of

Aveiro, 3810-193 Aveiro, Portugal 2 Chemical Research Center, Department of Chemistry and Biochemistry, Faculty of

Science, University of Porto, 4169-007 Porto, Portugal 3 Department of Biology, CESAM, University of Aveiro, 3810-193 Aveiro, Portugal

4 QOPNA, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal 5 CNC, University of Coimbra, 3004-504 Coimbra, Portugal

E-mail: tania.sintra@ua.pt

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 2,2-diphenyl-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-StG-337753.

132

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

1Department of Chemistry, CICECO – Aveiro Institute of Materials, University of

Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal

E-mail: tatiana.amarante@ua.pt

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 organic-inorganic 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 self-precipitating 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 = 1,2,4-triazole), 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-01-0124-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).

133

AN ALTERNATIVE EXTRACTION/CONCENTRATION APPROACH FO R 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

1CICECO - Aveiro Institute of Materials, Department of Chemistry, University of

Aveiro, 3810-193 Aveiro, Portugal 2Chemistry Department, CESAM, University of Aveiro, 3810-193 Aveiro, Portugal

3Instituto Politécnico de Coimbra, ESTESC-Coimbra Health School, Complementary Sciences, Rua 5 de Outubro, S. Martinho do Bispo, 3046-854 Coimbra, Portugal

E-mail: tbdinis@ua.pt

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.

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. 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.

134

MIXTURES OF IONIC LIQUIDS IN AQUEOUS BIPHASIC SYSTE MS: TAILORING THEIR FORMATION ABILITY AND EXTRACTION

EFFICIENCY

Teresa B. V. Dinis1, Helena Passos1, Mara G. Freire1, João A. P. Coutinho1

1CICECO - Aveiro Institute of Materials, Department of Chemistry, University of

Aveiro, 3810-193 Aveiro, Portugal 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. 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 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.

135

AN INVITATION TO MAGNETISM

V. S. Amaral1 and the MagLab team1,2

1Departamento de Física e CICECO

2 Departamento de Engenharia de Materiais e Cerâmica e CICECO

E-mail: vamaral@ua.pt

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-CT62-FEDER-002003, under the operation “capacitar o CICECO para internacionalizar a I&DT em materiais e incrementar a competitividade nacional”.

136

NOVEL BIOMEMBRANES BASED ON A PLA/CHOLINE BLEND SYS TEM

P. Barbosa1, J. M. Campos2, A. Turygin3, V. Shur3, A. Kholkin4 A. Barros-Timmons2, F.M. Figueiredo1

1CICECO - Aveiro Institute of Materials, Department of Materials & Ceramic

Engineering, U. of Aveiro, Portugal 2CICECO – Aveiro Institute of Materials, Department of Chemistry, U. of Aveiro,

Portugal 3Institute of Natural Sciences, Ural Federal University, 620000 Ekaterinburg, Russia

4CICECO – 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.