Highlighting CICECO Science: The Associate Laboratory Review 2013

free edition 3 A WORD FROM THE DIRECTORS A dozen years have passed since the associated laboratory CICECO was created in March 2002 at the University of Aveiro, Portugal. Entering the teenage years, we have matured and evolved into CICECO-Aveiro Institute of Materials, which better captures our present essence. Our Mission is developing the scientific and technological knowledge necessary for the innovative production and transformation of materials for a sustainable development and the benefit of society (from ceramics to soft matter and hybrids). By the end of 2013 we were 48 academic staff, 32 full-time researchers, 91 post-doctoral associates, 119 Ph.D. students and 77 other students working in the Departments of Chemistry, Physics, Materials and Ceramic Engineering and Biology. We are organized in 3 research themes, Information and Communication Technology, Energy and Industrial Applications, Sustainability and Health, and 5 research groups, Inorganic Functional Nanomaterials and Organic-Inorganic Hybrids, Multifunctional Ferroic Ceramics and Nanostructures, Materials for Energy and Functional Surfaces, Biorefineries, Biobased Materials and Recycling, Biomedical and Biomimetic Materials. These research highlights present some of the finest work done in the last three years. The word cloud in the cover and enclosed seizes some of the research areas where we are now most active. Words and papers we produce by the dozen but we never compromise with quality and are committed to continuously improve ourselves in the quest for scientific and cultural excellence. Aveiro, July 2014. João Rocha, Joaquim Vieira, Luís Carlos 4 Nanomaterials and Nanostructures 8 DIRECT IMAGING OF JOULE HEATING DYNAMICS AND TEMPERATURE PROFILING INSIDE A CARBON NANOTUBE INTERCONNECT Costa PMFJ, Gautam UK, Bando Y, Golberg D 8 GALVANIC REPLACEMENT REACTIONS IN METAL OXIDE NANOCRYSTALS Oh MH, Yu T, Yu SH, Lim B, Ko KT, Willinger MG, Seo DH, Kim, BH, Cho MG, Park JH, Kang K, Sung YE, Pinna N, Heyeon T 9 ALL-IN-ONE HEATER-THERMOMETER NANOPLATFORM OPERATIVE FROM 300 to 2000 K BASED ON Er3+ EMISSION AND BLACKBODY RADIATION Debasu ML, Ananias D, Pastoriza-Santos I, Liz-Marzan LM, Rocha J, Carlos LD 10 SENSING ACTIVE COATING ON THE BASIS OF NANOREACTORS CONTAINING pH INDICATING AGENT Maia F, Tedim J, Bastos AC, Ferreira MGS, Zheludkevich ML 11 DRY FERROFLUIDS Sousa FL, Trindade T, Silva NJO 12 SILVER-MODIFIED NANO-TITANIA AS AN ANTIBACTERIAL AGENT AND PHOTOCATALYST Tobaldi DM, Piccirillo C, Pullar RC, Gualtieri AF, Seabra MP, Castro PML, Labrincha JA 13 METAL-ORGANIC FRAMEWORKS BASED ON A PHOSPHONATE POLYMERIC ORGANIC LINKER Silva P, Vieira F, Gomes AC, Ananias D, Fernandes JA, Bruno SM, Soares R, Valente AA, Rocha J, Paz FAA 14 CHIRAL TRANSPOSING FROM DIPHOSPHONATE METAL-ORGANIC FRAMEWORK PRECURSORS TO POROUS LANTHANIDE PYROPHOSPHATES Shi FN, Paz FAA, Ribeiro-Claro P, Rocha J 15 MULTIFUNCTIONAL LANTHANIDE-ORGANIC FRAMEWORKS BASED ON A TRIPODAL PHOSPHONATE ORGANIC LINKER: PHOTOLUMINESCENCE AND HETEROGENEOUS CATALYSIS Vilela SMF, Firmino ADG, Mendes RF, Fernandes JA, Ananias D, Gomes AC, Valente AA, Ott H, Carlos LD, Rocha J, Tomé JPC, Paz FAA 16 FUNCTIONAL NANOSTRUCTURED COMPOSITE MATERIALS BASED ON BACTERIAL CELLULOSE Freire CSR, Silvestre AJD, Barros-Timmons A, Neto CP 16 SOFT NANOCOMPOSITES FOR STRONG SIGNAL ENHANCEMENT IN RAMAN SPECTROSCOPY Fateixa S, Daniel-da-Silva AL, Nogueira HIS, Trindade T 18 LANTHANOPOLYOXOMETALATE BASED COMPOSITE MATERIALS Nogueira HIS 19 EVIDENCE FOR ENTANGLEMENT AT HIGH TEMPERATURES IN AN ENGINEERED MOLECULAR MAGNET Brandão P, Moreira dos Santos A, Reis MS 20 USE OF INNOVATIVE ECO-BUILDING MATERIALS Tobaldi DM, Pullar RC, Seabra MP, Labrincha JA 21 SYNTHESIS AND STRUCTURE OF NOVEL INORGANIC LAYERED MATERIALS Lin Z, Wu ZY, Zhang XS, Brandão P, Dong JX 22 ANOMALY ON THE GRAIN GROWTH AND DIELECTRIC RESPONSE OF Ti-RICH STRONTIUM TITANATE CERAMICS Amaral L, Fernandes M, Reaney IM, Harmer MP, Senos AMR, Vilarinho PM 23 CAN POROSITY BE AN ADVANTAGE? YES, IT CAN! Ferreira P, Castro A, Laberty C, Boissière C, Grosso D, Sanchez C, Rodriguez B, Vilarinho PM 24 LOCAL BIAS INDUCED FERROELECTRICITY IN MANGANITES WITH COMPETING CHARGE AND ORBITAL ORDER STATES Figueiras FGN, Bdikin IK, Amaral VBS, Kholkin AL 25 AQUEOUS PROCESSING OF LEAD FREE 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TIO3 PIEZOELECTRIC CERAMIC MICRO-COMPONENTS FROM A POWDER SURFACE TREATED AGAINST HYDROLYSIS Kaushal A, Olhero SM, Ferreira JMF 26 NANOSCALE FERROELECTRICITY IN CRYSTALLINE Γ-GLYCINE Heredia A, Kholkin AL, Bdikin I, Gracio J, Meunier V, Balke N, Tselev A, Agarwal P, Sumpter BG, Kalinin SV 26 SYNERGISTIC CORROSION INHIBITION ON GALVANICALLY COUPLED MATERIALS Kallip S, Bastos AC, Ferreira MGS, Zheludkevich ML Energy, Lighting and Photonics 30 (3 + 3) DIMENSIONAL ‘HYPERCUBIC’ OXIDE-IONIC CONDUCTOR: TYPE II Bi2O3−Nb2O5 Ling CD, Schmid S, Blanchard PER, Pet í ek V, McIntyre GJ, Sharma N, Maljuk A, Yaremchenko AA, Kharton VV, Gutmann M, Withers RL 30 MATERIALS AND CONCEPTS FOR CARBON LEAN STEELMAKING BY PYROELECTROLYSIS Kovalevsky AV, Ferreira NM, Yaremchenko AA, Costa FM, Frade JR 31 SrTiO3 –BASED THERMOELECTRICS FOR EFFICIENT HIGH TEMPERATURE WASTE HEAT CONVERSION Kovalevsky AV, Yaremchenko AA, Populoh S, Weidenkaff A, Frade JR 32 Pr-SUBSTITUTED SrTiO3 AS PROSPECTIVE SOLID OXIDE FUEL CELL ANODE MATERIAL Yaremchenko AA, Patrício SG, Frade JR 33 OXYGEN-ION TRANSPORT IN Ba0.5Sr0.5Co0.8Fe0.2O3-d: DEVELOPMENTS OF ASYMMETRIC/MULTILAYER AND HOLLOW-FIBER CERAMIC MEMBRANES FOR OXYGEN SEPARATION Kovalevsky AV, Yaremchenko AA, Kolotygin VA, Buysse C, Middelkoop V, Snijkers F, Buekenhoudt A, Frade JR 34 CERAMIC TILES WITH CONTROLLED POROSITY AND LOW THERMAL CONDUCTIVITY BY USING POREFORMING AGENTS Novais RM, Seabra MP, Labrincha JA 35 MODULATING THE PHOTOLUMINESCENCE OF BRIDGED SILSESQUIOXANES FOR LUMINESCENT SOLAR CONCENTRATORS Correia SFH, André PS, Ferreira RAS, Carlos LD 35 PHOTONIC-ON-A-CHIP: A THERMAL ACTUATED MACH-ZEHNDER INTERFEROMETER AND A MOLECULAR THERMOMETER BASED ON A SINGLE DI-UREASIL ORGANIC-INORGANIC HYBRID Ferreira RAS, Brites CDS, Vicente CMS, Lima PP, Carlos LD, André PS 36 NOVEL BIFUNCTIONAL MAGNETIC-NEAR-INFRARED LUMINESCENT NANOCOMPOSITES: NEARINFRARED EMISSION FROM Nd and Yb Yu SY, Fu LS, Zhou YJ, Su Catalysis and Separation 40 SUPPORTED IONIC LIQUID SILICA NANOPARTICLES ARE EXCELLENT HETEROGENEOUS CATALYSTS FOR THE DEHYDRATION OF FRUCTOSE TO 5-HYDROXYMETHYLFURFURAL Sidhpuria KB, Daniel-da-Silva AL, Trindade T, Coutinho JAP 41 TARGETING BIO-DERIVED CHEMICALS BY TUNING THE PROPERTIES OF SOLID ACID CATALYSTS Antunes MM, Lima S, Neves P, Russo PA, Wiper PV, Fernandes A, Ferreira LR, Abrantes JP, Veiga JM, Pillinger M, Mafra L, Portugal I, Evtuguin DV, Pinna N, Rocha SM, Ribeiro MF, Valente AA 42 INVESTIGATION OF A DICHLORODIOXOMOLYBDENUM(VI)- PYRAZOLYLPYRIDINE COMPLEX AND A HYBRID DERIVATIVE AS CATALYSTS IN OLEFIN EPOXIDATION Amarante TR, Neves P, Paz FAA, Valente AA, Pillinger M, Gonçalves IS 43 IRON–SUBSTITUTED POLYOXOTUNGSTATES AND THEIR CATALYTIC APPLICATIONS Cavaleiro AMV, Nogueira HIS 44 COPPER(II) BIS(OXAZOLINE)-TYPE LIGANDS IMMOBILIZED ONTO MESOPOROUS SILICAS AND THEIR CARBON REPLICAS AS EFFICIENT ASYMMETRIC HETEROGENEOUS CATALYSTS FOR ORGANIC TRANSFORMATIONS Silva AR, Carneiro L, Guimarães V, Carvalho AP, Pires J 45 INTERCALATION OF MOLYBDENUM CARBONYL COMPLEXES IN LAYERED DOUBLE HYDROXIDES Gomes AC, Bruno SM, Gamelas CA, Valente AA, Abrantes M, Gonçalves IS, Romão CC, Pillinger M 46 CO2 ADSORPTION AND ACTIVATION BY AMINEMODIFIED NANOPOROUS MATERIALS STUDIED BY NMR AND 13CO2 ADSORPTION Pinto ML, Mafra L, Guil JM, Pires J, Rocha J INDEX 5 47 CARBOHYDRATES AND IONIC LIQUIDS IN AQUEOUS MEDIA: A MAJOR PATH TOWARDS A SUSTAINABLE DEVELOPMENT Freire MG, Louros CLS, Rebelo LPN, Coutinho JAP 48 ZEOLITIC INORGANIC MEMBRANES Lin Z, Cardoso SP, Silva CM 49 MODELING TRACER DIFFUSION COEFFICIENTS IN LIQUIDS, GASES AND SUPERCRITICAL FLUIDS Vaz RV, Magalhães AL, Gomes JRB, Silva CM 49 IONIC LIQUIDS MICROEMULSIONS: THE KEY TO CANDIDA ANTARCTICA LIPASE B SUPERACTIVITY Ventura SPM, Santos LDF, Saraiva JA, Coutinho JAP 50 SCALE-UP STUDIES OF THE SUPERCRITICAL FLUID EXTRACTION OF TRITERPENOIDS FROM EUCALYPTUS BARK Melo MMR, Silvestre AJD, Silva CM Biorefineries and Materials from Renewable Sources 54 2nd GENERATION BIOETHANOL PRODUCTION FROM DIFFERENT LIGNOCELLULOSIC RESIDUES Pereira SR, Fernandes MC, Gorwa-Grauslund MF, Evtuguin DV, Serafim LS, Xavier AMRB 55 ADVANCED CELLULOSE/SILICA HYBRID MATERIALS Evtuguin DV, Portugal I 56 TARGETED MODIFICATION OF CELLULOSIC MATERIALS USING ULTRAHIGH PRESSURE PROCESSING Evtuguin DV, Saraiva JA 56 POTENTIOMETRIC CHEMICAL SENSORS FROM LIGNIN-DERIVED NANOCOMPOSITES Rudnitskaya A, Evtuguin DV, Costa LC, Graça MPF, Correia, MRP, Fernandes AJS 57 GETTING VALUE FROM WASTES: BIOLOGICAL PRODUCTION OF BIODEGRADABLE PLASTICS Queirós DC, Xavier AMRB, Evtuguin DV, Rossetti S, Serafim LS 58 PLANT OIL-BASED LONG-CHAIN MONOMERS AND THEIR POLYMERS Vilela C, Silvestre AJD, Meier MAR 59 TWO STEPS FORWARD IN THE DEVELOPMENT OF FURAN-BASED POLYESTERS Sousa AF, Matos M, Freire CSR, Silvestre AJD, Coelho JFJ Biomedical Materials and Applications 62 SLOW RELEASE OF NO BY MICROPOROUS TITANOSILICATE ETS-4 Pinto ML, Rocha J, Gomes RJB, Pires J 63 QUANTIFYING WEAK PACKAGING INTERACTIONS IN THE HYDRATED AND ANHYDROUS FORMS OF ANTIBIOTIC CIPROFLOXACIN Mafra L, Santos SM, Siegel R, Alves I, Paz FAA, Dudenko D, Spiess HW 64 BACTERIAL CELLULOSE AS TRANSDERMAL DRUG DELIVERY SYSTEMS Silva NHCS, Silvestre AJD, Freire CSR, Neto CP 65 PHOTOTHERMALLY ENHANCED DRUG RELEASE BY HYDROGELS REINFORCED WITH CARBON NANOTUBES Estrada AC, Daniel-da-Silva AL, Trindade T 65 NOVEL BINUCLEAR COPPER COMPLEXES AS ALTERNATIVE ANTI-TUMORAL DRUGS: SYNTHESIS, CHARACTERISATION AND CYTOTOXIC STUDIES Brandão P, Ferreira BJML, Santos TM, Meireles M, Félix V 66 BONE MECHANICAL STIMULATION WITH PIEZOELECTRIC MATERIALS Reis J, Frias C, Silva FC, Potes J, Simões JA, Botelho ML, Castro CC, Marques AT 67 POLARIZATION SWITCHING IN HYDROXYAPATATIE: BONES CAN GROW FASTER Lang SB, Tofail SAM, Kholkin AL, Wojtaś M, Gregor M, Wang Y, Bauer S, Krause M, Plecenik A 69 CARBON NANOTUBE/BIOCERAMIC COMPOSITES FOR IN SITU ELECTRICAL STIMULATION OF BONE Mata D, Oliveira FJ, Neto MA, Bastos AC, Lopes MA, Gomes PS, Fernandes MHV, Silva RF 71 MODULATING CELLULAR RESPONSE WITH ENGINEERED HAP NANOPARTICLES Costa MEV, Almeida MM, Santos C 72 PIEZOELECTRIC PLLA AS A PLATFORM FOR TISSUE GROWTH Barroca N, Vilarinho PM, Daniel-da-Silva AL, Wu A, Fernandes MHV, Gruverman A 73 A NEW APPROACH TO THE PREPARATION OF PDMSSiO2 BASED HYBRIDS - A STRUCTURAL STUDY Almeida JC, Castro AGB, Salvado IMM, Margaça FMA, Fernandes MHV 74 SELECTIVE, ULTRASHSARP, BORON DOPED DIAMOND MICROELECTRODES Silva EL, Bastos AC, Neto MA, Silva RF, Ferreira MGS, Zheludkevich ML, Oliveira FJ 75 BIOMATERIALS FROM THE VALORISATION OF WASTE COD FISH BONES WITH APPLICATIONS IN PHOTOCATALYSIS, POLLUTION REMEDIATION AND SELF-STERILISING MATERIALS Piccirillo C, Pullar RC, Silva MF, Tobaldi DM, Pereira SIA, Braga da Cruz I, Marques APGC, Jorge R, Dunnill CW, Parkin IP, Labrincha JA, Castro PML, Pintado MM 76 SECOND TRIMESTER MATERNAL URINE FOR THE DIAGNOSIS OF TRISOMY 21 AND PREDICTION OF POOR PREGNANCY OUTCOMES Diaz SO, Barros AS, Goodfellow BJ, Duarte IF, Galhano E, Pita C, Almeida MC, Carreira IM, Gil AM 77 METABOLOMICS OF BLOOD PLASMA AND URINE SHOWS PROMISE IN LUNG CANCER DIAGNOSIS Rocha CM, Carrola J, Barros AS, Gil AM, Goodfellow BJ, Carreira IM, Bernardo J, Gomes A, Sousa V, Carvalho L, Duarte IF 78 POTENTIAL MARKERS OF CISPLATIN TREATMENT RESPONSE UNVEILED BY NMR METABOLOMICS OF HUMAN LUNG CELLS Duarte IF, Ladeirinha AF, Lamego I, Gil AM, Carvalho L, Carreira IM, Melo JB Computational Methods and Theory 82 HALOGEN-BONDING IN ANION RECOGNITION Costa PJ, Félix V, Beer PD 82 DEVELOPMENT OF SYNTHETIC ANION CARRIERS FOR REPLACEMENT THERAPIES: A COMPUTATIONAL APPROACH Félix V, Marques I, Colaço AR, Costa PJ, Busschaert N, Gale PA 84 DINUCLEAR RUTHENIUM(II) COMPLEXES FOR STABILIZING AND IMAGING AN ANTIPARALLEL FOLDED HUMAN TELOMERE SEQUENCE Félix V, Costa PJ, Williamson MP, Thomas JA, Wilson T 85 SIMPLE DESCRIPTORS FOR PREDICTING THE CATALYTIC ACTIVITY OF TRANSITION METAL SURFACES FOR O-H BOND DISSOCIATION REACTIONS Fajín JLC, Cordeiro MNDS, Illas F, Gomes JRB 86 ON THE ORIGINS OF THE MOLECULAR-SCALE PERIODICITY IN THE PORE WALLS OF PERIODIC MESOPOROUS ORGANOSILICAS Futamura R, Jorge M, Gomes JRB 87 COMBINING QUANTUM MECHANICS WITH MOLECULAR SIMULATION FOR PREDICTING ADSORPTION IN MOFS WITH UNSATURATED METAL SITES Jorge M, Fischer M, Gomes JRB 88 AB-INITIO VALIDATION OF A RELATION BETWEEN LOCAL ELECTRIC FIELD AND GLOBAL POLARIZATION IN FERROELECTRICS Gonçalves JN, Stroppa A, Correia JG, Butz T, Picozzi S, Fenta AS, Amaral V Outreach 90 “THE CHEMISTRY OF THINGS” MULTIMEDIA PROJECT Ribeiro-Claro P 91 WEBCAM-BASED SPECTROGRAPH FOR A STUDENT PROJECT Ferreira RAS, André PS 91 BRING DISCOVERY INTO THE CLASSROOM: HOW TO EVALUATE PLANCK’S CONSTANT USING SIMPLE EQUIPMENT Ferreira RAS, André PS Nanomaterials and Nanostructures Nanomaterials and Nanostructures14 CHIRAL TRANSPOSING FROM DIPHOSPHONATE METAL-ORGANIC FRAMEWORK PRECURSORS TO POROUS LANTHANIDE PYROPHOSPHATES Shi FN1, Paz FAA1, Ribeiro-Claro P1, Rocha J1 The synthesis of chirally-pure porous solids from achiral building blocks is an intriguing, nontrivial, and much promising field. The real challenge for chemists encompasses ensuring that only one of the possible enantiomorphs is formed in the syntheses. Among chiral inorganic materials most work has been concentrated on zeolites, some of which present chiral polymorphs, viz., zeolite-beta, SU32 and ITQ-37. ETS-10, a porous titanosilicate, also exhibits chiral polymorphs. In zeolite synthesis, chiral templating by addition of an organic molecule or cation to the synthesis medium has been a method of choice (although with limited success) to attempt imprinting the molecule’s chirality onto the inorganic framework. Chiral templating and chiral induction (the use of chiral solvents or chiral additives) methods utilized to engineer homochirality in porous solids have been reviewed recently [1]. We have reported the synthesis of chiral porous inorganic materials, lanthanide (Ln) pyrophosphates, from chiral porous Metal-Organic Framework (MOF) precursors, which upon thermal decomposition transpose their chirality and porosity onto the inorganic framework [2]. The crux of this single-crystal to single-crystal transformation lies in that the key structural modifications take place at a specific crystallographic site and, as a result, the topological features of the parent MOFs are transposed to the final crystalline inorganic frameworks, via an intermediate (also hybrid) material. Although the materials reported here possess relatively narrow pores they may be of interest for H2 storage or separation from gas mixtures. The hydrothermal reaction of etidronic acid (H5hedp) and lanthanide chlorides afforded a series of isotypical materials formulated as [Ln4(Hhedp)3(H2O)2] (Ln=Y3+, Ho3+, Dy3+ and Tb3) on the basis of single-crystal X-ray diffraction. A case in point, [Er4(Hhedp)3(H2O)2] (1) crystallizes in the chiral cubic I213 space (Figure 1). Heating 1 from ambient temperature to ca. 700 °C results in intriguing structural transformations, whose epicentre is the ligand itself (Figure 1). At ca. 450 °C, the water molecule coordinated to Er2 is released and the Hhedp4ligand decomposes around the central carbon atom (located on the two-fold axis) by releasing the -OH and -CH3 groups, which are replaced by a C-H group. A new hybrid material forms, [Er4(PO3-CH=PO3)3] (2), retaining the connectivity of the parent framework. At ca. 700 °C, 2 transforms into a purely inorganic pyrophosphate material, with the central C-H bond replaced by an oxygen atom, [Er4(PO3-OPO3)3] (3). Again, this structural transformation occurs at the two-fold site (C-H bond), with no modification of the overall network connectivity. Because the thermal structural modifications take place primarily at a specific crystallographic site, the topological features of the parent MOF material are imprinted onto the final crystalline inorganic framework 3, via the intermediate hybrid 2. We submit that it is worth considering extending these ideas to the synthesis of other chiral porous inorganic solids. Work along these lines is in progress. 1DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal References [1]Morris,RE,BuXH,Nature Chemistry,2010,2,353-361. [2]ShiF,PazFAA,Ribeiro-ClaroP,Rocha J,Chemical Communications,2013,49,11668-11670. Figure 1. Structural transformation of the frameworks and ligands, from room temperature to ca. 700 ºC: as-prepared [Er4(Hhedp)3(H2O)2]MOF1transformsintothehybrid[Er4(PO3-CH=PO3)3]network2atca.450ºC,whichuponfurtherheatingyields thepurelyinorganic[Er4(PO3-O-PO3)3]network3atca.700ºC. 1 Department of Chemistry, CICECO, University of Aveiro, 3810-193Aveiro,Portugal. 2 Central Analytical Laboratory, CICECO, University of Aveiro, 3810-193Aveiro,Portugal. Reference [1]SilvaP,VieiraF,GomesAC,AnaniasD,FernandesJA,Bruno SM, Soares R, Valente AA,Rocha J,PazFAA, Journal of the American Chemical Society,2011,133,15120-15138. Acknowledgments This research was funded by the European Union (QREN, COMPETE)andFCT(PTDC/QUI-QUI/098098/2008–FCOMP-010124-FEDER-010785). Nanomaterials and Nanostructures 15 reaction of the styrene oxide (PhEtO). Both MOFs exhibited excellent regioselectivity towards 2-methoxy-2-phenylethanol (always as the sole reaction product). They further showed to be truly heterogeneous catalysts that could be recycled by simple and efficient regeneration processes. Noteworthy, the 1D [La(H4bmt) (H5bmt(H2O)]∙3H2O material has much higher catalytic activity (conversion of 100% of PhEtO at 55 °C in only 30 min) than the 3D [La2(H3bmt)2(H2O)2]∙H2O material (conversion of 80% of PhEtO at 55 °C in 24 h). The outstanding catalytic activity of the 1D MOF catalyst is related with the amount of active sites available in its structure that are likely to be of Brönsted type. 1DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal 2DepartmentofChemistry,QOPNA,UniversityofAveiro,3810193Aveiro,Portugal 3Bruker AXS GmbH, Oestliche Rheinbrueckenstr, 49, 76187 Karlsruhe,Germany 4Department of Physics, CICECO, University of Aveiro, 3810193Aveiro,Portugal References [1]Vilela SMF, Ananias D, Gomes AC, Valente AA, Carlos LD, CavaleiroJAS,RochaJ,ToméJPC,PazFAA,Journal of Material Chemistry,2012,22,18354-18371. [2]VilelaSMF,FirminoADG,MendesRF,FernandesJÁ,Ananias D, Valente AA, Ott H, Carlos LD, Rocha J, Tomé JPC, Paz FAA, Chemical Communications,2013,49,6400-6402. Acknowledgments This research was funded by the European Union (QREN, COMPETE)andFCT(PTDC/QUI-QUI/098098/2008–FCOMP-01- -0124-FEDER-010785). MULTIFUNCTIONAL LANTHANIDE-ORGANIC FRAMEWORKS BASED ON A TRIPODAL PHOSPHONATE ORGANIC LINKER: PHOTOLUMINESCENCE AND HETEROGENEOUS CATALYSIS Vilela SMF1,2, Firmino ADG1,2, Mendes RF1, Fernandes JA1, Ananias D1, Gomes AC1, Valente AA1, Ott H3, Carlos LD4, Rocha J1, Tomé JPC2, Paz FAA1 Metal-Organic Frameworks (MOFs), also known as Coordination Polymers, are constructed from the self-assembly between metallic centers and organic ligands. This new class of materials opens the window to customizable high porosity materials, with high surface area, thermal, mechanical and chemical robustness, and to the design of luminescent, magnetic and catalytic devices. Because of this rich versatility MOFs may find applicability in distinct fields such as gas storage and separation, ionexchange, heterogeneous catalysis, magnetism, as optical sensors, among others. Our research group have been interested in the preparation of multifunctional Lanthanide-Organic Frameworks (LnOFs) based on multipodal phosphonate organic linkers. We have designed and prepared two families of LnOFs containing the new (benzene-1,3,5-triyl(methylene)triphosphonic acid (H6bmt) ligand (Figure 1):[1, 2] 1D [Ln(H4bmt)(H5bmt(H2O)]∙3H2O materials [where Ln3+ = La3+, (La0.97Eu0.03)3+ and (La0.97Eu0.03)3+] prepared using microwave irradiation (40 ºC for 5 min); 3D [Ln2(H3bmt)2(H2O)2]∙H2O frameworks [where Ln3+ = La3+, Ce3+, Pr3+, Nd3+, (La0.95Eu0.05)3+ and (La0.95Tb0.05)3+] prepared using both hydrothermal conditions (100 ºC for 1 day) or microwave irradiation (150 °C for 5 min). Isotypical 3D materials can be fully dehydrated under heating (above ca. 100 °C), with or without vacuum, while their crystalline structures remain unaltered. When kept in contact with atmospheric air, the dehydrated compounds are easily rehydrated. The zeolitic behaviour of the 3D Eu3+-based material led to an increase of the quantum efficiency in ca. 3.6 times (from ca. 15 to 54%). Both 1D and 3D Tb3+-based MOFs have remarkable absolute emission quantum yields (ca. 44 and 46%). The heterogeneous catalytic activity of the 1D [La(H4bmt)(H5bmt(H2O)]∙3H2O and the 3D [La2(H3bmt)2(H2O)2]∙H2O materials were investigated in the ring-opening Figure 1.(left)Schematicrepresentationofthepreparationofthe3D[La2(H3bmt)2(H2O)2]∙H2O,anditsdehydratedform[La(H3bmt)],andofthe1D[La(H4bmt)(H5bmt(H2O)]∙3H2Opolymer.(right) Catalyticactivityof[La2(H3bmt)2(H2O)2]∙H2O(onthetop)andof[La(H4bmt)(H5bmt(H2O)]∙3H2O(atthebottom)inthering-openingreactionofstyreneoxidewithmethanolat55ºC. Nanomaterials and Nanostructures16 In the last decades there has been an increasing awareness in the search for bio-based alternatives as sources of novel (nano)composites for application in several fields such as packaging, biomedical products and devices, as well as in high technology domains. Nanocellulose forms like bacterial cellulose (BC), biosynthesized by several bacteria as a 3D network of nanoand micro-fibrils, have gained particular attention in this context because of its unique features, namely high purity, water holding capacity, crystallinity, tensile strength and Young modulus, that can be successfully exploited in the development of innovative nanostructured composite materials.[1] Bacterial nanocellulose based composite materials can be prepared following different strategies, including compounding with synthetic thermoplastic matrices[2], combination/blending with other natural polymers[3,4] and in situ polymerization with different monomers[5-8]; resulting in functional materials with improved thermal stability and mechanical perFUNCTIONAL NANOSTRUCTURED COMPOSITE MATERIALS BASED ON BACTERIAL CELLULOSE Freire CSR1, Silvestre AJD1, Barros-Timmons A1, Neto CP1 formance and bearing properties such as transparency, biocompatibility, bioactivity, hydrophobicity, conductivity, among others (Figure 1). It is clearly demonstrated that bacterial nanocellulose is a suitable biopolymer for the development of innovative nanostructured composites following different approaches. The final properties of the nanocomposites can be tailored by changing the monomer type, the ratio polymer/ BC or the modification approach. These nanostructured porous composites could find applications in several fields namely in controlled release of drugs or other bioactive compounds, electronic devices, among others. 1 Department of Chemistry, CICECO, University of Aveiro, 3810-193Aveiro,Portugal References [1]FigueiredoARP,VilelaC,Neto CP,SilvestreAJD,FreireCSR, Bacterial cellulose based nanocomposites: a roadmap for innovative materials, in:Nanocellulose Polymer Nanocomposites: Fundamentals and Application(KumarV.Ed.),Wiley,inpress. ISBN:978-1-118-87190-4. [2]ToméLC,PintoRJB,TrovattiE,FreireCSR,SilvestreAJD,Neto CP,GandiniA,Green Chemistry,2011,13,419-427. [3]Trovatti E,Fernandes SCM,Rubatat L,Freire CSR,Silvestre AJD,NetoCP,Cellulose,2012,19,729-737. [4]ToméLC,FernandesSCM,PerezDS,SadoccoP,SilvestreAJD, NetoCP, MarruchoIM, FreireCSR,Cellulose,2013,20, 1807- -1818. [5]Fernandes SCM, Sadocco P, Alonso-Varona A, Palomares T, Eceiza A, Silvestre AJD, Mondragon I, Freire CSR, ACS Applied Materials and Interfaces,2013,5,3290-3297. [6]Lacerda PSS, Barros-Timmons AMMV, Freire CSR, Silvestre AJD,NetoCP,Biomacromolecules,2013,14,2063-2073. [7]FigueiredoA,FigueiredoA,Alonso-VaronaA,FernandesSCM, Palomares T, Rubio E, Barros-Timmons A, Silvestre AJD, Neto CP, Freire CSR, BioMed Research International, 2013, article number698141. [8]Gadim TDO, Figueiredo A, Vilela C, Rosero-Navarro NC, GamelasJAF,Barros-TimmonsA,NetoCP,SilvestreAJD,Freire CSR, Figueiredo FML, ACS Applied Materials and Interfaces, 2014,6,10,7864-7875. Figure 1.Examplesofnanostructuredcompositespreparedusingbacterialnanocelluloseanddifferentmethodologies. The Surface-Enhanced Raman Scattering (SERS) effect refers to a method of Raman spectroscopy (Fig.1) in which some chemical species exhibit strong Raman signal enhancement when interacting with metal surfaces, typically silver and gold.[1] The high sensitivity of SERS, that in certain conditions can reach the molecular level, associated to specifically designed plasmonic nanostructures makes SOFT NANOCOMPOSITES FOR STRONG SIGNAL ENHANCEMENT IN RAMAN SPECTROSCOPY Fateixa S1, Daniel-da-Silva AL1, Nogueira HIS1, Trindade T1 this a technique of choice for a number of nanotechnologies of practical interest in medicine and environmental monitoring. However, the widespread use of this technique is still dependent on a number of requisites, which include the availability of analytical platforms that are user friendly and easily processed using standard technologies. Our interest in this research problem led us to investigate the development of new nanocomposites as Nanomaterials and Nanostructures 17 new analytical platforms for SERS. These nanocomposites comprise a polymer matrix containing metal nanoparticles. Furthermore, we have been interested in exploiting new functionalities that might arise in these nanocomposites but not observed in the original components. Two selected examples of our recent research in this topic are described below, that involve the use of a synthetic and a natural polymer as the matrices, and Ag nanoparticles as the fillers. Organically capped Ag nanoparticles (average diameter ~11 nm) have been used as nanofillers in poly(t-butylacrylate) composites prepared by in situ polymerization via miniemulsions.[2,3] This synthetic strategy enabled the dual use of the final composites as SERS substrates, both as aqueous emulsions and as cast films, using thiosalycilic acid and adenine as molecular probes (Fig.2). The Ag/PtBA materials still showed SERS activity when submitted to temperature cycles (-60°C to 65°C), which suggests that the adsorbates were retained at Ag sites eventually protected by the surrounding polymer layers. This work demonstrated the potential of this approach to fabricate nanocomposites that can be regarded as scalable, versatile and handy SERS substrates contributing to the implementation of Raman analytical tools in a widen context. Carrageenan hydrogels containing Ag nanoparticles have been investigated as new colloidal platforms for SERS using 2,2’-dithiodipyridine as the analytical probe (Fig.3). These studies have been performed for a series of nanocomposites in which the gel strength was varied by using several strategies, including the increase of the polysaccharide content in the gel, the addition of KCl as cross-linker, and the variation of the type of carrageenan network. This research led to the first report of a direct correlation between the gel strength of a hydrogel composite used as substrate and its analytical SERS sensitivity.[2,4] A mechanism has been suggested for these findings that considers an increasing number of hot spots due to the formation of Ag particles nanojunctions when the biopolymer matrix tends to rearrange into stronger gels (Fig.3). 1DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal References [1]NogueiraHIS,Teixeira-DiasJJC,TrindadeT,Encyclopedia of Nanoscience and Nanotechnology,H.S.Nalwa(Ed),ASP,2004, 7, 699. [2]FateixaS,PhDThesis,2013,UniversityofAveiro. [3]FateixaS,GirãoAV,NogueiraHIS,TrindadeT,JournalofMaterialsChemistry,2011,21,15629. [4]FateixaS,Daniel-da-SilvaAL,NogueiraHIS, TrindadeT, The Journal of Physical Chemistry C, 2014, 118 (19), 10384- -10392. Figure 3.CarrageenanhydrogelscontainingAgnanoparticlesandvariablepolysaccharidecontentthatshowSERSsensitivitydependentontheinducedgelstrength. Figure 2.SERSactivenanocompositesintheformofanaqueousemulsioncontainingpoly(t-butylacrylate)beadsencapsulating Agnanoparticles. Figure 1.TheNobelPrizeinPhysics(1930)wasawardedtothe scientistChandrasekharaVenkataRamanforresearchonthe scatteringoflightandforthediscoveryoftheeffectnamedin hishonor. Nanomaterials and Nanostructures18 LANTHANOPOLYOXOMETALATE BASED COMPOSITE MATERIALS Nogueira HIS1 Polyoxometalates (POMs) are discrete cluster anions of metal oxides with a range of dimensions that goes from less than 1 nm (small anions with a few metal atoms like [Mo7O24]6-) to large anionic clusters in the nanometer range (one of the biggest being [HxMo368O1032(H2O)240( SO4)48]48- (x ≈ 16) with 5.4 nm width, the “nano-hedgehog”). POMs show very extensive and versatile properties, due to the variety on its composition and structural motifs. The idea of tailor-made POM design in synthetic chemistry is not far from what is achieved in current research. Still there is a big gap between POMs design and its specific applications. The assembly of these inorganic clusters in hybrid materials of adequate processability and stability, that keep the POM functionality, is a big challenge in POM research. There has been great interest on the use of lanthanopolyoxometalates (LnPOMs) as functional units in nanostructured composite materials. The presence of the lanthanide confers specific functionalities to LnPOM compounds, in particular the photoluminescent properties. We have reported a number of new photoluminescent materials based on LnPOMs incorporated into layered double hydroxides, layer-by-layer assemblies and LangmuirBlodget thin films or encapsulated in core-shell silica nanoparticles. Organicinorganic hybrid materials were prepared using LnPOM anions as inorganic building blocks and organic ligands such as 3-hydroxypicolinate[1]; in these materials intra-4f emission of Ln(III) (Ln = Eu, Tb and Er) ions is sensitized both by the 3-hydroxypicolinate ligand and the POM moiety. The preparation of LnPOM/graphene composites (Fig. 1) has been explored and the effect of graphene grafting on the luminescent properties studied[2]. Detailed photoluminescence studies have shown that there is efficient emission from the LnPOMs in those composite materials, in particular for the europium derivatives, with excitation paths that involve O→Eu and O→W ligand-to-metal charge-transfer transitions. A series of polysaccharide-based transparent composite films containing LnPOMs was prepared[3] using a water-soluble cationic chitosan derivative (HTCC = N-(2hydroxypropyl)-3-trimethylammonium chitosan chloride) and pullulan (PUL). HTCC was more adequate than pure chitosan due to its positive charge and solubility in water at a broad range of pH values. LnPOMs of [Ln(W5O18)2]9- (Ln(III) = Eu and Tb) type were incorporated in the polysaccharides (Fig. 2). EuPOMs encapsulated in amorphous silica shells were also incorporated in the polysacFigure 1. (a)TEMimageofthecompositeLnPOM/Graphene-Oxidewherethepresenceofelongatedstructures(1-LnPOMrods)is visible.(b)Amagnifiedviewoftheareaboxedin(a). Figure 2.Incorporationoflanthanopolyoxometalatessuchas[Eu(W5O18)2]9-(bottomstructure)inachitosanderivative(HTCC,top structure)originatescleartransparentfilmsthatshowthelanthanideemissionunderUV(photographunder366nmexcitation). Nanomaterials and Nanostructures 19 Entanglement, a sort of quantum correlation, plays an important role in quantum information science because it can be used as resource for many quantum information processing protocols[1]. Therefore, the study of entanglement in solid-state physics is of great relevance to the area of quantum information, since many proposals of quantum processors are solid-state based. The recent demonstration that entanglement can change the thermodynamic properties of solids, such as magnetic susceptibility, shows that entanglement can be related to significant macroscopic effects. Hence, this subject establishes an interesting connection between quantum information theory and condensed-matter physics, because magnetization, heat capacity, and internal energy can also be used to reveal spin entanglement among constituents of a solid. Quantum entanglement at elevated temperatures has been studied in several physical systems and the recent work by Vedral[2] summarizes this scenario. In that work it is recognized that some molecular magnets remain entangled at surprisingly high temperatures. Besides presenting robust entangled states, such materials can be engineered to enhance their quantum features and, consequently, to be better suited for quantum information applications. As an example, it was recently shown, through magnetic susceptibility measurements, that certain families of molecular magnets are entangled up to 630 K, and have the maximum degree of entanglement at temperatures as high as 100 K[3]. In order to obtain systems with the highest entanglement temperature, which should contain antiferromagnetically coupled magnetic ions with the highest possible spin states, a systematic study of molecular iron compounds was made, which resulted in the preparation of a new di-iron complex with formula [Fe2(μ2-oxo) (C3H4N2)6(C2O4)2]. The crystal structure consists of a di-nuclear μ-oxo Fe(III) complex where the bridging oxygen atom is at the crystallographic inversion center and the metal-to-metal distance is of 3.594(9) Å with a Fe–O–Fe angle of 180°. The Fe(III) center is six-coordinated in a distorted octahedra coordination in which the equatorial plane is composed of three nitrogen donors from imidazole ligands (2.095(2), 2.147(2) and 2.168(2) Å), and one oxygen atom of oxalate ligand (2.042(2) Å). The apical positions are occupied by the μ-oxo bridging atom (1.797(5) Å) and by the other oxalate oxygen (2.152(2) Å), as shown in figure 1. The magnetic susceptibility of this compound was measured from EVIDENCE FOR ENTANGLEMENT AT HIGH TEMPERATURES IN AN ENGINEERED MOLECULAR MAGNET Brandão P1, Santos AM2, Reis MS3 charides, in order to test the effect on the film processing of having a nanoparticles loading instead of LnPOM anions. The incorporation of LnPOMs or LnPOM-silica core-shell nanoparticles in either HTCC or PUL polysaccharides originated clear transparent films. These composite films are transparent under daylight exhibiting visible emission while under UV excitation (Fig. 3). 1DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal References [1] GranadeiroCM,FerreiraRAS,Soares-SantosPCR,CarlosLD, NogueiraHIS,European Journal of Inorganic Chemistry,2009, 5088-5095. [2]GranadeiroCM,CruzSMA,GonçalvesG,MarquesPAAP,Costa PMFJ, Ferreira RAS, Carlos LD, Nogueira HIS, RSC Advances, 2012,2,9443-9447. [3]PintoRJB,GranadeiroCM,FreireCSR,SilvestreAJD,NetoCP, FerreiraRAS,CarlosLD,CavaleiroAMV,TrindadeT,NogueiraHIS, European Journal of Inorganic Chemistry,2013,1890-1896. Acknowledgments ThisworkhasbeenfundedbyFCT(Portugal)andCOSTAction CM1203. Figure 3.PhotographsofPULfilmswithdifferentEuPOMloadings(a)2.5%,(b)5%,(c)10%,(d)40%andloadingsof(e)TbPOM,(f) EuPOM@SiO2and(g)EuL@SiO2,takenunder366nmradiation.Filmssizeisapproximately5cmx5cm. Nanomaterials and Nanostructures20 The energy efficiency and the carbon footprint of modern building are highly reduced. On the other hand, these airtight and sealed environments have created unexpected side effects, realising potentially harmful chemicals in the air, hence potentially causing negative impacts on human being. Our research group, involved in the European project ECO-SEE (ECO-innovative, Safe and Energy Efficient wall panels and materials for a healthier indoor environment), aims at addressing that emerging health problem, associated with modern low carbon buildings. The goal is to study the use of innovative eco-building materials that will not only address poor air quality, but also will radically improve the energy efficiency of buildings. One of our group involvements is the full development of highly novel photocatalytic coatings by the use of nanoparticle technology, which will decompose harmful chemicals when exposed to sunlight (simulating an outdoor environment) or visible light (recreating real indoor situation), preventing them from being released into the air. 1 Department of Materials and Ceramic Engineering, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal References [1]Tobaldi DM, Pullar RC, Seabra MP, Labrincha JA, Materials Letters,2014,122,345–347. [2]TobaldiDM,PullarRC,SeverŠkapinA,SeabraMP,Labrincha JA,Materials Research Bulletin,2014,50,183–190. Acknowledgments WethanktheEuropeanUnion’sSeventhFrameworkProgramme (grant agreement nº 609234) and FCT (PEst-C/CTM/ LA0011/2013andCincia2008programmes). Figure 2Photocatalyticresults,depictingtheinitial(20min)pseudo-firstorderkineticconstantsforsomecommercial(darkgrey), andsynthesisednanoTiO2samples(blue).ThemodelpollutantwasNOx,thelightsourceawhite-lightlamp(irradiance=7Wm–2), simulatinganindoorenvironment. USE OF INNOVATIVE ECO-BUILDING MATERIALS Tobaldi DM1, Pullar RC1, Seabra MP1, Labrincha JA1 2 to 300 K. The analysis of the susceptibility data using protocols developed for other spin singlet ground-state systems indicates that the quantum entanglement would remain at temperatures up to 732 K, significantly above the highest entanglement temperature reported to date[4]. The large gap between the ground state and the first-excited state (282 K) suggests that the spin system may be somewhat immune to decohering mechanisms. Our measurements strongly suggest that molecular magnets are promising candidate platforms for quantum information processing. 1 Department of Chemistry, CICECO, University of Aveiro, 3810-193Aveiro,Portugal 2NSSD,OakRidgeNationalLaboratory,OakRidge,Tennessee 37831-6475,USA 3 InstitutodeFísica,UniversidadeFederalFluminense,24210- -340,RiodeJaneiro,Brasil References [1]Vedral V, Introduction to Quantum Information Science (OxfordUniversityPress),2006. [2]VedralV,Scientific American,2011, June issue,2011,38. [3]Souza AM, Soares-Pinto DO, Sarthour RS, Oliveira IS, Reis MS,BrandãoP,SantosAM,Physical Review B,2009,79,054408. [4]Reis MS, Soriano S, Santos AM, Sales BC, Soares-Pinto DO, BrandãoP,EPL,2012,100,50001. Figure 1. Crystal structure details of [Fe2(μ2-oxo) (C3H4N2)6(C2O4)2];left-Molecularstructure;right–irondimmer polyhedralrepresentation. Figure 1.BanneroftheECO-SEEproject(www.eco-see.eu). Nanomaterials and Nanostructures 21 The development of a new technology requires a continuous search for new materials and/or new properties of traditional materials. With the advent of the nanotechnology era, the increasing interest turns to the use of layered materials for device applications. Layered materials have been delaminated. The exfoliated layers have thickness at nano scale and can be used as additives to improve the gas selectivity of polymer membrane and as a solid lubricant additive to improve the load-carrying capacity. On the other hand, the knowledge on the structure will help us to explain properties and to predict the applications. Copper zirconium phosphate (CuZr(PO4)2∙4H2O,) was usually prepared by high temperature Cu(II) ion exchange from Zr(HPO4)2∙H2O and was used in different application for long time although its structure is not clearly known yet. Rare earth borates are important due to their excellent properties, especially for optics. The synthesis research showed that their formation is sensitive to the synthesis conditions. By hydrothermal synthesis, high crystalline copper zirconium phosphate [with more precise chemical formulae from the structure point of view, Cu(OH)2Zr(HPO4)2∙2H2O, Cu-α-ZrP] has been directly obtained. Its crystal structure has been determined ab initially by using laboratory powder X-ray diffraction data, showing a laminar structure with ZrPO layers and Cu(II) between them. In the structure, Cu(II) was located in an exchangeable position and was certified to be exchangeable by the proton. Cu-α-ZrP was evaluated as an additive of grease in a four ball test, showing better effect in improving the load-carrying capacity of lithium grease than MoS2, a typical solid lubricant additive. The maximum non-seizure load (PB, represent the load-carrying capacity) of base grease containing Cu-α-ZrP was increased from 353 N to 1235 N. The excellent load-carrying capacity can be explained by its easier cleavage and adherence to the worn surface forming the tight protective layer (Fig.1).[1] By careful selection of synthesis conditions, three samarium polyborates have been prepared hydrothermally in very similar experimental conditions, of which two [SmB6O8(OH)5×B(OH)3 (1), SmB6O8(OH)5×B(OH)3×H2O (2)] possess new structures and their structures have been determined by single-crystal X-ray diffraction data.[2] The two layered materials are structurally related and constituted by hexaborate chains. The hexaborate chains are connected by samarium polyhedra, forming dense sheets which further interact with each other by hydrogen bonding via isolated boric acid between these sheets (Fig.2). The compound 2 also has hydrogen bonded water molecules between dense sheets. From structure point of view, the new layered samarium borate compound 2 may be able to transform to compound 1 and NaNdB6O9(OH)4 by careful selection of treatment conditions. The distance between dense sheets of compound 2 can be easily altered by heating or ion exchange with Na, being expected easy cleavage of layers. 1Department of Chemistry, CICECO, University of Aveiro, 3810-193,Aveiro,Portugal 2ResearchInstituteofSpecialChemicals,TaiyuanUniversityof Technology,Taiyuan,030024,Shanxi,P.R.China References [1]Zhang XS, Xu H, Zuo ZJ, Lin Z, Ferdov S, Dong JX, Applied Materials & Interfaces,2013,5,7989-7994. [2]WuZY,BrandãoP, LinZ, Inorganic Chemistry,2012,51, 3088-3093. SYNTHESIS AND STRUCTURE OF NOVEL INORGANIC LAYERED MATERIALS Lin Z1, Wu ZY1, Zhang XS2, Brandão P1, Dong JX2 Figure 2. Crystalpackingofcompounds1and2.GreenballsrepresentsamariumwhiledashedlinesrepresentO-H…Ohydrogen bondinteractions. Figure 1. Cu(OH)2Zr(HPO4)2∙2H2Ostructureanditsapplication toimprovetheload-carryingcapacityoflithiumgrease. Nanomaterials and Nanostructures22 Strontium titanate based materials have a great interest for a wide range of applications in microelectronics namely in tunable microwave devices, due to the high electric-field dependence of the permittivity and more recently as a possible thermoelectric material where special attention is being paid to the important role of grain boundaries to improve the figure of merit of this material. Grain boundaries in ceramics are mainly formed during the sintering process and are moving, enabling the coarsening of the microstructures by grain growth. We have investigated the grain growth of 0.5 mol% Ti-rich SrTiO3 composition over a wide range of sintering temperatures, from 1400 up to 1650 °C, in air, and the evolution of bulk and grain boundary electrical response with the sintering temperature was assessed by impedance spectroscopy. This technique allows to address separately the grain boundary impedance response and therefore to detect changes in the grain boundary dielectric properties. A grain growth anomaly in Ti-rich strontium titanate ceramics is here reported: discontinuities on the evolution of grain growth with the sintering temperature were observed, defining four grain growth regimens with transitions at temperatures around 1500, 1550 and 1605 °C (Figures 1 and 2). These transitions correspond to grain size decreases, despite the increasing sintering temperature. We also show that similar discontinuities can be observed in the dependence of the grain boundary activation energy for conductivity and in the grain boundary thickness, assessed by impedance spectroscopy (Figure 2). These notable coincidences are reported for the first time and strongly support the formation of different grain boundary complexions in polycrystalline oxides with transitions in between the observed grain growth regimens, which may be correlated to different grain boundary mobility and dielectric properties. Grain boundary dielectric response was much more affected by the sintering temperature than that of the bulk counterpart, strongly reinforcing the idea of the key role played by the grain boundaries in the anomaly in the grain growth observed for Ti-rich SrTiO3. We postulate that this anomalous behavior is directly related to a 1st order reverse change of complexions driven by the temperature effect on the grain boundary wettability and electrostatic potential. These new insights have great scientific and technological relevance in tailoring the microstructure and dielectric response of SrTiO3-based materials and related systems and using grain boundary complexion behavior for materials properties design. 1Department of Materials and Ceramic Engineering, CICECO, UniversityofAveiro,3810-193Aveiro,Portugal 2Center for Advanced Materials and Nanotechnology, Lehigh University,Bethlehem,Pennsylvania18015,UnitedStates 3DepartmentofEngineeringMaterials,UniversityofSheffield, Sheffield,S13JD,UK References [1]AmaralL,FernandesM,SenosAMR,VilarinhoPM,HarmerMP, Microscopy and Microanalysis,2012,18(S5),123-124. [2]AmaralL,FernandesM,ReaneyIM,HarmerMP,SenosAMR, VilarinhoPM,The Journal of Physical Chemistry C,2013,117 (47),24787–24795. ANOMALY ON THE GRAIN GROWTH AND DIELECTRIC RESPONSE OF TI-RICH STRONTIUM TITANATE CERAMICS Amaral L1, Fernandes M1, Reaney IM3, Harmer MP2, Senos AMR1, Vilarinho PM1 Figure 1.SEMmicrostructuresofsamplessinteredatseveraltemperatures(indicatedontheimages).Inspiteofthecontinuous increaseofthesinteringtemperature,thedecreaseofthegrainsizeisobvious.Arrowssignalizetheregimentransitionswithdecreasingofthegrainsize. Figure 2.Illustrationofthesimilartrendsobservedforthedependenceoftheaveragegrainsize,grainboundaryactivation energyforconductivityandgrainboundarythicknessonthe sinteringtemperature. Nanomaterials and Nanostructures 23 CAN POROSITY BE AN ADVANTAGE? YES, IT CAN! Ferreira P1, Castro A1, Laberty C2, Boissière C2, Grosso D2, Sanchez C2, Rodriguez B3, Vilarinho PM1 In 1965, Moore’s predicted that the number of transistors per integrated circuit will double approximately every two years. This trend, known as Moore´s law has been verified up to recently, however due to size and thermal management, this miniaturization trend is reaching the limits. Indeed a new trend emerged in the Semiconductor Industry Roadmap encompassing functionalities that do not necessarily scale, but provide additional value to the end customer in different ways, allowing the development of valueadded systems. The Electroceramics group has been actively engaged in developing strategies to prepare porous ferroic films to be used as startup matrices for multifunctional materials, namely for multiferroics. Multiferroic materials have been actively studied as a route to control magnetoelectric coupling and to enable a range of applications whereby magnetism can be controlled by an electric field. Single phase, room temperature multiferroics are rare, because of that a variety of approaches to prepare composite multiferroic materials have been tried. In a collaboration involving Researchers from Group 2 of CICECO, the University Pierre et Marie Curie, France and the University College Dublin, Ireland we have successfully prepared porous ferroelectric thin films[1] and systematically studied the effect of porosity on the local electric properties.[2] Nanoporous piezoand ferroelectric barium titanate and lead titanate thin films (~100 nm calculated from ellipsometric data) were prepared starting from sol−gel solutions modified with a commercially available block-copolymer and evaporation-induced self-assembly methodology. The tuning of the thermal treatment followed by in situ ellipsometry allows the decomposition of the organic components and of the structuring agent leading to the formation of porous tetragonal crystalline perovskite structures as observed by XRD, HRTEM, SEM, and ellipsoporosimetry. Both nanoporous barium titanate and lead titanate thin films present local piezoelectric and ferroelectric behavior measured by piezoresponse force microscopy (PFM). A recent study aiming the understanding of the effect of porosity on the electric properties at the nano-scale demonstrated the crystallization of the tetragonal phase at lower temperatures in porous than in dense films. Nanoporous films with improved tetragonality exhibit enhanced piezoelectric coefficients, switchable polarization and low local coercivity (Figure 1).By providing a means of achieving enhanced properties, nanoporosity may have a broad impact in applications of ferroelectric thin films by themselves and also as platforms to reach multifunctional devices. 1 Depart.MaterialsandCeramicsEngineering,CICECO, UniversityofAveiro,3810-193Aveiro,Portugal 2 Lab. Chimie de la Matière Condensée de Paris, UMR-7574 CNRS,UPMCUniversité,Paris06,France 3 SchoolofPhysics,UniversityCollegeDublin,Dublin,Ireland References [1]FerreiraP,HouRZ,WuA,WillingerMG,VilarinhoPM,MosaJ, Laberty-RobertC,BoissièreC,GrossoD,SanchezC,Langmuir, 2012,28,2944. [2]CastroA,FerreiraP,RodriguezBJ,VilarinhoPM,Journalof MaterialsChemistryC,2014,accepted. Acknowledgments ThisworkwasfundedbyFCT,FEDER,EuropeanUnionthrough theprojectsFCOMP-01-0124-FEDER-009356(Refª.FCTPTDC/ CTM/098130/2008) and FCOMP-01-0124-FEDER-037271 (Refª.FCTPEst-C/CTM/LA0011/2013). Figure 1.SEM,topographicandPFMimagesandlocalhysteresisloopsobtainedinnanoporousanddensePbTiO3filmsafterthermal treatmentat:550and575ºC,respectively.Ferroelectricpropertiesareenhancedinnanoporousfilms. Energy, Lighting and Photonics30 The high-temperature cubic form of bismuth oxide, δ-Bi2O3, is the best intermediate-temperature oxide-ionic conductor known. The well-established way of stabilizing δ-Bi2O3 to room temperature, while preserving a large part of its conductivity, is by doping with higher valent transition metals to create wide solid-solutions fields with exceedingly rare and complex (3+3)-dimensional incommensurately modulated ‘hypercubic’ Type II structures. These materials remain poorly understood because no such structure has ever been quantitatively solved and refined, due to the complexity of the problem and lack of adequate experimental data. In the present work, this was addressed by growing a large (centimeter scale) crystal using a novel refluxing floating-zone method, collecting highquality single-crystal neutron diffraction data, and treating its structure together with X-ray diffraction data within the superspace symmetry formalism[1]. The Type II structure can be understood as an ‘inflated’ pyrochlore, in which the cornerconnected NbO6 octahedral chains move smoothly apart to accommodate the solid solution. While some oxide vacancies are ordered in these chains, others are distributed throughout a continuous threedimensional network of wide δ-Bi2O3like channels (Figure 1), explaining the superior oxide-ionic conductivity of incommensurate Type II phase compared to commensurately modulated Type III phases in the same pseudobinary system (Figure 2). 1SchoolofChemistry,TheUniversityofSydney,Australia 2InstituteofPhysics,ASCR,v.v.i.,TheAcademyofSciencesof theCzechRepublic 3InstitutLaue-Langevin,Grenoble,France 4 Leibniz Institute for Solid State and Materials Research Dresden,Germany 5 Department of Materials and Ceramic Engineering, CICECO, UniversityofAveiro,3810-193Aveiro,Portugal 6 ISIS, Science and Technology Facilities Council, Rutherford AppletonLaboratory,UK 7ResearchSchoolofChemistry,AustralianNationalUniversity, Canberra,Australia Reference [1]LingCD, SchmidS,Blanchard PER,Pet í ekV,McIntyreGJ, SharmaN,MaljukA,YaremchenkoAA,KhartonVV,GutmannM, WithersRL, Journal of the American Chemical Society,2013, 135,6477-6484. (3 + 3) – DIMENSIONAL ‘HYPERCUBIC’ OXIDE-IONIC CONDUCTOR: TYPE II Bi2O3−Nb2O5 Ling CD,1 Schmid S,1 Blanchard PER,1 Pet í ek V,2 McIntyre GJ,3 Sharma N,1 Maljuk A,4 Yaremchenko AA,5 Kharton VV,5 Gutmann M,6 Withers RL7 Figure 1.RefinedstructureofTypeII(Bi2O3)0.795(Nb2O5)0.205:view along the <110000> direction, drawn over 8×8×8 fluoritetypesubcells.Biatomsarepurple,andNbatomsandpolyhedra aregreen. Figure 2. Partial oxide-ionic (σO) and electronic (σe) conductivitiesfortheceramicsamplesofTypeIIandTypeIII (Bi2O3)0.76(Nb2O5)0.24. Pyroelectrolysis emerged as a key factor for feasible production of aluminium and is also providing breakthrough approaches for production of strategic metals from molten halite/oxide systems. Expected gains in energy efficiency by thermal activation at very high temperatures also raise prospects for challenging low-CO2 steelmaking, to overcome the environmental impact of classical extractive metallurgy. However, this requires challenging new concepts to meet harsh conditions imposed by very high temperatures and very corrosive nature of molten media, such as consumable anode materials, freeze lining cathodes and autothermal self regulation. One proposed the concept of consumable anodes relying on slowly consumable magnetite-based spinels, to tackle the materials challenges of electrical conductivity and other required properties, without undue contamination of the molten electrolyte and produced steels, and acting as a supplementary raw material. However, the redox stability of magnetite is insufficient for prospective operating conditions (temperature, oxidizing atmospheres and anodic polarization). Thus, one demonstrated strategies for higher refractoriness and enhanced redox stability over wider ranges, by codoping of magnetite with redox stable Mg and Al oxides in the concentration range where aluminium provides improvement of refractoriness without significant deterioration of electric properties, whilst magnesium increases tolerance against oxidative decomposition.[1] Guidelines for improved compromise between stability and electrical properties were also drawn for (Fe,Mg)3O4 spinels, with additions of transition metal oxides. The oxidation state of substituting cation, and preference for tetrahedral or octahedral MATERIALS AND CONCEPTS FOR CARBON LEAN STEELMAKING BY PYROELECTROLYSIS Kovalevsky AV1, Ferreira NM1,2, Yaremchenko AA1, Costa FM2, Frade JR 1 Energy, Lighting and Photonics 31 coordination determine the fractions of Fe2+ in spinel lattice, with impact on tolerance to oxidative decomposition, and effects on Fe2+:Fe3+ ratio in octahedral sites, which determines electronic transport. Trade-off relations (Fig. 1) show good prospects for application of (Fe,Al,Mg)3O4 and (Fe,Ti,Mg)3O4 spinels as slowly consumable ceramic anodes. [2] Preliminary electrochemical studies of such electrodes in contact with molten magnesium aluminosilicate glass showed that the level of anodic polarization must also be controlled to ensure redox and chemical stability in molten electrolyte. One also demonstrated an alternative concept of pyroelectrolysis based on yttriastabilized zirconia cells (Fig. 1), and used this configuration to study mechanisms and possible limitations of iron extraction by pyroelectrolysis. Electrochemical measurements and post-mortem SEM/ EDS analyses indicated that high current yields are possible in electron-blocking mode using the solid electrolyte membrane. Faradaic efficiency was assessed by integrating the time dependence of electrolysis current; this revealed limitations imposed by parasitic electrochemical processes, mainly on lowering the Fe concentration in the molten electrolyte. These results suggest that the concept of solid electrolyte membrane for separation of cathodic and anodic compartments may become essential, if one seeks pyroelectrolysis with high current yields. They also show that the concentration of iron oxide in the molten electrolyte may be optimized. 1Department of Materials and Ceramic Engineering, CICECO, UniversityofAveiro,3810-193Aveiro,Portugal 2 i3N,Department ofPhysics,UniversityofAveiro, 3810-193 Aveiro,Portugal References [1]Kovalevsky AV, Yaremchenko AA, Naumovich EN, Ferreira NM,MikhalevSM,CostaFM,FradeJR,Journal of the European Ceramic Society,2013,33,2751-2760. [2]FerreiraNM,KovalevskyAV,NaumovichEN,YaremchenkoAA, ZakharchukKV,CostaFM,FradeJR,JJournal of the European Ceramic Society,2014,34,2339-2350. Acknowledgments ThisworkwassupportedbyFCT,PortugalandbytheEuropean UnionResearchFundforCoalandSteel(RFCS). Figure 1. (under right) Total electrical conductivity in air for Fe2.6Me0.2Mg0.2O4 spinel-type materials; (left and upper right) ElectrochemicalYSZcellforassessingthemechanismofpyroelectrolysisprocessandrepresentativeresults. Thermoelectric materials are very flexible for thermoelectric cooling and raise good prospects for natural or waste heat recovery. Thermoelectric conversion requires both p-type and n-type materials. Their dimensionless figure of merit (ZT=sa2×T/k), which increases with electrical conductivity (s) and Seebeck coefficient (a), and decreases with thermal conductivity (k), determines the gap between the actual efficiency of thermoelectric generation and Carnot efficiency hcC TT /1 −=η . This implies that efficiency increases rapidly with temperature of heat source Th for its effects on Carnot efficiency and figure of merit, provided that this is not limited by thermal and/ or redox stability. Thus, oxides are best suited for high temperature waste heat recovery due to stability limitations of Teor Se-based thermoelectric materials, skutterudites and related intermetallic compounds. Donor-substituted strontium titanate is, probably, the most promising n-type oxide thermoelectrics. One engineered its thermoelectric properties by defect chemistry and structural changes, accomplished by A-site substitution with rare-earth elements or B-site substitution with Nb, and high temperature firing under reducing conditions. One demonstrated enhanced thermoelectric performance of SrTiO3 by A-site substitution with praseodymium[1], attaining maximum figure of merit for Sr0.90Pr0.10TiO3 (ZT ~0.23 at 670 K and ~0.34 at 1170 K). One also addressed, for the first time, A-site cation deficiency as a structural engineering approach yielding higher thermoelectric performance[2]. Formation of oxygen vacancies was found to suppress lattice thermal conductivity at low and intermediate temperatures. For both Prand Nbsubstituted titanates, nominal A-site deficiency results in significant enhancement of thermoelectric performance (Fig. 1). The positive impact of oxygen deficiency on thermoelectric properties inspired further studies of other rare-earth substituted strontium titanate ceramics, preSrTiO3 –BASED THERMOELECTRICS FOR EFFICIENT HIGH TEMPERATURE WASTE HEAT CONVERSION Kovalevsky AV1, Yaremchenko AA1, Populoh S2, Weidenkaff A2, Frade JR1 Energy, Lighting and Photonics32 Donor-doped strontium titanate is known to be stable in both oxidizing and reducing conditions and to exhibit substantial electronic conductivity (if reduced at high temperatures), and, therefore, is considered as a prospective sulfur-tolerant component for solid oxide fuel cell anodes. The present work was focused on appraisal of praseodymium-substituted SrTiO3 for possible application in SOFC anodes, with emphasis on phase relationships and structural stability under different conditions, electrical transport properties, thermochemical expansion and its compatibility with solid electrolytes, and dimensional stability in redox cycles. Sr1-xPrxTiO3±δ and Sr1-1.5xPrxTiO3±δ (x = 0.020.30) ceramic samples were prepared by conventional solid-state reaction route and sintered under either oxidizing (air, 1600-1750°C) or reducing (10%H2-N2, 1400-1500°C) conditions. XRD studies confirmed the formation of single-phase ceramic materials with perovskite-like structure in both oxidizing and reducing atmospheres, although microstructural studies indicated a minor precipitation of TiO2 in reduced Sr-deficient ceramics with high Pr content. XPS analysis in combination with XRD demonstrated that praseodymium cations substitute into strontium sublattice in mixed 4+/3+ oxidation state (~ 1:1 ratio) and are essentially insoluble in titanium sublattice under applied conditions. Taking into account the lattice electroneutrality condition, all oxidized materials exhibit oxygen excess correlated with praseodymium content and accommodated, most likely, in a form of extended defects (such as rock-salt layers characteristic for Ruddlesden-Popper structures of Srn+1TinO3n+1). Thermogravimetric analysis showed that under reducing conditions Sr1-xPrxTiO3±δ solid solutions retain overall oxygen overstoichiometry, while Sr1-1.5xPrxTiO3±δ are characterized with minor oxygen deficiency. Reduction at elevated temperatures results in 2-3 orders of magnitude increase of n-type electronic conductivity with respect to oxidized materials. The electrical conductivity of Sr0.90Pr0.10TiO3±δ and Sr1-1.5xPrxTiO3±δ (x = 0.10-0.20) at 600-800°C under reducing conditions reaches as high as 130-340 S/cm (Fig.1). TGA and electrical studies (Fig.2) demonstrated however very slow reduction kinetics at temperapared in strongly reducing conditions. A marked improvement in performance was observed for Sr0.9R0.1TiO3±δ (R= Nd, Sm, Dy) by sintering in 10%H2-90%N2 at 1773 K for 10 h, reaching ZT values as high as 0.42 at 1190-1225 K (Fig. 2). This performance exceeds previous limits for SrTiO3-based bulk thermoelectrics and is attributed to enhanced phonon scattering in oxygen-deficient perovskite layers. These results also show that highly-reducing conditions are needed for micro/ nanostructural engineering to suppress thermal conductivity, without undue effects on electrical conductivity and Seebeck coefficient, and while retaining outstanding thermal and redox stability. 1Department of Materials and Ceramic Engineering, CICECO, UniversityofAveiro,3810-193Aveiro,Portugal 2Empa,SolidStateChemistryandCatalysis,Ueberlandstr.129, CH-8600Duebendorf,Switzerland References [1]Kovalevsky AV, Yaremchenko AA, Populoh S, Weidenkaff A, FradeJR.,Journal of Applied Physics,2013,113,053704. [2]Kovalevsky AV, Yaremchenko AA, Populoh S, Weidenkaff A, FradeJR,The Journal of Physical Chemistry C,2014,118, 4596-4606. Acknowledgments ThisworkwassupportedbyFCT,Portugal. Pr-SUBSTITUTED SrTiO3 AS PROSPECTIVE SOLID OXIDE FUEL CELL ANODE MATERIAL Yaremchenko AA1, Patrício SG1, Frade JR1 Figure 1. Temperature dependence of electrical conductivity ofreducedSr1-xPrxTiO3±d(A)andSr1-1.5xPrxTiO3±d(B)ceramicsin 10%H2-N2atmosphere(p(O2)~10-19atmat900°C). Figure 1. Temperature dependence of the dimensionless figure of merit and lattice counterpart of the thermal conductivityforA-sitestoichiometricanddeficient(Sr,Pr) TiO3±dandSryTi0.8Nb0.2O3±d. Figure 2. Thermoelectric properties of Sr0.9R0.1TiO3±d titanates, preparedinstronglyreducingconditions. Energy, Lighting and Photonics 33 Figure 2.Variationsofelectricalconductivityofporousoxidized Sr0.90Pr0.10TiO3±d (A) and Sr0.85Pr0.10TiO3±d (B) ceramic samples in one redox cycle at 900°C. Thick green line indicates the conductivity value for dense reduced ceramics in 10%H2-N2 atmosphereat900°C. Dense ceramic membranes with mixed ionic and electronic conductivity provide a viable alternative to cryogenic distillation for oxygen separation, and are expected to offer significant economic benefits if integrated in industrial energy conversion processes such as coal gasification and oxyfuel combustion. Oxygen transport across ceramic membrane occurs via diffusion of oxygen ions in the crystal lattice of oxide material, thus providing absolute theoretical selectivity of oxygen separation. This work addresses several factors determining the performance of ceramic membranes made of Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF, a perovskite-like oxide with highest reported oxygen permeability) and relevant for the developments of membranes with multilayer supported architecture and capillary (or hollow-fiber) geometry. The oxygen transport studies of dense BSCF ceramic membranes demonstrated that the permeation rate is predominantly controlled by surface exchange kinetics when the membrane thickness is smaller than 1.00 mm. In order to improve oxygen exchange, an asymmetric membrane concept including two porous layers (with one thick porous layers acting as a support) and one thin dense central layer was implemented (Fig.1A). The amount of graphite as a pore-forming additive, powder compaction and sintering conditions were optimized to produce threelayer membranes having appropriate mechanical strength and microstructure. Comparison of the data on oxygen permeation through three-layer and dense 1.00 mm thick symmetric membranes indicated that a moderate improvement of the overall performance was achieved due to asymmetric architecture. The oxygen fluxes through the membrane with 170 µm dense layer and porous layers with thicknesses of 1.05 mm and 100 µm at 900°C were found to be ∼1.5-1.8 times higher compared to 1.00 mm thick symmetric membrane. Analysis of oxygen permeability data suggests however that three-layer architecture introduces additional permeation-limiting factor – gas diffusion in porous layers, thus indicating a need for further microstructural optimization. Another issue relates to the effect of sulphur contamination on the performance of BSCF membranes. Capillary and hollow-fiber ceramic membranes are commonly prepared by phase-inversion process using polysulphone or polyethersulphone as a binder. The decompositures below 1273 K associated mainly with nearly frozen equilibrium in cation sublattice and low oxygen vacancy concentration in oxidized materials. All oxidized and reduced materials exhibit moderate almost p(O2)-independent thermal expansion coefficients ((11.3-12.6)×10-6 K-1 at 251100°C), which ensure the compatibility with common solid electrolytes, and favorably small chemical expansion on reducing oxygen partial pressure. 1Department of Materials and Ceramic Engineering, CICECO, UniversityofAveiro,3810-193Aveiro,Portugal Reference [1]Yaremchenko AA, Patrício SG, Frade JR, Journal of Power Sources,2014,245,557-569. Acknowledgments This work was supported by the FCT, Portugal (projects BPD/75943/2011, PTDC/CTM-CER/118933/2010 and PEst-C/ CTM/LA0011/2011,andCiência-2008program). OXYGEN-ION TRANSPORT IN Ba0.5Sr0.5Co0.8Fe0.2O3-δ: DEVELOPMENTS OF ASYMMETRIC/MULTILAYER AND HOLLOW-FIBER CERAMIC MEMBRANES FOR OXYGEN SEPARATION Kovalevsky AV1, Yaremchenko AA1, Kolotygin VA1, Buysse C2, Middelkoop V2, Snijkers F2, Buekenhoudt A2, Frade JR1 Figure 1. SEM micrographs of fractured cross-section of (A) asymmetricthree-layerBSCFmembrane(thickporouslayer: 1.05mm,denselayer:170µm,thinporouslayer:60µm),and (B)sulphur-contaminated BSCFmembranewithsulphur-free BSCFporoussurfacelayer. Figure 2. Comparison of the oxygen permeation fluxes (j) throughsulphur-free(nS)andsulphur-contaminatednon-modified(S)andsurface-activated(S-activated)BSCFmembranes at950and850°C.p2andp1arefeed-sideandpermeate-side oxygenpartialpressures,respectively,anddisthemembrane thickness. Energy, Lighting and Photonics34 tion of the sulphur-containing binder during the calcination/sintering leads to the formation of sulphates, which negatively affect the oxygen permeation through the membrane. In present work, the comparative analysis of the oxygen transport through sulphur-free and sulphur-contaminated BSCF membranes indicated that sulphates decrease the permeation rate mostly due to the partial blocking of the surface oxygen exchange, whilst the bulk ambipolar conductivity remains essentially unchanged. SEM/EDS studies revealed segregation of BaSO4 at the grain boundaries, which are presumably responsible for the fast surface oxygen exchange in phase-pure BSCF. The negative impact of sulphur contamination on oxygen permeation was more pronounced at temperatures below 850°C. It has been demonstrated that by surface activation (i.e. application of thin porous layer of S-free BSCF at the membrane surface (Fig.1B)) the oxygen flux through sulphur-contaminated BSCF membranes can be increased to the level characteristic for sulphur-free membranes (Fig.2). 1Department of Materials and Ceramic Engineering, CICECO, UniversityofAveiro,3810-193Aveiro,Portugal 2Flemish Institute for Technological Research, VITO NV, Boeretang200,B-2400Mol,Belgium References [1]Kovalevsky AV, Yaremchenko AA, Kolotygin VA, Shaula AL, KhartonVV,SnijkersFMM,BuekenhoudtA,FradeJR,Naumovich EN,Journal of Membrane Science,2011,380,68-80. [2]Yaremchenko AA, Buysse C, Middelkoop V, Snijkers F, BuekenhoudtA,FradeJR,KovalevskyAV,Journal of Membrane Science,2013,428,123-130. Acknowledgments This work was supported by the FCT, Portugal (projects PTDC/CTM/64357/2006 and PEst-C/CTM/LA0011/2011, and Ciência-2008program),BelgianFederalSciencePolicyfoundation(FODSciencepolicy),andtheGermanHelmholtzAlliance project‘‘MEM-BRAIN’’. This work reports the influence of two pore forming agents (polypropylene – PP, and polymethyl methacrylate – PMMA), their incorporation content and particle size distribution on the bi-layered ceramics porosity, mechanical resistance and thermal conductivity. The porosity level was independent of porogen particle size distribution; nevertheless, pore area and number were heavily dependent on the porogen’s particle size distribution. Smaller pore formers prompted a high number of pores, while larger particles had the opposite effect. The upper-layer (dense layer) of the bi-layered ceramic showed typical microstructure of a commercial product, thus the release of gases from the bottom layer did not induce additional porosity. The incorporation of porosity into the bilayered ceramics promotes thermal conductivity attenuation and simultaneously decreases the ceramics mechanical resistance, however maintaining suitable mechanical strength. The thermal conductivity attenuation is adjustable as a function of volume and size of the generated pores. Attenuation up to 79% was achieved in comparison with standard porcelain stoneware compositions. These results demonstrate that bi-layered ceramics can be prepared with variable thermal conductivity, tailored for specific applications. The prepared tiles limit the energy loss, in comparison with conventional stoneware tiles, thus increasing the thermal comfort inside buildings, and energy savings. The nature of the pore forming agent did not affect the bi-layered ceramics properties, and both PMMA and PP generated, after burn out, high open porosity levels. Even if PMMA is most frequently used as a pore forming agent, our work demonstrated that PP presents similar behavior, and thus great potential as a pore forming agent. The large scale production and availability of PP reduce its production costs, which represent an important asset in comparison with other pore forming agents. 1Department of Materials and Ceramic Engineering, CICECO, UniversityofAveiro,CampusUniversitriodeSantiago,3810193Aveiro,Portugal Reference [1]NovaisRM,SeabraMP,LabrinchaJA,Ceramics International, 2014, 40,8,A,11637–11648. Acknowledgments We thank Portuguese Innovation Agency (ThermoCer, project nº23143)andFCT(PEstC/CTM/LA0011/2013). CERAMIC TILES WITH CONTROLLED POROSITY AND LOW THERMAL CONDUCTIVITY BY USING PORE- -FORMING AGENTS Novais RM1, Seabra MP1, Labrincha JA1 Figure 1.a)Imageofabi-layeredceramictile(10x10cm)andopticalmicroscopycharacterizationofthesintereddiscscontaining distinctPMMAcontentinthebottompart:b)2.5wt%,c)10wt%,d)15wt%ande)20wt%. Figure 2.Thermalconductivityoftheporousceramic,prepared withPMMAandPP,asfunctionofporosity. Energy, Lighting and Photonics 35 In the framework of a collaboration with Institut Charles Gerhardt, Montpellier, France, new urea-bipyridine derived bridged organosilanes have been synthesized in the presence of Eu3+ [1,2] and Tb3+ [2] salts led to luminescent thin films (thickness ca. 50 nm). The Eu3+-derived films (Figure 1) exhibit one of the highest emission quantum yields reported so far for films of Eu3+-containing hybrids (0.34±0.03) and an interesting potential as new luminescent solar concentrators (LSCs) with an optical conversion efficiency of ∼4%. The ratio between the light guided to the film edges and the one emitted by the surface of the film was quantified through the mapping of the intensity of the red pixels (in theRGB colormodel) froma film image. This quantification enabled a more accurate estimation of the transport losses due to the scattering of the emitted light in the film (0.40), thereby correcting the initial optical conversion efficiency to a value of 1.7% [1]. This is a very rare example of the use of Ln3+-containing hybrid thin films for LSCs. Moreover, through the optimization of the optical conversion efficiency by increasing the Eu3+ concentration, film thickness, and geometry, opens the possibility of increasing the photocurrent generated by solar cells coupled to the LSC edges, relative to the same cells facing the sun. 1Department of Physics, CICECO, University of Aveiro, 3810193Aveiro,Portugal 2 Instituto de Telecomunicações, University of Aveiro, 3810193,Aveiro,Portugal 3Department of Electric and Computer Engineering and Instituto de Telecomunicações Instituto Superior Técnico, UniversidadedeLisboa,Lisbon,Portugal References [1]GraffionJ,CattoënX,Chi-ManMW,FernandesVR,AndréPS, FerreiraRAS,CarlosLD,Chemistry of Materials,2011,23,4773. [2]GraffionJ,CojocariuAM,CattoënX,FerreiraRAS,Fernandes VR, André PS, Carlos LD, Chi-Man MW, Bartlett JR, Journal of Materials Chemistry,2012,22,13279. Acknowledgments Funding was provided by Fundação para a Ciência e a Tecnologia (FCT), FEDER, COMPETE, under contracts PEst-C/ CTM/LA0013/2011 and PTDC/CTM/101324/2008 and SFRH/ BD/91263/2012(SFHC). MODULATING THE PHOTOLUMINESCENCE OF BRIDGED SILSESQUIOXANES FOR LUMINESCENT SOLAR CONCENTRTATORS Correia SFH1,2, André PS3, Ferreira RAS1, Carlos LD1 Figure 1.a)SchematicrepresentationofthepossibleinteractionsbetweentheEu3+ion(fullcircle)andonedi-ureido-2,20-bipyridineligand.b)Photographandc)intensitymapoftheredpixelofthe Eu3+-basedfilmexcitedat365nm.Thetopedgeofthephotographcorrespondstothemoreintenseprofileintheintensitymap. In the framework of collaboration with Instituto de Telecomunicações and the VTT Technical Research Centre of Finland an integrated photonic-on-a-chip device based on a single organic-inorganic di-ureasil hybrid was fabricated for optical waveguide and temperature sensing. The device is composed by a thermal actuated Mach-Zehnder (MZ) interferometer patterned on the surface of the di-ureasil films operating with a switching power of 0.011 W and a maximum temperature difference between branches of 0.89 °C. The MZ interferometer is covered by a Eu3+/ Tb3+ co-doped di-ureasil luminescent molecular thermometer with a temperature uncertainty of 0.1°C and a spatial resolution of 13 µm. This is an uncommon example in which the same material (an organic-inorganic hybrid) that is used to fabricate a particular device (a thermalactuated MZ interferometer) is also used to measure one of the device intrinsic properties (the operating temperature). Moreover, the photonic-on-a-chip example discussed here can be applied to sense temperature gradients with a resolution of 10−3 °C·μm−1 in chip-scale heat engines PHOTONIC-ON-A-CHIP: A THERMAL ACTUATED MACH- -ZEHNDER INTERFEROMETER AND A MOLECULAR THERMOMETER BASED ON A SINGLE DI-UREASIL ORGANIC-INORGANIC HYBRID Ferreira RAS1, Brites CDS1, Vicente CMS1,2, Lima PP1, Carlos LD1, André PS3 Energy, Lighting and Photonics36 or refrigerators, magnetic nanocontacts and energy-harvesting machines, for instance. 1Department of Physics, CICECO, University of Aveiro, 3810193Aveiro,Portugal 2Instituto de Telecomunicações, University of Aveiro, 3810193,Aveiro,Portugal 3Department of Electric and Computer Engineering and Instituto de Telecomunicações Instituto Superior Técnico, Uni- versidadedeLisboa,Lisbon,Portugal Reference [1]FerreiraRAS,BritesCDS,VicenteCMS,LimaPP,BastosARN, MarquesPG,HiltunenM,CarlosLD,AndréPS,Laser & Photonics Reviews,2013,7,1035. Acknowledgments Funding was provided by Fundação para a Ciência e a Tecnologia (FCT), FEDER, COMPETE, under contracts PEst-C/ CTM/LA0013/2013, PTDC/CTM/101324/2008, SFRH/ BPD/34365/2006 (PPL), SRFH/BPD/87473/2012 (CV) and SFRH/BPD/89003/2012(CDSB).TheOrganicElectronicsgroup fromInstituto deTelecomunicações-Portugalisgratefullyacknowledgedtomakeavailableamaterialsinkjetprinting. In recent years, research toward nearinfrared (NIR) emitting systems based on lanthanide (Ln) complexes, such as neodymium (Nd), ytterbium (Yb), and erbium (Er), has become increasingly prevalent, even though visible fluorophores still dominate the luminescence field. However, for many applications, it is quite troublesome for lanthanide-based NIR materials to separate small particles from liquid. Considerable attention has been drawn to the nanoparticles with magnetic property, as a type of important functional material, because of their great potential applications in magnetic fluids, catalysis, biotechnology/biomedicine, magnetic resonance imaging (MRI), magnetic recording devices, and environmental remediation. Among magnetic particles, magnetite (Fe3O4) has received more attention because of its potential applications in nanobiotechnology. Therefore, Ln-based NIR materials combined with Fe3O4 magnetic nanoparticles can be conveniently separated from the aqueous phase by application of an external magnetic field. Herein, we report the synthesis of novel magnetic-NIR luminescent bifunctional nanomaterials, in which Fe3O4 magnetic particles were embedded in the silica nanospheres and Nd-PABI and Yb-PABI (PABI = N-(4-benzoic acid-yl)- N’-(propyltriethoxysilyl)urea) complexes were covalently bonded to the surface of magnetic silica.[1] The synthesis process is shown in Fig. 1. NOVEL BIFUNCTIONAL MAGNETIC-NEAR-INFRARED LUMINESCENT NANOCOMPOSITES: NEAR-INFRARED EMISSION FROM Nd AND Yb Yu SY1,2, Fu LS2, Zhou YJ2, Su1 Figure 1.SchematicrepresentationoftheMZinterferometergeometryshowingthemetalliccontacts,(lightgrey),MZinterferometer (blue)anddi-ureasillayerthermometer(red).Imageselectedbythepublisherasback-coverofthereferencepaper. Figure 1.Synthesisofbifunctionalmagnetic-opticalnanoparticles. Energy, Lighting and Photonics 37 The TEM images of bifunctional magnetic-NIR luminescent nanoparticles Fe3O4@SiO2@Ln-PABI (Ln = Nd, Yb) show the two kinds of particles with diameter ranged from 150 to 180 nm. The presence of core Fe3O4 nanoparticles and the core-shell structure are also confirmed, which show obvious differences in terms of contrast between the core and its surroundings. The magnetic properties of these two nanocomposites were characterized using a VSM with fields of up to 1 T. The saturation magnetizations of the Fe3O4@SiO2@ Nd-PABI and Fe3O4@SiO2@Yb-PABI nanoparticles at room temperature reach the saturation moment of 12.5 and 14.8 emu per gram, respectively. The more obvious proof for the magnetic properties could be found in the following designed experiments (Fig. 2). When a handheld magnet was placed close to the glass vial, the bifunctional nanoparticles were attracted toward the magnet very quickly. We can easily drag the nanoparticles from the bottom to the middle of glass vial by elevating the magnets. This observation further proves the bifunctional materials will be easy to control. The emission spectra of Fe3O4@SiO2@ Ln-PABI@SiO2 nanocomposites were measured by excitation of the Nd3+ and Yb3+ ion at 355 nm. For Nd material, the emission spectrum consists of three bands at 895, 1065, and 1325 nm, attributed to the 4F3/2→4I9/2, 4I11/2, and 4I13/2 transitions, respectively. For Yb material, the typical 2F5/2→2F7/2 transition at 980 nm was detected. These bifunctional nanocomposites exhibit superparamagnetic behaviour, high fluorescence intensity and color purity. 1CollegeofChemistry&ChemicalEngineering,InnerMongolia University,Hohhot010020,PRChina 2Department of Physics, CICECO, University of Aveiro, 3810193,Aveiro,Portugal Reference [1]Yu SY, Fu LS, Zhou YJ and Su HQ, Photochemical & Photobiological Sciences,2011,10(4),548-553. Acknowledgments ThisworkwassupportedbyFCT(Portugal)andNSFC(China). Figure 2. An aqueous suspension of bifunctional magneticoptical nanoparticles (a), after magnetic capture (b), and movement of the magnet dragging the concentrated nanoparticles(c). Catalysis and Separation Catalysis and Separation46 Global warming and climate changes are probably among the most difficult challenges for the humankind in the next century. Carbon dioxide emissions from anthropogenic sources are the main causes of the greenhouse effect and associated climate changes. Nanoporous materials functionalized with amine groups selectively retain large amounts of CO2 and may be regenerated, suggesting that they be used in cyclic processes for the CO2 separation from the remaining flue gases. The interaction of CO2 with the amine groups at the gas/solid interface is, however, not well understood, hindering the design of improved material for its capture or conversion to other high-value chemicals. In this work we have studied the interaction of gaseous CO2 with the surface of nanoporous clays functionalized with primary amines using several techniques. Adsorption of CO2 experiments and adsorption microcalorimetry revealed high adsorption capacity and strong interaction with the clays surfaces at low pressures, due to the presence of amine groups (Figure 1). Considerable surface heterogeneity and high initial adsorption heat (125 kJ mol-1) were observed, although the adsorption was reversible with hysteresis at low pressures and very slow desorption kinetics. The interaction between 13CO2 and the surface of the nanoporous clay materials was investigated by 13C and 15N magic-angle spinning NMR. 13C NMR resonances at ca. 164 and 160 ppm were assigned to, respectively, carbamate and carbamic acid, and the stability of these species have been studied (Figure 2). Peak areas and the amount of 13CO2 adsorbed allowed the determination of the concentration of carbamate and tween the LDH layers upon reaction of the intercalated dicarbonyl complexes with TBHP (Fig. 1). Following this work, we have successfully immobilized other molybdenum carbonyl complexes in LDHs, namely the tetracarbonyl complex cis-[Mo(CO)4(bpdc)] by an ion-exchange method, and the cyclopentadienyl complex (η5-C5H5) Mo(CO)3(CH2COO–) by a direct coprecipitation route. These inorganic/organometallic host-guest systems may find applications in several important fields such as nonlinear optics and biomedicine. 1DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal 2InstitutodeTecnologiaQuímicaeBiológicadaUniversidade NovadeLisboa,2780-157Oeiras,Portugal 3Centro de Quıímica Estrutural, Complexo Interdisciplinar, Instituto Superior Técnico, Universidade Técnica de Lisboa, 1049-001Lisboa,Portugal References [1]GomesAC,BrunoSM,GamelasCA, ValenteAA,AbrantesM, GonçalvesIS,RomãoCC,PillingerM,Dalton Transactions,2013, 42,8231-8240. [2]Gamelas CA, Gomes AC, Bruno SM, Paz FAA, Valente AA, PillingerM,RomãoCC,GonçalvesIS,Dalton Transactions,2012, 41,3474-3484. Acknowledgments The authors acknowledge FEDER, COMPETE and the FCT for the projects CICECO - FCOMP-01-0124-FEDER-037271 (FCT ref. PEst-C/CTM/LA0011/2013) and FCOMP-01-0124FEDER-029779(FCTref.PTDC/QEQ-SUP/1906/2012). CO2 ADSORPTION AND ACTIvATION bY AMINEMODIFIED NANOPOROUS MATERIALS STUDIED bY NMR AND 13CO2 ADSORPTION Pinto ML1, Mafra L1, Guil JM3, Pires J2, Rocha J1 Figure 1.DifferentialcalorimetricisothermsofCO2adsorptiononnanoporousclaywithprimaryamines.Thedatacorrespondsto adsorption(circles),readsorptionaftervacuumoutgassingfor1night(squares),andwithreadsorptionpointsdisplaced0.06mmol g-1totherightalongthex-axis(crosses). Figure 2. Single-pulse 13C (1H decoupled) NMR spectra of nanoporous clay with a) adsorbed 13CO2, b)-d) submitted to vacuumandheated50and100ºC,for4hours(raisebaseline at 100-140 ppm is probe background). Representation of the species formed in the pores of the amine functionalized material. Figure 2.Dependenceofcycloocteneoxideyield(orolefinconversion)ontimeofreactionofcyclooctene(Cy)withTBHPat 70ºCusing1@LDHascatalystprecursor(Mo:Cy:TBHPmolar ratioof1:150:230). Catalysis and Separation 47 carbamic acid. To the best of our knowledge, this is the first time that solid-state NMR is used to establish the amine-CO2 bonding at the surface of amine-modified nanoporous materials and to identify the nature of the species formed. The results shed light on the mechanism of CO2 activation, because the adsorption of CO2 on the surface of these materials is the activation step allowing further reactions to occur. The instability of the carbamate and carbamic acid species formed at the surface is important in explaining the reactivity of these intermediates and supports the application of these materials in CO2 activation. 1DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal 2DepartmentofChemistryandBiochemistry,andCQB,Faculty ofSciences,UniversityofLisbon,1749-016Lisboa,Portugal 3Instituto de Química Física ‘Rocasolano’, CSIC, E-28006 Madrid,Spain Reference [1]Pinto,M.L.,Mafra,L.,Guil,J.M.,Pires,J.,Rocha,Chemistry of Materials,2011,23,1387–1395. Sustainability concerns have led to intense activity in the development of unconventional solvents and extraction techniques. Aqueous biphasic systems (ABS) are an efficient and clean alternative for the separation and purification of a broad range of biomolecules through their partitioning between two aqueous liquid phases. Due to the aqueous environment, ABS are regarded as biocompatible systems. Recent advances in ABS have suggested that ionic liquids are viable replacements to polymers commonly employed. The interest on using ionic liquids in ABS stems from their unique combination of physicochemical properties (negligible volatility, non-flammability, and high thermal and chemical stability), which make them benign solvents. However, the major advantage of using ionic liquids as the phase-forming component of ABS is their improved solvation/extraction ability. The judicious design of the ionic liquid’s cation/anion combination allows tailoring the polarities of the co-existing phases and, thus, to optimize the extraction efficiencies of various types of biomolecules and added-value products. Besides the interest devoted to ionic liquids-based ABS formed by the addition of salts, the use of much less investigated carbohydrates may lead to more biocompatible and benign extraction routes. Carbohydrates are a non-charged, biodegradable, nontoxic and renewable feedstock. The combination of non-volatile and tailored ionic liquids with renewable bio-sourced organic compounds (carbohydrates) may lead to greener processes. In this work, we proposed novel ionic liquids-carbohydrate-based ABS by combining the water-stable ionic liquid 1-butyl-3methylimidazolium trifluoromethanesulfonate ([C4mim][CF3SO3]) and a plethora of carbohydrates (monosaccharides, disaccharides and polyols). The phase diagrams, tie-lines and tie-line lengths were determined at 25 ºC to infer on the monophasic/biphasic regimes in which ABS may be applied as liquid-liquid extractive strategies. Aiming at evaluating these novel ionic liquids-carbohydratebased ABS as potential extractive media, from biomass matrices and biorefinery processes, three representative model biomolecules were screened via their partitioning between the two aqueous phases. Caffeine and β-carotene were chosen as bioactive substances belonging to the alkaloids and terpenoids families. These compounds are usually present in the biomass and have multiple therapeutic effects and pharmacological activities. L-tryptophan is an aminoacid essential to humans, required for the production of the neurotransmitter serotonin, that may be produced by fermentative processes. The novel systems investigated showed very high extraction efficiencies (50% - 95%, in a single step) for all the studied biomolecules. A macroscopic view of the almost complete extraction of the carotenoid into the IL-rich phase is depicted in Fig. 1. The use of carbohydrates in ionic liquidsbased ABS is a step forward into sustainable extractions from biomass, allowing the recovery of a broad range of bio-based products. We are now actively engaged in studies aiming at finding high-molecular weight polysaccharides and ionic liquids capable of forming ABS. 1 DepartmentofChemistry,CICECO,UniversityofAveiro,3810193,Aveiro,Portugal 2 InstitutodeTecnologiaQuímicaeBiológica,UNL,2780-901, Oeiras,Portugal Reference [1]Freire MG, Louros CLS, Rebelo LPN, Coutinho JAP, Green Chemistry,2011,13,1536. CARbOHYDRATES AND IONIC LIQUIDS IN AQUEOUS MEDIA: A MAJOR PATH TOWARDS A SUSTAINAbLE DEvELOPMENT Freire MG,1 Louros CLS1, Rebelo LPN,2 Coutinho JAP1 Figure 1.Extractionofβ-caroteneusingcarbohydrate+ionic liquidaqueousbiphasicsystems. Catalysis and Separation48 The separation of H2 from gaseous mixtures using inorganic membranes is still a matter of considerably effort. An affordable H2-permselective membrane could be a definitive advantage in the implementation of challenging processes, among them purification of hydrogen-containing streams and H2 proton-exchange membrane (PEM) fuel cells. Small pore zeolitic materials, such as AM-3, grant them potential for the separation of H2-containing mixtures [1]. In our research, the zeolitic membranes were synthesized in-situ from a gel or clear solution, following the general procedure shown in Figure 1. The reagents are mixed to get a gel or clear solution first, and the zeolitic membranes are hydrothermally synthesized by using the seeded growth approach on the surface of porous support tubes. Seeding is performed by immersing the support into a water suspension of seeds and then dried at 150ºC for 20 minutes. The seeded support is put into an autoclave and then the precursor is added. In order to improve the quality of the membranes, samples can be prepared by repeating the preparation, i.e., after a certain synthesis time, the sample is placed into fresh gel and all steps repeat. These efforts result in small pore AM-3 and AV-7 membranes on tubular alumina support [1]. The new membranes are then structurally and dynamically characterized to evaluate their performance, i.e. the existence of defects and the range of permeance values. Prior to the dynamic tests, several heating/cooling cycles are carried out between room temperature and ca. 120ºC, since the presence of adsorbed compounds, like water from air humidity, affects significantly the results. In Figure 2 it is shown a sequence of experiments of this kind for an AM-3 membrane. The dynamic tests involve not only the continuous measurement of pure gas permeance as function of temperature at fixed transmembrane pressure drop (e.g. in Figure 2) but also steady state measurements at fixed pressure and temperature. Our work comprehends also the phenomenological modelling of permeation of pure gases and mixtures through the zeolitic membranes, where the MaxwellStefan approach has being adopted with advantage [2–4]. The main transport mechanisms that prevail in porous media are primarily related with pore diameter, dp (see Figure 3) [4]: viscous flow, Knudsen regime, and activated or configurational diffusion. In this case, if molecules retain their gaseous state inside small micropores, one has gas translational or activated gaseous diffusion; on the other hand, the strong interactions with the solid framework make them to move as an adsorbed phase (surface diffusion). For details, a deep and recent review may be consulted [4], where new expressions for thermodynamic and Maxwell-Stefan factors are also derived. 1 DepartmentofChemistry,CICECO,UniversityofAveiro,3810193,Aveiro,Portugal References [1]LiXW,ZhouCF,LinZ,RochaJ,LitoPF,SantiagoAS,SilvaCM, Microporous Mesoporous Materials,2011,137,43-48. [2]LitoPF,ZhouCF,SantiagoAS,RodriguesAE,RochaJ,LinZ, SilvaCM,Chemical Engineering Journal,2010,165,395-404. [3]Lito PF, Santiago AS, Cardoso SP, Figueiredo BR, Silva CM, Journal of Membrane Science,2011,367,21-32. [4]LitoPF,CardosoSP,RodriguesAE,SilvaCM,Separation and Purification Reviews,2014(inPress). ZEOLITIC INORGANIC MEMbRANES Lin Z1, Cardoso SP1, Silva CM1 Figure 1.Flowchartofthesynthesisprocedureofzeoliticmembranes. Figure 2. Sequences of heating and cooling cycles at programmedtemperatureofanAM-3membrane.Transmembrane pressuredrop=0.5bar,permeationgas=He. Figure 3.Masstransfermechanismsinvolvedingastransport throughporousmaterials[4]. Catalysis and Separation 49 The diffusion coefficient in dense phases is fundamental for simulation, design and scale-up of rate-controlled processes. Here, compressed gases and supercritical fluids get special attention due to their remarkable ability to be applied to masstransfer operations, phase transition processes, reactive systems, materials related processes, and nanostructured materials, either at industrial capacity application or yet under development. During last years several models have been developed in our group for the calculation of tracer diffusion coefficient (D12) in liquids, supercritical fluids and gases. In the whole, they provide very reliable and accurate results for extremely different binary systems in terms of symmetry, mass, size and even polarity. They may be divided into molecular-based equations (derived for model fluids like hard spheres, Lennard-Jones, or Stockmayer, and then extended to real substances; e.g. in Figure 1), semi-empirical expressions, free-volume equations, and improved hydrodynamic equations. To validate them, the largest database published in the literature has been compiled, including globally 630 binary systems, 9500 experimental points and 360 different molecules. From previous models, the correlations provide very low deviations (2.70-4.40%) [1-6] but embody one or two system-specific parameters (e.g., solute/solvent diameters and interaction energy), which prevents their application to unknown systems. Therefore, recently, we are focusing predictive models for D12 estimation[7,8]. They are particularly desirable in supercritical solvents, since a large number of natural compounds and unknown systems are increasingly being identified and studied under the context of biorefinery. One may cite several Stokes-Einstein based equations (e.g. [7]) and one model with improved behaviour near the critical point[8]. In this case, D12 is given by a regular or background equation plus a singular contribution specifically introduced to correct the behaviour of D12 in the critical region (error = 6.20%), particularly in the vicinity of the critical point where common models usually fail. Presently, the phenomenological modelling is being complemented with classical molecular dynamics (MD) simulations in order to disclose the influence of solute chemical groups, substituents, alkyl chain size, and molecular symmetry upon D12 values. Accordingly, alkanes, alcohols and ketones in supercritical CO2 are being computed to analyze their local structures based on radial distribution functions and coordination numbers. The MD simulations are based on boxes with several thousands of particles and are employing the Gromacs code together with potential parameters taken from the literature. 1 DepartmentofChemistry,CICECO,UniversityofAveiro,3810193,Aveiro,Portugal References [1]MagalhãesAL,Da SilvaFA, SilvaCM, Chemical Engineering Journal,2011,166,49-72. [2]Magalhães AL, Da Silva FA, Silva CM, The Journal of Supercritical Fluids, 2011,55,898-923. [3]MagalhãesAL,Da SilvaFA, SilvaCM, Chemical Engineering Science,2012,73,151-168. [4]Magalhães AL, Da Silva FA, Silva CM, The Journal of Supercritical Fluids,2013,74,89-104. [5]MagalhãesAL,LitoPF,DaSilvaFA,SilvaCM,The Journal of Supercritical Fluids,2013,76,94-114. [6]Lito PF, Magalhães AL, Gomes JRB, Silva CM, Journal of Chromatography A,2013,1290,1-26. [7]VazRV,MagalhãesAL,SilvaCM,Fluid Phase Equilibria,2013, 360,401-415. [8]VazRV,MagalhãesAL,SilvaCM,Journal of Supercritical Fluids, 2014,91,24-36. MODELING TRACER DIFFUSION COEFFICIENTS IN LIQUIDS, GASES AND SUPERCRITICAL FLUIDS Vaz RV1, Magalhães AL1, Gomes JRB1, Silva CM1 Figure 1. Exampleofthestepsinvolvedinthedevelopmentofnewtracerdiffusioncoefficientmodelforrealsystems. An ionic liquid system compatible with the lipase Candida antarctica lipase B (CaLB) to enhance its activity was developed. The use of a simple method based on 1-decyl-3-methylimidazolium chloride [C10mim]Cl to increase the lipase activity was reported. The effect of different ionic liquid molar concentrations on the relative lipase activity (ActIL/ActBf) was investigated (Figure 1, green dots). The lipase activity increases with the ionic liquid molar concentration, achieving a maximum six-fold increase for 0.090 M ionic liquid. These results suggest that the activity increment does not result from changes in the reaction mechanism or enzyme structure, since the enzyme activation energy is not affected by the ionic liquid presence but, instead, may be explained by the formation of microemulsions due to the ionic liquid alkyl chain self-aggregation IONIC LIQUIDS MICROEMULSIONS: THE KEY TO CANDIDA ANTARCTICA LIPASE b SUPERACTIvITY Ventura SPM,1 Santos LDF,1 Saraiva JA,2 Coutinho JAP1 Catalysis and Separation50 The supercritical fluid extraction (SFE) of Eucalyptus globulus bark has been studied in order to produce green extracts enriched in triterpenic acids (TTAs) such as ursolic, oleanolic and betulinic acids (see Figure 1) [1-4]. Recently we are focusing scale-up studies, by performing modeling and experiments at three different scales: nominal volumes of 0.5, 5.0 and 80.0 L (see Figure 2); the higher units belong to Natex, our industrial partner [5]. The operating conditions of the SFE (pressure, temperature, ethanol content, and CO2 mass flow rate) have been optimized at lab scale (0.5 L) using design of experiments and response surface methodologies combined with phenomenological (Figure 2). In fact, the formation of microemulsions in long chain imidazolium ionic liquids, including this one, was previously demonstrated. To evaluate if the aggregation of [C10mim]Cl was related with the observed activity increase, the critical micelle concentrations (CMC) of [C10mim]Cl in the potassium phosphate buffer with and without the presence of the substrate p-nitrophenyl laurate (pNFL) were determined by electric conductivity (mS.cm-1) measurements (Figure 1). Considering the CMC results in the presence (red diamonds) and absence (blue triangles) of the substrate, it is shown that the p-NFL significantly contributes to lower the system CMC. A comparison of the relative enzyme activity and conductivity data, presented in Figure 1, shows that the increase of ActIL/ActBf is observed for molar concentrations of [C10mim]Cl above the CMC for the system with the substrate p-NFL. The behavior reported here is being studied as the basis for novel methodologies of enzyme activation using aqueous solutions of ionic liquids. 1 DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal 2 DepartmentofChemistry,QOPNA,UniversityofAveiro,3810193Aveiro,Portugal Reference [1]Ventura SPM, Santos LDF, Saraiva JA, Coutinho JAP, Green Chemistry,2012,14,1620-16-25. Figure 2. Illustrationofthelipaseinamicroemulsionenvironment. SCALE-UP STUDIES OF THE SUPERCRITICAL FLUID EXTRACTION OF TRITERPENOIDS FROM EUCALYPTUS bARK Melo MMR1, Silvestre AJD1, Silva CM1 Figure 1.MaintriterpenicacidsfoundintheextractsofE. globulusbark. Figure 2.Supercriticalfluidextractionunitsusedinthescale-up studies. Figure 1.RelativeenzymeactivityofCaLBasfunctionoftheIL molarconcentrationandeffectofthesubstrate(p-NFL)onthe conductivityandCMCof[C10mim]Claqueoussolutions. Catalysis and Separation 51 modelling [3-4,6]. Several extraction curves have also been measured and modelled with the objective to disclose the dominant mechanisms of the process. The Logistic, Desorption, Simple Single Plate, and Diffusion equations have been selected for the calculations, and the higher adequacy of the last two expressions pointed that the intraparticular diffusion controls the separation [4]. In view of these results, the ratio between the CO2 flow rate and the bark weight was fixed in 10 h-1, being established as the appropriate scale-up criterion. The remaining variables were 200 bar, 40ºC, 2.5 wt.% ethanol. The alcohol plays an important role, since it improves the affinity of TTAs to the supercritical solvent, increases the extraction yield, and thus allows lower operating pressure. The total extraction yield and the TTAs concentration in the extracts obtained at 0.5, 5.0 and 80.0 L are plotted in Figure 3. The results evidence good agreement, therefore confirming the validity of the adopted scale-up criterion and the technical viability of the process at commercial scale. In the whole, the scale-up results are essentially concordant, taking into account that they were obtained using three units with distinct geometries, packing efficiency, and operators. 1 DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal References [1]DominguesRMA,OliveiraELG,FreireCSR,CoutoRM,Simões PC, Neto PC, Silvestre AJD, Silva CM, International Journal of Molecular Sciences,2012,13,7648-7662. [2]MeloMMR,OliveiraELG,SilvestreAJD,SilvaCM,The Journal of Supercritical Fluids, 2012,70,137-145. [3]DominguesRMA,MeloMMR,OliveiraELG,NetoCP,Silvestre AJD,SilvaCM,The Journal of Supercritical Fluids, 2013,74,105- -114. [4]DominguesRMA,MeloMMR,NetoCP,SilvestreAJD,SilvaCM, The Journal of Supercritical Fluids,2012,72,176-185. [5]NATEXProzesstechnologieGesmbH(www.natex.at). [6]MeloMMR,SilvestreAJD,SilvaCM,The Journal of Supercritical Fluids,2014,92,115-176. [7]MeloMMR,DominguesRMA,SovaM,LackE,SeidlitzH,Lang JRF,SilvestreAJD,SilvaCM,The Journal of Supercritical Fluids, submitted. Acknowledgments We acknowledge Associate Laboratory CICECO (Pest-C/CTM/ LA0011/2013)andthe7thFrameworkProgrammeFP7/20072013forfundingprojectAFORE(CP-IP228589-2). Figure 3.Cumulativecurvesof(A)totalextractionyieldand(B)TTAsconcentrationfortheSFEofE. globulusbarkatpilot(80.0L), intermediate(5.0L)andlab(0.5L)scales.Operatingconditions:200bar,40ºC,2.5wt.%ethanol,QCO2w-1 bark=10h-1[7]. Biorefineries and Materials from Renewable Sources Biorefineries and Materials from Renewable Sources54 According to the directive 2009/28/EC, biofuels should comprise at least 10 % of transport fuel in every Member State of European Union in 2020. In Portugal there is a search for bioethanol production in order to blend it with gasoline from the next year. Bioethanol is one of the most attractive biofuels and can be obtained from renewable ligninocelulosic feedstocks, contributing to the decrease of fossil fuels dependence and the reduction of CO2 build-up. Also, environmental concerns about the removal of industrial by-products and wastes are increasing the search for biotechnological integrated processes with the objective of obtaining their valorisation and economical profit via biorefinery namely by bioethanol production. Three different lignocellulosic residues produced in Portugal were tested for 2nd generation bioethanol production, the first from paper pulp industry, the second from a winery and the third from forest managing to prevent forest fires. Hardwood spent sulphite liquor (HSSL) is the main effluent resulting from the acidic sulphite pulping process and produced in large amounts. Besides other compounds HSSL is rich in monossaccharides that can be fermented to bioethanol by Scheffersomyces stipitis. Two different strategies were studied: the first one was focused in the bio-detoxification of HSSL with Paecilomyces variotii that would allow S. stipitis to grow in HSSL [1]. At the same time the fungal biomass produced was analysed for single-cell protein production. The second approach consisted in the adaptation of S. stipitis to the HSSL without the detoxification step. The obtained adapted population was then studied and compared with the parental strain in order to optimise bioethanol production. The study of bioprocess microaerophilic conditions is being developed in order to promote a fermentative metabolism of S. stipitis for bioethanol production optimization. The winemaking sector produces high amounts of by-products with significant economic potential. Bioethanol production from grape skins from white grape pomaces was studied. Sugars aqueous extraction provided an extract rich in hexoses and suitable for yeast fermentation. Saccharomyces cerevisiae batch fermentation was successful attaining bioethanol productivity of 1.34 g ethanol L−1 h−1 and a high yield of 0.51 g ethanol per gram of sugar [2]. Thermochemical pretreatment, saccharification and fermentation of Cistus ladanifer (rockrose) wildly grown in Alentejo were studied in order to valorize this forest residue. Rockrose was subjected to steam explosion treatment (SE) and a subsequent alkali treatment (SEOH). Enzymatic hydrolysis of untreated, SE and SE-OH materials was compared. The biomass resulting from the best pretreatment was used for a comparative study in Separate Hydrolysis and Fermentation (SHF), and Simultaneous Saccharification and Fermentation (SSF) assays. Fermentation was carried out in SHF and SSF modes with SE-OH rockrose, commercial cellulase and cellobiase, showing that SSF process is more efficient than SHF process with an overall efficiency of 66%, allowing the production of 14.8 g/L of bioethanol with a productivity of 0.62 g L−1 h−1 after 24h of saccharification and simultaneous fermentation. 1 DepartmentofChemistry,CICECO,UniversityofAveiro,3810‑ ‑193Aveiro,Portugal 2 CentrodeBiotecnologiaAgrícolaeAgro‑AlimentardoAlentejo (CEBAL)/InstitutoPolitécnicodeBeja,Portugal 3 Division of Applied Microbiology, Department of Chemistry, LundUniversity,Sweden References [1]PereiraSR,IvanušaŠ,EvtuguinDV,SerafimLS,XavierAMRB, Bioresource Technology,2012,103,131–135. [2]MendesJAS,XavierAMRB,EvtuguinDV,LopesLPC,Industrial Crops and Products,2013,49,286–291. 2nd GENERATION BIOETHANOL PRODUCTION FROM DIFFERENT LIGNOCELLULOSIC RESIDUES Pereira SR1, Fernandes MC2, Gorwa-Grauslund MF3, Evtyugin DE1, Serafim LS1, Xavier AMRB1 Figure 1.BioethanolproductionfromHSSL.Strategy1:HSSLbio‑detoxificationbyPaecilomyces variotiiwithproductionofsinglecell protein(SCP);Strategy2:adaptationofS. stipitistoHSSL. Biorefineries and Materials from Renewable Sources 55 Cellulosic fibres have been modified by a mild sol–gel process, at room temperature, using silicon alkoxides as silica precursors, an acidic catalyst and aqueous solution or aqueous organic solvents. Silica is deposited on the fiber surface as isolated or aggregated mesoparticles (0.1–2 mm diameter, Fig. 1.a) or as a discontinuous film comprising round-shape domains (0.05–0.3 mm, Fig. 1.b) depending on the synthesis conditions.[1] The strong hydrogen bonds formed between silica and the hydroxyl groups of cellulose create an impermeable interface that reduces water adsorption as revealed by the net isosteric heat of sorption.[2] Hence, cellulose silica hybrids (CSH) have lower hydrophilicity (expressed as water retention value) than the parent cellulosic fibers. At the same time, the presence of silica improves dimensional stability in water, fire resistance and bending strength. Altogether, these properties are appealing for packaging applications of CSHs materials that are being explored within the FP7 project nanobarrier. The surface properties of CSHs may be radically changed if the silica formulations contain tetraethyl orthosilicate (TEOS) and smaller amounts of prehydrolyzed trialkoxysilanes bearing distinct functions (propylamine, allyl, alkyl, etc.). Some of these functionalities may be used to bind active substances (e.g. catalysts, sensors, scavengers, etc.) that widely expand the application areas of cellulosic hybrid materials. For instance CSHs possessing aminopropyl groups were examined as ion exchange materials for arsenates removal from aqueous solutions (in the range 26-172 mg As/L, at 25 ºC and pH 3.5) and revealed specific sorption properties that can be explored for water purification.[3] CSHs bearing amine groups chemically bonded to reversible redox catalysts such as polyoxometalates (Fig. 1.c) are suitable as barrier coatings, active filters, etc. In particular CSH materials functionalized with 2% of [PMo11VO40]4or [PV2Mo10O40]5showed particularly high activity towards degradation of volatile organic compounds (VOC) present in urban and indoor air at high concentration levels, thus anticipating future environmental applications.[4] Furthermore, the basic redox cycle of POM which includes VOCs oxidation via electron transfer and radical mechanisms, followed by room temperature catalyst re-oxidation with atmospheric O2 (or O3), is easily visualized by CSHs colour change (from green to yellow) due to the reduction of vanadium atoms (VV → VIV).[4] In a further embodiment, 2-3 g/m2 of silicabased formulations (nanocoating) were applied on the surface of paper sheets with a significant impact on surface properties related to printability. Adjusting the composition of the silica formulation enables the fine-tuning of surface microporosity and effective parameters (contact angle, surface energy and the corresponding polar and dispersive counterparts, among others) to improve colour reproduction and printing firmness (Fig. 2) when using both inkjet and laser printers. Thus paper surface modification by silica based formulations is suggested as a prospective tool for surface engineering towards tailored printing performance. 1 DepartmentofChemistry,CICECO,UniversityofAveiro,3810‑ 193Aveiro,Portugal References [1]SequeiraS,EvtuguinDV,PortugalI,EsculcasAP,Materials Science and Engineering: C,2007,27,172‑179. [2]PortugalI,DiasVM,DuarteRF,EvtuguinDV,TheJournal of Physical Chemistry B,2010,114,4047‑4055. [3]MartinsC,DuarteRF,MagalhãesMCF.,EvtuguinDV,Materials Science Forum,2013,730‑732,563‑568. [4]Gamelas JAF, Evtyugina MGI, Portugal I, Evtuguin DV, RSC Advances,2012,2(3),831‑839. ADvANCED CELLULOSE/SILICA HyBRID MATERIALS EvtuguinDV1,PortugalI1 Figure 2. Ink jet printing tests of uncoated (series a) and DEDMS/TEAP/TEOScoatedpaper(seriesb): firmnessofpoint(1),firmnessofline(2)andinter‑color‑bleed‑ ing(3).(Silicaformulation:94%Tetraethoxysilane(TEOS)+3% triethoxysilanaminopropyl(TEAP)+3%diethoxydimethylsilane (DEDMS)) Figure 1.Celulose/SilicaHybrids:(a)SEMimageofcellulosefibrescoveredbysilica;(b)thepresenceofasilicafilmwasassessed bySEM/EDSandAFMappliedinatappingmode;coveredbyasilicafilm;(c)schematicrepresentationofthecellulosechainbonded toasilicanetworkfunctionalizedwithPOM. Biomedical Materials and Applications62 Nitric oxide (NO) acts as an important agent in the body for expanding blood vessels (its role in Viagra and related medicines for erectile dysfunction), preventing the formation of blood clots, aiding nerve signals, and repairing wounds. NO’s multipurpose role makes it an exciting prospect for new drug development, but current NO delivery systems sometimes cause undesirable side effects. Besides good NO adsorption capacity, materials must also present an appropriate releasing kinetics, to maintain a given concentration in the surrounding milieu. Often, a slow releasing kinetics is preferred because it allows for easier and safer control of the NO concentration, for longer periods. Clearly, new materials and technologies are needed to store and target-deliver NO in biological amounts. A novel approach to design nitric oxide storage and releasing microporous agents based on very stable, zeolite-type silicates possessing framework unsaturated (e.g., pentacoordinated Ti4+) transition-metal centers has been proposed[1]. This idea has been illustrated with ETS4 [Na9Si12Ti5O38(OH)·xH2O], a titanosilicate (Fig. 1a) which displays excellent NO adsorption capacity and a slow releasing kinetics (Fig. 2). The performance of these materials has been compared with the performance of titanosilicate ETS-10, [(Na,K)2Si5TiO13·xH2O], of benchmark zeolites mordenite and CaA, and of natural and pillared clays. DFT periodic calculations have shown that the presence of water in the pores of ETS-4 promotes the NO adsorption at the unsaturated (pentacoordinated) Ti4+ framework ions (Fig. 1b). The ability of ETS-4 to release biologically relevant NO amounts was tested using the oxyhemoglobin method, which is based on the principal reaction of oxyhemoglobin with NO to form methemoglobin and nitrate. This reaction also accounts for the inhibitory effect of hemoglobin on the biological effects of endogenous formed or exogenous applied NO. 1DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro 2DepartamentodeQuímicaeBioquímicaeCQB,Faculdadede CiênciasdaUniversidadedeLisboa,1749-016Lisboa Reference [1]Pinto ML, Rocha J, Gomes JRB, Pires J, Journal of the AmericanChemicalSociety,2011,133,6396–6402. SLOW RELEASE OF NO BY MICROPOROUS TITANOSILICATE ETS-4 Pinto ML1,2, Rocha J1, Gomes RJB1, Pires J2 Figure 2. Kinetic profiles of NO desorption on the studied adsorbentmaterials,inhighvacuumat25°C,afteradsorption at80kPa. Figure 1. (Left)ModelofthestructureofETS-4usedintheDFTcalculations;(Right)coordinationofNOtothepentacoordinatedTi4+centre.Coloredspheresrepresentatomsofsodium(purple), hydrogen(whitesmall),oxygen(red),silicon(grey)andtitanium(cyan);NO:oxygen(darkblue),nitrogen(green). Biomedical Materials and Applications 63 Understanding how molecular systems self-assemble in the solid-state remains a challenge. In this regard, H bonding and van der Waals interactions play major roles as structure-driving entities in the construction of supramolecular arrangements. This is of particular relevance in pharmaceutical sciences, as multiple crystal forms of the same active pharmaceutical ingredient occur frequently, posing diverse problems in the pharmacokinetics, stability, and formulation of drugs. In an attempt to better understand how drug hydrates self-assemble in the solidstate and reorganize to produce anhydrous forms, we presented a comprehensive NMR, X-ray diffraction (XRD), and computational study of packing interactions of different types, such as weak/ strong H-bonds and π···π interactions, that constitute the supramolecular assemblies of two crystalline forms of the antibiotic ciprofloxacin (Figure 1f) [1]: one anhydrate (form I) and one hydrate (form II) forming water wormholes, emphasizing the effect of nonconventional hydrogen bonds and water on NMR chemical shifts. The complete assignment of up to 51 and 54 distinct 13C and 1H resonances for the hydrate was reported, using a toolbox of advanced high-resolution 2D 1H CRAMPS-based NMR experiments and high magnetic fields (Figure 1a-e) combined with GIPAW calculations of 1H/13C chemical shifts. The effect of crystal packing on the 1H and 13C NMR chemical shifts, including weak interionic hydrogen bonds and π···π interactions, was quantified through in silico structure deconstruction of I and II (Figure 2). For example, 1H chemical shift changes up to ca. −3.5 ppm for CH···π contacts and ca. +2 ppm (CH···O(−)); ca. +4.7 ppm ((+) NH···O(−)) were estimated for hydrogen bonds. Water intake induced chemical shift changes up to 2 and 5 ppm for 1H and 13C nuclei, respectively. We showed that such chemical shifts are sensitive detectors of hydration/dehydration in the highly insoluble ciprofloxacin hydrates. 1 DepartmentofChemistry,UniversityofAveiro,CICECO,3810193Aveiro,Portugal 2 Max-Planck-Institut fr Polymerforschung, Ackermannweg 10,55128Mainz,Germany Reference [1]MafraL,SantosSM,Siegel R,Alves I,Paz FAA,Dudenko D, Spiess HW, Journal of the American Chemical Society, 2012, 134,71-74. QUANTIFYING WEAK PACKAGING INTERACTIONS IN THE HYDRATED AND ANHYDROUS FORMS OF ANTIBIOTIC CIPROFLOXACIN Mafra L1, 2, Santos SM1, Siegel R1, Alves I1, Paz FAA1, Dudenko D2, Spiess HW2 Figure 2.(Left)Stemplotsshowingthecontributionofthecrystalpacking(bluestems)andwatermolecules(redstems)tothe calculated1Hchemicalshifts(positiveΔδvaluesindicatelow-fieldshifts)oftheciprofloxacinformsIandII.InII,eachofthethree stemspernucleicorrespondstothecrystallographicallydistinctciprofloxacinmolecules1,2,and3(fromlefttoright);(right)detailedviewofintermolecularinteractionsinpackingsofIandII. Figure 1.2D1H−13CPRESTO-HETCORofciprofloxacinforms(a)Iand(c)IIrecordedat800MHz.(b,d)13CCPMASspectrarecordedat 400MHz.(e)1HMASandwDUMBOspectraofIareshownforcomparisonwiththeF1projectionof(a).(f)Labellingschemeadopted forciprofloxacin.ThecapabilityofPRESTOtransfertoselectonlythedirectlybondedC−Hismanifestedbycomparisonwiththe13C CPMASspectra[i.e.,(a,c)vs.(b,d)] Biomedical Materials and Applications64 Cellulose is the most abundant biopolymer, and although it is mainly biosynthesized by plants, several bacteria (mainly of the Gluconacetobacter genus), can also produce an extra-cellular form of cellulose, commonly referred to as bacterial cellulose (BC), which is normally produced in the form of highly swollen membranes. BC is obtained with high purity and shows remarkable properties, resulting from its unique tridimentional nanofibrilar structure, which have been explored in a wide range of applications [1], notably in the biomedical field as wound healing membranes, scaffolds for tissue engineering, artificial blood vessels and drug delivery systems. BC is particularly advantageous in the design of transdermal drug delivery systems because of the straightforwardness and effectiveness of preparation of the drug loaded BC membranes and the fact that they are only composed of a single layer. Furthermore, their ability to absorb exudates and to adhere to irregular skin surfaces, along with their conformability and intrinsic skin compatibility [2] are additional issues that are crucial for several clinical situations. In this vein BC membranes have been loaded by absorption of solutions of selected drugs (lidocaine [3,4], ibuprophen [4] caffeine [5] and diclofenac [6] ), containing a few percent of glycerol (to improve flexibility of the membranes), followed by oven drying of the solvent. The drugs are uniformly distributed over the membranes, as confirmed by SEM analysis, and the in vitro skin permeation tests revealed that with the exception of ibuprophen, all the drugs have low permeation rates than conventional formulations [Figure 2], which is a clear advantage for situations where long term release of the drug is required. These results clearly demonstrate the potential of BC as a drug release system. New and promising perspectives might be opened with its testing on oral applications, particularly when combined in nanocomposite materials with other polymeric matrices. 1 DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro References [1]FigueiredoARP,VilelaC,NetoCP,SilvestreAJD,Freire CSR, Bacterial cellulose based nanocomposites: a roadmap for innovative materials, in:Nanocellulose Polymer Nanocomposites: Fundamentals and Applications(KumarV.Ed.),Wiley,inpress. [2]AlmeidaIF,Pereira T,Silva NHCS,Gomes FP,Silvestre AJD, Freire CSR, Sousa Lobo JM, Costa PC, European Journal of Pharmaceutics and Biopharmaceutics,2014,86,332–336. [3]TrovattiE,SilvaNHCS,DuarteIF,RosadoCF,AlmeidaIF,Costa P,FreireCSR,SilvestreAJD,NetoCP,Biomacromolecules,2011, 12,4162–8. [4]TrovattiE,FreireCSR,PintoPC,AlmeidaIF,CostaP,Silvestre AJD,NetoCP,RosadoC,International Journal of Pharmaceutics, 2012,435,83–87. [5]SilvaNHCS,DrumondI,AlmeidaIF,CostaP,RosadoCF,Neto CP,FreireCSR,SilvestreAJD,Cellulose,2014,21,665–674. [6]Silva NHCS, Rodrigues AF, Almeida IF, Costa PC, Rosado C, Neto CP, Silvestre AJD, Freire CSR, Carbohydrate Polymers, 2014,106,264–269. Acknowledgments FCT and POPH/FSE are acknowledged for the Associate LaboratoryCICECOfunding(PEst-C/CTM/LA0011/2013). BACTERIAL CELLULOSE AS TRANSDERMAL DRUG DELIvERY SYSTEMS Silva NHCS1, Silvestre AJD1, Freire CSR1, Neto CP1 Figure 1.Visualimageofawet(A)and(B)drugloadedBCmembraneappliedoverskin. A B Figure 2.DrugspermeationprofilesacrosshumanepidermisforA:lidocaine;B:ibuprophen;C:caffeine;D:diclofenac, comparedwithconventionalformulations. A C B D Biomedical Materials and Applications 65 One of the emerging strategies in drug delivery consists in the development of hydrogel carriers with remote controlled capabilities. The release of an encapsulated drug can be triggered remotely by external stimuli, providing a flexible control of the release rate and profile, according to the specific needs of the patient. Most studies on remotely triggered drug release have dealt with magnetically driven carriers upon the exposure to an alternate magnetic field. Near-infrared (NIR) light is harmless and deeply penetrates in the living tissues, hence being an attractive stimulus source for remotely controlled bioapplications. Nevertheless the number of studies reporting NIR activated platforms for drug delivery is still modest. At the University of Aveiro, researchers from CICECO have succeeded in the fabrication of NIR responsive platforms based on hydrogel nanocomposites. These composites comprised matrices of thermosensitive hydrogels reinforced with carbon nanotubes (CNTs), which absorb NIR light and convert the absorbed energy into heat very effectively. CNTs acted as multifunctional fillers by enhancing the mechanical properties of the hydrogels and conferring light responsive characteristics to the composites. The composite hydrogels showed reversible heat induced gelto-sol phase transition, either by using temperature or NIR light irradiation as external stimuli. The release of a model drug from the hydrogels containing nanotubes could be induced by NIR irradiation, in which the CNTs acted as a nanoheater to raise the local temperature of the gel via the photothermal conversion of the CNTs. In face of these promising results, these hydrogel composites are promising materials for the development of remotely controlled light activated drug delivery systems. 1DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal Reference [1]Estrada AC, Daniel-da-Silva AL, Trindade T, RSC Advances, 2013,3,10828-10836. PHOTOTHERMALLY ENHANCED DRUG RELEASE BY HYDROGELS REINFORCED WITH CARBON NANOTUBES Estrada AC1, Daniel-da-Silva AL1, Trindade T1 Figure 1.(left)Visualobservationofthephotoinducedgel–soltransitioninhydrogelscontainingCNTsand(right)drugmodelrelease profilesinPBSat37ºCfromtheblankhydrogelandhydrogelcomposites,withandwithoutexposuretoNIRlight. NOvEL BINUCLEAR COPPER COMPLEXES AS ALTERNATIvE ANTI-TUMORAL DRUGS: SYNTHESIS, CHARACTERISATION AND CYTOTOXIC STUDIES Brandão P1, Ferreira, BJML1, Santos TM1, Meireles M2, Félix V1,3 Over the past decades, metal complexes have had enormous success as cytotoxic drugs against cancer related diseases. Cisplatin, cis-[Pt(NH3)2Cl2], is the paradigmatic example of a “small” transition metal complex which had been widely used as an anti-tumoral drug, particularly against testicular, ovarian, bladder, and head/neck tumours [1,2]. However, its effectiveness was early clouded by several undesirable side effects along with acquired drug resistance. This clearly showed that selectivity and specificity are indeed the main keys to design and produce better and effective cytotoxic and anti-tumoral new drugs. Because of these drawbacks, the development of other anticancer metal-based drugs with more specificity and less toxicity is nowadays the object of the attention of a great number of researchers, who have directed their efforts towards the synthesis of polynuclear Pt, Ru, Rh, Pd, [3-5] and more recently to Au, Cu and Fe complexes [6-8], which can overcome both the natural and the acquired resistance of human cancer cells to cisplatin and analogous drugs. Among this array of multi-metal centred complexes, those with copper have been much less explored, which seems to be a paradox taking into account the availability and bio-compatibility of both metals. A further benefit of the use of this metal is that is much cheaper than the “traditional” metals (platinum, ruthenium, rhodium and gold) currently used in the preparation of metal based anticancer agents. Recent studies have demonstrated that certain dinuclear copper complexes showed much higher cleavage efficiency than their mononuclear analogues [9,10]. These recent findings prompted us to invest on the design of new polynuclear Biomedical Materials and Applications66 The commercially available biomaterials for bone replacement and reinforcement do not take into account the bone natural piezoelectric properties and thus its use is accompanied by a break in bone natural electro physiologic continuum [1]. Arthroplasty causes strong changes on adjacent bone strain levels and distribution. The work explored in vitro and in vivo use of a piezoelectric polymer substrate for providing bone mechanical stimulation. Osteoblastic line cells MC3T3-E1 were seeded on the coated and electrically insulated surface of polyvinylidene fluoride (PVDF) films and subjected to static and dynamic conditions, as described by Frias et al. (2010). In dynamic conditions the substrates were deformed by applying a 5 V current, at 1 Hz and 3 Hz for 15 min every 24 hours. Electronic speckle pattern interferometry method showed the maximum substrate displacement was 0.6 μm, in the central area of the devices; displacement was minimum in the encastre (clamped) region. The assessment of cell viability and proliferation evidenced a material’s poorer performance when compared to control standard culture vessel. Higher viability values were registered on mechanically stimulated substrates, although the differences between static and dynamic samples were not statistically significant. To evaluate effectiveness of mechanical stimulation nitric oxide (NO) was measured in culture medium samples immediately after stimulation. NO is a messenger molecule produced in response to mechanical stimulation of osteoblasts and osteocytes, with a large variety of biological functions. Culture medium NO measurements in the samples subjected to mechanical stimulation were significantly higher than static samples. The in vitro study showed therefore evidence of effective bone cell mechanical transition metal complexes as an effort to discover new biologically active metalodrugs more selective and less toxic, when compared to classical drugs. The copper centres will be assembled using as bridging ligands DNA based motifs or pyridyl ligands with extended aromatics systems. The coordination sphere of copper centre will be completed with DNA type bases or ancillary pyridyl ligands. The first ligands can interact with DNA through the formation of hydrogen bonds while the second ones can form T-T staking interactions with the base pairs. The presence of these two types of ligands in the same complex is a very important advantage: it can lead to a stronger binding affinity and to an increased selectivity for DNA. For this purpose we have synthesized three binuclear copper complexes with adenine and 1-10-phenantroline, compound 1, and only with adenine, compound 2 and 3 (figure 1). In these compounds the nucleobase adenine links the copper(II) atoms in a bridging mode by the N(3) and N(9) donor (as bi-dentate). All copper complexes exhibit significant anti-tumoral activity against HeLa cells, leading to IC50 values approximately of 1, 60 and 94 μM, respectively (figure 1). We believe that the study of such class of metal complexes can open the doors for new research toward the preparation of alternatives anti-tumoral drugs. 1 DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal 2 Department of Chemistry and Biochemistry, University of Lisbon,Lisboa,Portugal 3Department of Health Sciences, University of Aveiro, 3810193Aveiro,Portugal References [1]LippardSJ,et al.,Current Opinion in Chemical Biology,2003, 7,481. [2] RosenbergB,et al.,Nature,1969,222,385. [3]Kettunen,et al.,Current Opinion in Chemical Biology,2006, 13,1337. [4]DysonPJ,et al.,Platinum Metals Review, 2001,45, 62. [5]HadjikakouSK,et al.,Coordination Chemistry Reviews, 2009, 253,235. [6]Aldrich-WrightJ,et al.,Chemical Communications,1018,2004. [7]SerratriceM,et al.,Inorganic Chemistry,2012,51,3161. [8]MegensRP,et al.,Chemistry - A European Journal, 2009,15, 1723. [9]ZhaoY,et al.,Chemistry - A European Journal,2006,12,6621. [10]Medina-MolnerA,et al., Chemical Communications,20121961. Figure 1.Molecularstructureofcoppercompound1[Cu2(µ-adenine)2(phen)2(H2O)2]·4(NO3)·2(H2O);coppercompound2[Cu2(µadenine)4(µ-OH)(H2O)2]·3(NO3)·(H2O).adenine;andcoppercompound3[Cu2(µ2-OH)2(µ-adenine)2(H2O)4]·2(NO3)·H2O,andinvitro cytotoxicityassaysforallthreecoppercomplexesagainstHeLacells. BONE MECHANICAL STIMULATION WITH PIEZOELECTRIC MATERIALS Reis J1,2, Frias C3, Capela-Silva F4,5, Potes J1,5, Simões JA6, Botelho ML7, Castro CC7, Marques ATM3 Biomedical Materials and Applications 67 stimulation, and the concept was further explored in vivo. An actuator device was developed, composed of microcontroller (eZ430-RF2500, Texas Instruments, USA) and a set of six actuators. A similar, but static, control device was also developed, sterilized and implanted The actuator device was implanted in the left hind limb and the control static device was implanted in the right hind limb of a 4 year old merino ewe, under general inhalatory anaesthesia. Six osteotomies were made on the tibial proximal physis and distal femoral physis, using especially metal designed guides. The biological response around the osteotomies was assessed through histology and histomorphometry in non-decalcified sections and histochemistry and immunohistochemistry in decalcified sections, namely through Masson’s trichrome, and labeling of osteopontin, proliferating cell nuclear antigen and tartrate resistant acid phosphatase. After one-month implantation, total bone area and new bone area were significantly higher around actuators when compared to static controls. Bone deposition rate was also significantly higher in the mechanically stimulated areas (Figure 1). In these areas, osteopontin increased expression was observed. The results suggest that piezoelectric materials and the converse piezoelectric effect may be used to effectively stimulate bone growth. Actuators with improved biocompatibility should be developed [2,3]. 1DepartmentofMaterialsandCeramicsEngineering,CICECO, UniversityofAveiro,3810–193Aveiro,Portugal 2DepartmentofVeterinaryMedicine,UniversityofÉvora,7002554Évora,Portugal 3Department ofMechanical Engineering, Universityof Porto, 4200-465Porto,Portugal 4DepartmentofBiology,UniversityofÉvora,7002-554Évora, Portugal 5Institute of Mediterranean Agricultural and Environmental Sciences (ICAAM), University of Évora, 7002-554 Évora, Portugal 6DepartmentofMechanicalEngineering,UniversityofAveiro, 3810-193Aveiro,Portugal 7InstitutoTecnológicoeNuclear,2686-953Sacavém,Portugal References [1]ReisJ,Capela-SilvaF,QueirogaC,Lucena,S,PotesJ,Journal of Biomedical and Bioengineering,2011,2,37-44. [2]ReisJ,FriasC,CastroCC,BotelhoML,MarquesAT,Simões JA, Capela-Silva F, Potes J, Journal of Biomedicine and Biotechnology,2012,ID613403,1-7. [3]ReisJ,FriasC,Capela-SilvaF,PotesJ,Simões JA,Botelho ML,CastroCC,MarquesATM,InNatural Polymers, Biopolymers, Biomaterials, and Their Composites, Blends, and IPNs(Thomas etal.Eds.),2012,Chapter25,293-306. Acknowledgments The work was partially supported by FEDER Funds through the Operational Programme for Competitiveness Factors – COMPETE and National Funds through FCT – Foundation for Science and Technology under the Strategic Project PEst-C/ AGR/UI0115/2011. Authors acknowledge also the financial supportfromthePortugueseScienceFoundation(FCT)inthe formsofprojectsPTDC/EME-PME/65749/2006andPTDC/EMEPME/70824/2006;andBD/31895/2006. Figure 1.Newlyformedbonearoundapiezoelectricactuator, labelledwithcalceingreenandalizarinred,onemonthpostimplantationinsheep(tibia,non-decalcifiedsection). POLARIZATION SWITCHING IN HYDROXYAPATATIE: BONES CAN GROW FASTER Lang SB1, Tofail SAM2, Kholkin AL3, Wojtaś M3, Gregor M4, Wang Y5, Bauer S6, Krause M6, Plecenik A4 Ferroelectricity is a property of reversibility of spontaneous polarization (Ps) by the application of a small electric field. Such property is shown by a small subset of pyroelectric materials that belongs to one of the ten crystal classes that possess no center of symmetry and a spontaneous polarization. Hydroxyapatite (HA) nanocrystals are one of the fundamental building blocks of bone and the primary determinant of bone density and mechanical stability. Hydroxyapatite concretions are even found in the pineal gland of the brain. Synthetic hydroxyapatite is widely used in bone grafts and prosthetic coatings as it binds strongly with natural bone –a critical requirement especially when the host bone-density is low due to age or diseases (e.g. osteoporosis). A piezoelectric effect in bone was first observed by Fukada and Yasuda in 1957 [1]. Until very recently, the effect was believed to be due to the collagen component of bone because another part of bone – hydroxyapatatite was considered to be centrosymmetric [2]. It was contested in 2005 when Haverty et al. [3] proposed two polar Figure 1.Aschematicrepresentationofthehydroxylionorientationandenergeticsofthenonpolar(P21/b)andpolarsymmetries (P21andP63)ofhydroxyapatite. Biomedical Materials and Applications68 symmetries for HA: a monoclinic P21 and a hexagonal P63, which are not restricted by the presence of a centre of symmetry. These polar, non-centrosymmetric structures originated from a ferroelectric ordering of the hydroxyl ions (OH) along the crystallographic c axis ([001] direction (Fig.1). The small energy difference between these polar symmetries and the centrosymmetric (P21/b) meant that smaller size in HA crystals may lead to the stability of these polar structures due to the availability of large amount of surface energy [4]. Here we show that hydroxyapatite thin films show reversible spontaneous polarization of a ferroelectric nature [5]. The remnant polarization is about a quarter of that measured for a lead-zirconate-titanate film measured under similar conditions. While ferroelectricity in soft tissues such as aortic wall have been claimed for a long time, hard tissues (e.g. lamellar bone) and its constituents typically exhibited antiferroelectric order. In contrast, hydroxyapatite reveals a ferroelectric order, which is stabilized due to the nanoscale dimension of HA films. Figure 2 shows the local piezoresponse image (d33) and hysteretic dependences of d33 measured at two different locations. The amplitude of the piezoresponse and phase (which sign indicates polarization direction) were measured immediately after the application of poling pulses. The dependencies of both d33 and phase with respect to bias voltage show a strongly hysteretic dependence typical for polarization switching in ferroelectrics. This finding will stimulate new understanding on the mechanism of biomineralisation and the formation of the characteristic hierarchical structure of bone. Reversible spontaneous polarization in hydroxyapatite will also open up a number of novel technical applications such as in electronics, microelectromechanical systems (MEMS), in vivo energy harvesting and biosensors. 1Ben-GurionUniversityoftheNegev,BeerSheva,Israel 2Department of Physics and Energy, University of Limerick, Limerick,Ireland 3Department of Materials and Ceramic Engineering, CICECO, UniversityofAveiro,3810-193Aveiro,Portugal 4ComeniusUniversity,Bratislava,Slovakia 5HongKongPolytechnicUniversity,HongKong 6JohannesKeplerUniversity,Linz,Austria References [1]FukadaE,YasudaI,Journal of the Physical Society of Japan, 1957,12,1158-1162. [2]KayMI,YoungRA,PosnerAS,Nature,1964,204,1050. [3]HavertyD,TofailSAM,StantonKT,McMonagleJB,Physical Review B,2005,71,9410. [4]AmisEJ,RumbleJ,Certificate of analysis,SRM2910:Calcium hydroxyapatite,2003. [5]LangSB,TofailSAM,KholkinAL,WojtaśM,GregorM,Gandhi AA,WangY,BauerS,KrauseM,PlecenikA,Scientific Reports 3, 2013,2215. Figure 2.RepresentativePFMimage(upperpart)andrecordedferroelectrichysteresisloops(lowerparts)inplacesindicatedby arrows. Biomedical Materials and Applications 69 Bone regenerative medicine has noticed huge progress in the past decades driven by the great socioeconomic interest in treating skeletal diseases. Despite tremendous improvements of synthetic bone grafts, most are incapable of fully repair severe bone injuries. Yet, biomaterials can still be reinvented to become universal bone regeneration solutions. Following this roadmap, “smart” bone grafts have been designed with new functionalities able to stimulate specific bone cells responses. Regarding the beneficial effects of endogenous electrical signals in bone, electron conductivity emerge as an exciting functionality. The electrical currents found in healthy bone are not expected to exist at the fractured bone site. By applying exogenous electrical stimuli at the damaged bone together with conductive bone grafts is expectable an improved efficiency of charge transfer voltage at the substrate-cell interface allowing the spatial-temporal control of bone regeneration. This stimulation efficiency is thought to be related to the high density of electric field lines crossing the cell (Fig. 1), which boosts opening of voltage-gated channels at multi-locations in the cell membrane, and raises action potentials’ magnitude. Those conductive composite grafts containing metal fillers for such purpose are precluded due to corrosion phenomenon that induces cytotoxicity. Alternatively, the characteristics of carbon nanotubes (CNTs), namely lowcost, ultimate electrical conductivity and low percolation thresholds, make them promising candidates to obtain conductive biomaterials with preserved biological profiles. This work aims to develop a CNT/ Bioglass/HA composite having adequate mechanical, electrical and, most important, biological characteristics, to be used as an electroconductive bone graft in the electrotherapy of injured bone. Composites with controlled CNT agglomeration were processed by an optimized functionalization-free route with minor contaminant levels and damage to CNTs. These phases worked as efficient toughening agents in composites improving the fracture toughness of the ceramic matrix, making it closer to the one of cortical bone. The remaining mechanical and electrical properties of the composite outperformed those of the bone. The use of AC impedance spectroscopy (Figs. 2a and b) and of vibrating voltage probe measurements (Figs. 2c and d) in α-MEM cell culture medium reveal the converging effects that the conductive composite material have on the electric field and current flow paths. In vitro studies evidence that CNT composites allowed cell adhesion and proliferation, further enhancing the functional activity and modulating the orientation of the cell growth along the alignment of the CNT agglomerates. The results on the in vitro AC electrical stimulation of bone cells highlight that the conductive CNT composite significantly improved cell functional activity under an appropriate electrical stimulation protocol, compared to the Bioglass/HA matrix. The cell metabolic activity and DNA content were increased by 130% and 60%, relatively to the non-stimulated condition, after only Figure 2.(a)Photographsoftheelectrochemicalcellswithsixsamplesimmersedin12mlofα-MEMandplatinumspiralelectrodes. (b)Plotsshowingthedependenceofthemodulusofimpedance|Z|oftheelectrochemicalcellsonthesignalfrequency.(c)Set-up ofthevibratingvoltageprobemeasuringsystemofaelectrochemicalcellcontainingonesampleimmersedin12mlofα-MEMand parallelgraphiteelectrodes.(d)Plotofthevariationofthecurrentdensitylineprofile(fromItoIIlabels)inthezzdirectionwiththe electricalconductivityofthesampleatafixedsample-probedistanceof50µm. CARBON NANOTUBE/BIOCERAMIC COMPOSITES FOR IN SITU ELECTRICAL STIMULATION OF BONE Mata D1, Oliveira FJ1, Neto MA1, Belmonte M2, Bastos AC1, Lopes MA3, Gomes PS4, Fernandes MH4, Silva RF1 Figure 1. (a)Topviewschematicimages ofthe electricfield (currentdensity)linesdistributionofa(a)dielectricanda(b) conductive spherical samples interfacing with osteoblastic cells(ellipticalpurplesketches)immersedinahomogeneous α-MEMculturemedium. Biomedical Materials and Applications70 3 days of daily stimulation of 15 μA for 15 min (Figs. 3a-c). Moreover, the osteoblastic gene expression for Runx2, OC and ALP was enhanced by 80%, 50% and 25%, after 5 days of stimulation (Figs. 3df). These observations were related to the local increase of the α-MEM conductivity and the confinement of electrical fields on the surface of the conductive material (Fig. 2). The results validate the hypothesis that CNT/Bioglass/HA bone grafts could be used together with a non-invasive electrical stimulation technique to boost cell growth by an efficient stimuli delivering mechanism. Reducing the cost and time of bone treatment can make the electrotherapies of clinical relevance. These novel non-metallic graft materials offer new possibilities, not only in bone regeneration, but also in other excitable tissues (e.g. neuronal). Future research should consider animal model tests applying the optimized in vitro stimulation protocol to validate the efficiency of bone formation on conductive bone grafts. 1Department of Materials and Ceramic Engineering, CICECO, UniversityofAveiro,3810-193Aveiro,Portugal 2InstituteofCeramicsandGlass,CSIC,28049Madrid,Spain 3CEMUC,MetallurgicalandMaterialsEngineeringDeptartment, Faculty of Engineering, University of Porto, 4200-465 Porto, Portugal 4LaboratoryforBoneMetabolismandRegeneration,Facultyof DentalMedicine,UniversityofPorto,4200-465Porto,Portugal References [1]MataD,SilvaMR,FernandesAJS,OliveiraFJ,CostaPMFJ,Silva RF,Carbon,2012,50,3585-3606. [2]MataD,OliveiraFJ,FerroM,GomesPS,FernandesMH,Lopes MH,SilvaRF,Journal of Biomedical Nanotechnology,2013,9, 1-19. [3]Mata D, Horovistiz AL, Branco I, Ferro M, Ferreira NM, BelmonteM,LopesMA,SilvaRF,OliveiraFJ,Materials Science and Engineering: C,2014,34,360-8. [4]MataD,OliveiraFJ,FerreiraNM,AraújoRF,FernandesAJS, LopesMA,GomesPS,FernandesMH,SilvaRF,Nanotechnology, 2014,25,145602. [5]Mata D, Oliveira FJ, Neto MA, Belmonte M, Bastos AC, LopesMA,GomesPS,FernandesMH,SilvaRF,Nanomedicine: Nanotechnology, Biology and Medicine,submitted. Acknowledgments The work was carried out with the financial support of FCT (SFRH/BD/36273/2007)andPEst-C/CTM/LA0011/2013. Figure 3. (a-c)Cellviability/proliferationofosteoblasticcellculturesgrownoverstandardcellculturecoverslips,Glass/HAmatrixandCNT/Glass/HAcomposite,andcharacterized24hafter1,3,and 5dailyelectricalstimuli,underdifferentstimulationconditions.(d-f)Expressionofosteoblastic-relatedgenesbycellculturescharacterized24hafter5dailyelectricalstimuliunder15μA,15min. Resultsareexpressedaspercentageofvariationfromnon-stimulatedcultures.DensitometricanalysisoftheRT-PCRbandsnormalizedtothecorrespondingGAPDHvalue.*Significantlydifferentfrom non-stimulatedcultures.CLSMappearanceofosteoblasticcellculturesgrownover(g)Glass/HAmatrixand(h)CNT/Glass/HAcomposite,andobserved24hafter3dailyelectricalstimuli,under15μA, 15min.CellswerestainedforF-actincytoskeleton(green)andnucleus(red). Biomedical Materials and Applications 71 Hydroxyapatite (Hap) is a calcium phosphate (CaP) with a chemical composition (Ca10(PO4)6(OH)2) that closely approaches that of the mineral constituents of hard tissues (i.e. teeth and bones) thus explaining its natural and excellent biocompatibility and hence its wide medical use. The biological genesis of bone mineral phase implies a deposition process mediated by a living tissue, consisting of a continuous synthesis, resorption and replacement of CaP under the action of living cells. This dynamic process modulates the composition and structure of bone mineral phase which are both space and time variable, reflecting the variability of body metabolism and the specificity of bone local cellular functions. The bone CaP consists of nanosized crystals of nonstoichiometric Hap, having a needle or plate like shape and thicknesses ranging from 30 to 120 nm, densely packed into woven collagen fibrils. The attempts to mimic the biological bone Hap nanoparticle (NP) morphology by different synthesis methods are plentiful but the subsequent follow up of the bone cell response induced by the synthesized particles is still scarce. Consequently the correlations between the morphological characteristics of the individual NP and the elicited cell response are still poorly established. A research focused on Hap NP is thus crucial for mapping NP route and its interaction with cells and tissues and thus benefit the current applications of Hap like biomineralization processes associated to Hap NP based scaffolds or drug delivery efficiency of Hap NP based drug carriers, in which the implications of Hap NP morphology are not yet clarified. The synthesis of Hap NPs with different morphological features and their impact on the osteoblastic cell response are here addressed. Two different synthesis methods were used to produce Hap NPs with distinct shape and size: prismatic rod-like and needle-like NP with a specific surface area of 55m2/g and 170m2/g, respectively. In addition to their morphology features, the differences between the NPs also include their crystallinity, surface electrical charge and surface adsorbed species which are also dissimilar. Considering that the ultimate application requires the target NP to be sterilized before subsequent in vivo appliMODULATING CELLULAR RESPONSE WITH ENGINEERED HAP NANOPARTICLES Costa MEV1, Almeida MM1, Santos C1 Figure 2.RepresentativeTEMmicrographsofosteoblasticcellculturesexposedtosterilizedrod-like(A,BandC)andtoneedle-like Hapnanoparticles(E,FandG),50and500μg/ml,duringdifferentperiods.TheemissionofpseudopodssurroundingadjacentnanoparticlesisobservedinAandD(3hours,50μg/ml),B(3days,50μg/ml)andE(3hours,500μg/ml);CandF(24hours,500μg/ml) depictsclustersofnanoparticlesentrappedinendosomes. Figure 1.TEMimagesofHapnanoparticles(NP):“asprepared”needle-likeandrod-likeNPandsterilizedNPs. Biomedical Materials and Applications78 creased glucose, citrate, formate, acetate, several amino acids (alanine, glutamine, histidine, tyrosine, valine) and methanol (Figure 1). An equally good discrimination between lung cancer and healthy subjects was obtained by NMR profiling of urine [4], highlighting a number of consistently altered metabolites, such as hippurate and trigonelline (reduced in patients), and b-hydroxyisovalerate, α-hydroxyisobutyrate, N-acetylglutamine and creatinine (elevated in patients relatively to controls). Notably, possible confounders (age, gender, smoking habits) were found to have a lower impact on the biofluids composition compared to the presence of the disease. Moreover, the changes detected in both plasma and urine were present at initial disease stages, thus supporting the promising value of NMR metabolomics in lung cancer screening and early detection. 1DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal 2DepartmentofChemistry,QOPNA,UniversityofAveiro,3810193Aveiro,Portugal 3Laboratory of Cytogenetics and Genomics, Faculty of Medicine,UniversityofCoimbra,3000Coimbra,Portugal 4CIMAGO, Faculty of Medicine, University of Coimbra, 3000 Coimbra,Portugal 5UniversityHospitalsofCoimbra,3000-075Coimbra,Portugal 6Institute of Pathological Anatomy, Faculty of Medicine, UniversityofCoimbra,3000Coimbra,Portugal References [1]DuarteIF,GilAM,Progress in Nuclear Magnetic Resonance Spectroscopy,2012,51-74. [2]Duarte IF, Rocha CM, Gil AM, Expert Review of Molecular Diagnostics,2013,13(7),737-48. [3]RochaCM,CarrolaJ,BarrosAS,GilAM,GoodfellowBJ,Carreira IM,BernardoJ,GomesA,SousaV,CarvalhoL,DuarteIF,Journal of Proteome Research,2011,10(9),4314-4324. [4]CarrolaJ,RochaCM,BarrosAS,GilAM,GoodfellowBJ,Carreira IM,BernardoJ,GomesA,SousaV,CarvalhoL,DuarteIF,Journal of Proteome Research,2011,10(1),221-230. Figure 1.LoadingsplotobtainedbyPartialLeastSquaresDiscriminantAnalysis(PLS-DA)of1HNMRplasmaspectraofhealthysubjects(n78)andlungcancerpatients(n85).Positive/negativesignalsrefer,respectively,tocompoundsincreased/decreasedin patientsrelativelytocontrols.Thecolourscalereflectstheimportantofvariablesforclassdiscrimination. Based on the premise that drugs consistently affect cellular metabolism, metabolic profiling (or metabolomics) of cultured cells has the potential to provide new insights about drugs’ mechanisms of action and to reveal new endpoint markers of drug toxicity and/or efficacy. 1H High Resolution Magic Angle Spinning (HRMAS) Nuclear Magnetic Resonance (NMR) spectroscopy is particularly powerful in this context, as it allows wellresolved spectra to be obtained directly from cells (or cell lysates), providing rapid information on the quantitative variations in both small metabolites and mobile lipids, simultaneously (Figure 1). In this work, 1H HRMAS NMR was used to characterize the intracellular composition (endometabolome) of A549 human lung adenocarcinoma cells exposed to cisplatin, an alkylating drug commonly used in chemotherapy for several cancer types (including lung cancer) [1]. One of the most striking differences between control and treated cells regarded lipid signals, namely those arising from triglycerides (TG) and cholesterol esters, which significantly increased upon cisplatin exposure. Moreover, TG accumulating in treated cells were shown to have greater average fatty acyl chain length and unsaturation degree, compared to those detected in control cells. Other than lipid-related changes, consistent variations were observed for nucleotide sugars (UDP-GNAc) and sorbitol (increased in treated cells), niacinamide and several amino acids (decreased in treated cells). The marked increase in nucleotide sugars, especially in uridine diphosphate N-acetylglucosamine (UDP-GlcNAc), was a particularly interesting observation as these compounds, produced from glucose via the hexosamine biosynthetic pathway (HBP), act as donor molecules for glycosylation of proteins and lipids, a modification known to be important in a number of biological processes and diseases, including cancer. Moreover, a strong correlation was observed between lipids and nucleotide sugars’ variations, suggesting that the biogenesis of lipid droplets and the hexosamine biosynthesis and/or glycosylation pathways may be mechanistically associated. Overall, these results show that in vitro NMR metabolomics is a powerful tool for detecting variations in a range of intracellular compounds upon drug exposure, thus offering the possiPOTENTIAL MARKERS OF CISPLATIN TREATMENT RESPONSE UNvEILED BY NMR METABOLOMICS OF HUMAN LUNG CELLS Duarte IF1, Ladeirinha AF2, Lamego I1, Gil AM1, Carvalho L3,4,5, Carreira IM2,5, Melo JB2,5 Biomedical Materials and Applications 79 bility of identifying candidate metabolite markers for in vivo monitoring of tumour responsiveness to treatment. 1DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal 2Laboratory of Cytogenetics and Genomics, Faculty of Medicine,UniversityofCoimbra,3000Coimbra,Portugal 3UniversityHospitalsofCoimbra,3000-075Coimbra,Portugal 4Institute of Pathological Anatomy, Faculty of Medicine, UniversityofCoimbra,3000Coimbra,Portugal 5CIMAGO, Faculty of Medicine, University of Coimbra, 3000 Coimbra,Portugal. Reference [1]DuarteIF,LadeirinhaA,LamegoI,GilAM,CarvalhoL,Carreira IM, Melo JB, Molecular Pharmaceutics, 2013, 10(11), 42424251. Figure 1.Average1HHRMASNMRspectraofa)controlandb)cisplatin-treatedA549lungcells,at48hours.Someassignmentsareindicated:Three-lettercodeusedforaminoacids,Adoadenosine,Chocholine,f.a.fattyacylgroups,GPCglycerophosphocholine,GSH reducedglutathione,PCphosphocholine,PTCphosphatidylcholine,TGtriglycerides,UDP-GalNAcuridinediphosphategalactosamine, UDP-GlcNAcuridinediphosphateglucosamine,UDP-GNAcuridinediphosphatehexosamine,Urduridine. Computational Methods and Theory Computational Methods and Theory82 The anion transmembrane transport is essential to cell functioning and depends on several mechanisms, such as anions channels. The dysfunction of these channels is currently linked with the occurrence of several pathologies, including cystic fibrosis and male infertility, caused by defective transmembrane transport of chloride and bicarbonate anions. The lack of natural alternative anionophores led to great interest in the development of synthetic molecules able to promote passive anion transport with the potential to be applied as replacement therapeutics. Molecular Dynamics (MD) simulations are a powerful tool to investigate the impact of the artificial transporters on the structural and dynamic properties of the phospholipid bilayers. Moreover, MD simulations also give valuable insights on how these molecules mediate the anion transmembrane transport. Following our research interests on this field of supramolecular chemistry, we have studied the potential of a calix[4]arene derivative (1) as chloride anion transporter by MD simulations in a DOPC bilayer. This putative transporter has four protonated NH3 + binding groups in the upper rim and four hydrophobic aliphatic tails in the lower rim. Unconstrained MD simulations show that the interaction of 1 with DOPC occurs via the NH3 + groups, which are able to establish electrostatic interactions and multiple hydrogen bonds with the DOPC phosphate groups, while the aliphatic tails point towards the water phase (when 1 was initially positioned in the water phase) or to the membrane (when 1 starts within the bilayer). The interaction does not induce any relevant DEVELOPMENT OF SYNTHETIC ANION CARRIERS FOR REPLACEMENT THERAPIES: A COMPUTATIONAL APPROACH Félix V1, Marques I1, Colaço AR1, Costa PJ2, Busschaert N3, Gale PA3,4 Halogen bonding is the attractive intermolecular interaction between an electron deficient positively polarized halogen atom and a Lewis base. Although anion recognition in solution takes advantage of the ubiquitous hydrogen bonding, the halogen bonding is rapidly becoming an established field in its own right. An extensive collaboration between our group and the group of Prof. Paul Beer (University of Oxford) resulted in the development and application of halogen bonding in the field of anion recognition. In our first work, anion templation was used to prepare the first halogen bonding catenane, which binds and senses selectively chloride and bromide in CH3CN solution [1]. Molecular dynamics simulations were performed in explicit CH3CN using the structure of the halogen bonding catenane bound to chloride and, among other analyses, a representative snapshot was extracted (Fig. 1). Two simultaneous halogen bonds are established between the bromine atoms of both macrocycles and the chloride anion. A p–p stacking interaction between one hydroquinone and a naphthalene group was also observed throughout the course of a molecular dynamics simulation, corroborating the experimental data. In our second work, a new family of fluorescent halogen bonding macrocyclic halo-imidazolium receptors was described showing that the bromoand iodoreceptors bind selectively iodide and bromide, respectively, in the competitive CD3OD/ D2O (9:1) aqueous solvent mixture, sensing these anions exclusively via a fluorescence response [2]. The remarkable affinity of both receptors towards bromide was investigated by means of Density Functional Theory calculations and molecular dynamics simulations. The DFT optimized structure of the iodo-imidazolium receptor binding bromide is depicted in Fig. 2 and show that indeed the receptor is able to bind bromide with great affinity and relatively short C-I···Br− distances (3.192 Å). The subsequent molecular dynamics simulations showed that those two simultaneous halogen bondings were stable in explicit CH3OH/H2O mixtures, helping to complement the experimental characterization. 1DepartmentofChemistryandSecçãoAutónomadeCênciasda Saúde,CICECO,UniversityofAveiro,3810-193Aveiro,Portugal 2Chemistry Research Laboratory, Department of Chemistry, UniversityofOxford,MansfieldRoad,Oxford,OX13TA,UK References [1]CaballeroA,ZapataF,WhiteNG,CostaPJ,FélixV,BeerPD, Angewandte Chemie International Edition, 2012, 51, 18761880. [2]Zapata F, Caballero A, White NG, Claridge TDW, Costa PJ, Félix V, Beer PD, Journal of the American Chemical Society, 2012,134,11533-1154. HALOGEN-BONDING IN ANION RECOGNITION Costa PJ1, Félix V1, Beer PD2 Figure 1Representativeco-conformationoftheXB catenane boundtochlorideinCH3CNsolution.ThetwoC-Br···Cl−halogen bondsaredrawnaslightbluedashedlines. Figure 2DFToptimizedstructureoftheiodo-imidazoliumreceptorbindingbromide,showingthecorrespondinghalogenbondinginteractionsasyellowdashedlines. Computational Methods and Theory 83 perturbation on the biophysical properties of the bilayer, apart from a systematic increase in the order parameter of the C2 carbon atom of the sn-1 lipid tail. Steered Molecular Dynamics (SMD) simulations were performed in order to simulate the permeation of the bilayer by 1 and as well to evaluate the energy barrier associated with this event. To the best of our knowledge, this SMD simulation is the first evidence at molecular level of the occurrence of chloride transport assisted by a synthetic molecule, as illustrated by the sequence of events shown in Figure 1, in agreement with anion carrier mechanism. Furthermore, the Potential of Mean Force (PMF) indicates a barrier of ca. 58 kJmol-1 for 1 to cross the membrane.[1] Moreover, we are also in collaboration with the colleague Philip Gale (University of Southampton), in an effort to obtain insights regarding several series of potential anion transmembrane transporters. One highlight of this combination of theoretical and experimental efforts is the study of the interaction of six synthetic chloride transmembrane transporters with a POPC bilayer by means of MD simulations. The general Amber force field (GAFF) was set to describe the transporters, while LIPID11 was used for the POPC lipids. These transporters are structurally simple molecules, based on the tris(2aminoethyl)amine scaffold, containing three thiourea binding units coupled with three n-butyl (2), phenyl (3), fluorophenyl (4), pentafluorophenyl (5), trifluoromethylphenyl (6), or bis(trifluoromethyl)phenyl (7) substituents. The passive diffusion of 2–7 ⊃ Cl− was evaluated with the complexes initially positioned either in the water phase or inside the bilayer. In the first scenario the chloride is released in the water solution before the synthetic molecules achieve the water–lipid interface and permeate the membrane (Figure 2). In the second scenario, the anion is released to the water phase only when the chloride complex reaches the interface (Figure 3). Independently of the transporter used in the membrane system, the bilayer structure is preserved and the synthetic molecules interact with the POPC molecules at the phosphate headgroup level, via N–H···O hydrogen bonds. Overall, the MD simulations’ results indicate that the small tripodal molecules in this series have a low impact on the bilayer and are able to diffuse with chloride inside the lipid environment, potentially as anion carriers.[2] 1DepartmentofChemistryandSecçãoAutónomadeCênciasda Saúde,CICECO,UniversityofAveiro,3810-193Aveiro,Portugal 2DepartmentofChemistryandSecçãoAutónomadeCênciasda Saúde,QOPNA,UniversityofAveiro,3810-193Aveiro,Portugal 3 Chemistry,UniversityofSouthampton,Southampton,UK 4 DepartmentofChemistry,FacultyofScience,KingAbdulaziz University,Jeddah21589,SaudiArabia References [1]CostaPJ,MarquesI,FelixV,Biochimica et Biophysica Acta, 2014,1838,890-901. [2]MarquesI,ColacoAR,CostaPJ,BusschaertN,GalePA,FelixV, Soft Matter,2014,10,3608-3621. Figure 1.Thetransmembranetransportoftwochlorideanionsassistedby1 isillustratedwithfourconsecutivesnapshots.The transporterandphosphorusatomsarerepresentedinsphereswithhydrogenatomsinwhite,oxygenatomsinred,nitrogenatomsinblueandcarbonatomsinyellow(transporter)orwheat(phospholipids)colour,whilethechlorideionsareshownasgreen spheres.ThelipidsC–Hatomsandthewaterslabswereomittedforclarity. Figure 2.Theapproachof4tothewater–lipidinterfaceofthebilayerisillustratedwithfiveconsecutivesnapshots.Thetransporter andphosphorusatomsarerepresentedinsphereswithhydrogenatomsinwhite,oxygenatomsinred,nitrogenatomsinblueand carbonatomsinpurple(transporter)orwheat(phospholipids)colour,whilethechlorideandsodiumionsareshownasgreenand pinkspheres,respectively.ThelipidsC–Hatomsandthewaterslabswereomittedforclarity. Figure 3.Thediffusionof4fromthebilayercoreandthereleaseofthechlorideanionisillustratedwithfiveconsecutivesnapshots. Thetransporterandphosphorusatomsarerepresentedinsphereswithhydrogenatomsinwhite,oxygenatomsinred,nitrogenatomsinblueandcarbonatomsinpurple(transporter)orwheat(phospholipids)colour,whilethechlorideandsodiumionsareshown asgreenandpinkspheres,respectively.ThelipidsC–Hatomsandthewaterslabswereomittedforclarity. Computational Methods and Theory84 Telomeres can fold into quadruplex structures in vivo and shortening of telomeres on chromosomal replication is considered to be a major cause of senescence. Additionally, cancer cells have been shown to generate an immortal phenotype by upregulating telomerase. Since the activity of telomerase is inhibited by the presence of G-quadruplexes there is a great potential in novel compounds able to bind and stabilize quadruplexes as anticancer agents. This Highlight focuses on an ongoing collaboration between the group of Macromolecular Modelling and Computational Biophysics (UA) and colleagues from University of Sheffield which ambitions to develop luminescent metal complexes as sequence and structure specific DNA binding substrates. In this context, the quadruplex binding properties of dinuclear ruthenium(II) complexes containing the tetrapyrido[3,2a:2′,3′-c:3′′,2′′-h:2′′′,3′′′-j]phenazine (tpphz) depicted in Figure 1were studied using a combination of NMR experiments and Molecular Dynamics (MD) simulations. Both [{Ru(bipy)2}2tpphz]4+, 1, and [{Ru(phen)2}2tpphz]4+, 2, (where bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline), bind to quadruplex DNA but the ΛΛ isomer binds approximately 40 times more tightly than the ΔΔ, with a stronger luminescence. The structures based on NMR experimentally derived restraints show that the ΛΛ isomer fits neatly under the diagonal loop, whereas the ΔΔ isomer is unable to bind here and binds at the lateral loop end. In order to try to explain this selectivity, we performed unrestrained MD simulations to evaluate the impact of ΛΛ-1 and ΔΔ-1 complexes on the quadruplex structure when binding under the diagonal loop. The results suggest that, although both ΛΛ-1 and ΔΔ-1 complexes can fit under the loop (see Figure 2), sufficient HTS loop conformational freedom to permit the complex entrance into the prefolded G-DNA structure is only present for ΛΛ1. In contrast, the stereochemistry of ΔΔ-1 appears to induce increased rigidity on the loop, preventing complex entrance into the loop arch. This structural feature is depicted in Figure 3, which shows a surface representation built from the positions occupied by the tpphz ligand (excluding the hydrogen atoms) over a 50 ns collection period for the HTS association with each one of the diastereomers. In ΛΛ-1-HTS, the tpphz ligand is able to “float” over the G-tetrad interacting with the four guanines. In contrast, in ΔΔ-1HTS, the tpphz ligand remains “locked” over two guanines of the G-tetrad throughout the entire simulation time. In other words, ΔΔ-1 does not bind under the diagonal loop because the loop arch does not fulfill the complex’s “stereochemical requirements”. In summary, this work showed that ΛΛ-1, as well as ΛΛ-2, is a useful tool for specifically stabilizing and imaging antiparallel basket structures with a diagonal loop and confirms that the antiparallel structure of HTS can be selectively targeted. DINUCLEAR RUTHENIUM(II) COMPLEXES FOR STABILIZING AND IMAGING AN ANTIPARALLEL FOLDED HUMAN TELOMERE SEQUENCE Félix V1,3, Costa PJ2,3, Williamson MP4, Thomas JA5, Wilson T4,5 Figure 1.(A)Structures ofcomplexesstudied.(B) Thetwopossibleenantiomersofeachofthemetalcenters in1and2.(C) Schematicofthetwodiastereomersof1and2relevanttothisstudy:leftΛΛ;rightΔΔ. Figure 2.RepresentativesnapshotsofsimulationsΛΛ-1-HTS(top,magenta)andΔΔ-1-HTS(bottom,aquamarine)showingboth complexesunderthediagonalloop.Sideandtopviewsarepresentedontheleftandcenter,respectively.Rightpicturesrepresent thecomplexesstackedoverthetopG-quartet. Computational Methods and Theory 85 1DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal 2DepartmentofChemistry,QOPNA,UniversityofAveiro,3810193Aveiro,Portugal 3SecçãoAutónomadeCiênciasdaSaúde,UniversityofAveiro, 3810-193Aveiro,Portugal 4DepartmentofMolecularBiologyandBiotechnology,UniversityofSheffield,UK 5DepartmentofChemistry,UniversityofSheffield,UK Reference [1]WilsonT,CostaPJ,FélixV,WilliamsonMP,ThomasJA,Journal of Medicinal Chemistry,2013,56,8674−8683. Figure 3.Surfacerepresentingthehistogramofpositionsoccupiedbythetpphzatomsoverthe50nscollectionperiodinΛΛ-1-HTS (left)andΔΔ-1-HTS(right). Chemical processes often consist of a number of elementary reaction steps where bond making and bond breaking occur. One of such important elementary steps concerns the cleavage of the RO─H functional group since this is present in many common compounds such as alcohols, organic acids or even water. There are several heterogeneous catalytic processes where elementary steps involving the cleavage of O─H bonds either in reactants or intermediate species play a key role. The water gas shift reaction (WGS: CO + H2O → CO2 + H2) is essential in the production of clean hydrogen, and the ability of the catalyst to dissociate the O─H bonds in the water molecule becomes crucial. The scission of O─H bonds is also involved in the selective oxidation of alcohols to carboxylic compounds over heterogeneous recyclable catalysts and, in general, the mechanism for alcohol oxidation involves the formation of an adsorbed alkoxy species. Due to the important role of the O─H bond in many chemical processes it would be important to rationalize the vast number of available results and to develop tools for predicting the activities of catalysts towards the reaction of O─H bond dissociation. Previously, based on energetic data calculated through density functional theory (DFT), we have found that it is possible to estimate/predict the activity of metal-based surfaces for the catalysis of the O─H bond scission in water by consideration of Brønsted-Evans-Polanyi (BEP) type relationships connecting the energy barrier required to break the bond and several descriptors that may be easily calculated or found in the literature, such as the reaction energy, the adsorption energy of the reaction products, or even the adsorption energy of an oxygen atom [1]. Now, we extended these ideas and developed a new BEP relationship for predicting the activities of planar or stepped metal surfaces and metal particles towards the catalysis of the O─H bond scission in any compound [2]. The adsorption energy of the reaction products was found SIMPLE DESCRIPTORS FOR PREDICTING THE CATALYTIC ACTIVITY OF TRANSITION METAL SURFACES FOR O-H BOND DISSOCIATION REACTIONS Fajín JLC1, Cordeiro MNDS1, Illas F2, Gomes JRB3 Figure 1.RelationshipbetweentheactivationenergybarrierfortheROH*+*→RO*+H*reactionandtheco-adsorptionenergyof theROandHspeciesonplanarandsteppedmetallicorbimetallicsurfacesandplatinumnanoparticles,withR=HO,CH3O,CH3CH2O andROH=water,methanolandethanol,respectively.E,F,NandPstandforethanol,formicacid,Ni(111)andPd(111),respectively. *denotesanadsorptionsiteavailableonthecatalystmodelsurface. Computational Methods and Theory86 Periodic mesoporous organosilicas (PMOs) are materials presenting unique structural properties due to their hybrid building blocks, based on organic and inorganic (silicate) moieties, which self-assemble in aqueous solutions of surfactants under basic conditions to create ordered architectures with nanometer-thick walls and uniform pores between 2 - 30 nm in width. The syntheses of the first examples of PMOs were accomplished from bis(trialkoxysilyl) ethane, or bis(trialkoxysilyl)ethylene or bis(trialkoxysilyl)benzene precursors and solutions containing alkyltrimethylammonium bromide surfactants. The benzenesilica and ethylenesilica materials display both mesoand molecular-scale periodicity, with clearly alternating organic and inorganic layers on the pore surface. Molecular scale is absent when the materials were prepared from ethanesilica. Differences were attributed to the size of the organic linker and to the strength of the organosilicate–organosilicate interactions but no explicit evidence was presented. Molecular dynamics (MD) simulations using atomistic models were performed with the aim of unveiling the role of the organic linker in the structural differences observed between PMOs synthesized with different organosilicates.[1] The simulations considered three different highpH decyltrimethylammonium bromide, water and organosilica solutions, where the linker is benzene, ethylene or ethane, i.e., linkers that were found to lead to a high degree, to a lower degree, and to no molecular-scale periodicity, respectively. Figure 1 shows the evolution of the mass average micelle size with simulation time, where it is clear that benzenesilica or ethylenesilica promote the formation of larger aggregates than those seen in the solution with ethanesilica. This most probably originates from the higher concentration of silica species in the regions close to the surfactant heads in the two former cases as can be seen in the density profiles shown in Figure 2. Note that not only the inorganic but also the organic parts of the organosilicates are found in the space between the surfactant heads, but the densities of the silicate moieties in the tail/head interface region are visibly larger when the linker is benzene or ethylene than when the linker is ethane. The density profiles for the organic linkers follow closely the behavior observed for the inorganic parts of the organosilicates, i.e., for the solution containing benzenesilica there is a well-defined peak for the organic part and the peak becomes visibly broader in the case of ethylenesilica and virtually disappears in the case of ethanesilica. Thus, most of the organosilicates interact with the micelle surface and are located in between the head groups in the former cases. A contrasting behavior is found for the solution with ethanesilica, for which the maximum of the silica density is outside the highest density region for the surfactant head groups. In this case, the organic linkers seem to be much more mobile and a well-defined peak is absent. Thus, results show that the presence or absence of molecularscale periodicity in the pore walls of the PMO materials is due to different mechanisms of interaction between surfactant ON THE ORIGINS OF THE MOLECULAR-SCALE PERIODICITY IN THE PORE WALLS OF PERIODIC MESOPOROUS ORGANOSILICAS Futamura R1, Jorge M2, Gomes JRB1 to be the most convenient descriptor for the RO─H bond break with the resulting fitting shown in Figure 1. The validity of the relationship has been explored by considering cases not included in the database of energy barriers and adsorption energies used to its development. The use of this descriptor allows a fast and easy screening of the cases of interest on a rather large number of metallic surfaces, bimetallic surfaces and nanoparticles without needing to carry out tedious calculations for transition state structure location and characterizations or keeping this to a minimum number on potential candidate systems. Therefore, explicit calculation of the activation energy barriers are limited to a few, previously detected, interesting cases only. 1Department of Chemistry, REQUIMTE, Faculty of Sciences, UniversityofPorto,Portugal 2Department of Chemistry, IQTQUB, Faculty of Chemistry, UniversityofBarcelona,Spain 3DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal References [1]Fajín JLC, Cordeiro MNDS, Illas F, Gomes JRB, Journal of Catalysis,2010,276,92-100. [2]Fajín JLC, Cordeiro MNDS, Illas F, Gomes JRB, Journal of Catalysis,2014,313,24-33. Figure 1.Mass-averagemicellesizeasafunctionofsimulation time for the solutions with benzenesilica, ethylenesilica and ethanesilica. Figure 2. Density profiles of micelles with ~20 surfactants formedinsolutionswitha)benzenesilica,b)ethylenesilicaand c)ethanesilica. Computational Methods and Theory 87 micelles and organosilicates at the very early stages of the templated synthesis process. Precursors that adsorb strongly and orient their Si–Org–Si axis parallel to the micelle surface may lead to materials with molecular-scale periodicity, while with more flexible precursors that are less ordered this periodicity is not observed. 1DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal 2LSRE/LCM,FacultyofEngineering,UniversityofPorto,Portugal Reference [1]Futamura R, Jorge M, Gomes JRB, Physical Chemistry Chemical Physics,2013,15,6166-6169. Metal-Organic Frameworks (MOFs) allow for simultaneously tuning the pore structure and the surface chemistry of the adsorbent, thus opening the possibility of a priori material design to suit particular adsorption applications, including gas storage and separation. MOFs have shown tremendous potential for challenging gas separation applications, an example of which is the separation of olefins from paraffins. Some of the most promising MOFs show enhanced selectivity for olefins due to the presence of coordinatively unsaturated metal sites. CuBTC, or HKUST-1, is a commercial MOF containing unsaturated Cu sites that are able to selectively bind unsaturated hydrocarbons by interacting with the p-orbitals of these molecules. Unfortunately, it is still not possible to accurately predict adsorption in MOFs with unsaturated metal sites, since most classical models are unable to cope with this phenomenon. A new approach to model adsorption in MOFs with unsaturated metal sites in CuBTC is presented [1,2]. It combines electronic density functional theory (DFT) calculations with grand canonical Monte Carlo (GCMC) simulations at the classical level (Figure 1). The DFT calculations were used to calculate the energy profile for ethylene adsorption on the unsaturated metal sites of CuBTC. Then, an empirical function for modelling the specific Cu-p interaction energy profile was calculated from UCu-p (r) = UDFT (r) – URep (r), where UDFT is the DFT interaction energy between ethylene and the CuBTC cluster, UCu-p is the contribution to the energy due to the specific interaction between the Cu atom and the olefin double bond, URep is the repulsion contribution and made equal to the repulsive contribution of the Lennard-Jones potential, and r is the distance between the center of the double bond and the closest Cu atom of the MOF. With this approach, the remainder of the model, i.e., the LJ interactions between each adsorbate site and all the other adsorbate and adsorbent sites in the system (including the metal), were kept unchanged relatively to the standard DREIDING force field that can tackle correctly the interaction between alkanes and CuBTC. It presents obvious advantages: i) it allows to simplify the problem, without the need for a full reparameterization of all the fluid-solid potential parameters; ii) it increases the chances that the model will be transferable to other MOFs; and iii) the model will benefit directly from independent force field developments. Using this new approach, it was possible to accurately predict adsorption isotherms not only for ethylene on CuBTC, which was the adsorbate used to derive the new function, but also for ethane, propane and propylene (Figure 2). Crucially, it was found that good predictions can only be obtained in the case of the olefins only when the specific interactions between the metal sites and the olefin double bonds are explicitly taken into account in the simulations. 1DepartmentofChemicalandProcessEngineering,University ofStrathclyde,UnitedKingdom 2FachbereichGeowissenschaften,UniversityofBremen,Germany 3DepartmentofChemistry,CICECO,UniversityofAveiro,3810193Aveiro,Portugal References [1]FischerM,GomesJRB,FröbaM,JorgeM,Langmuir,2012,28, 8537-8549. [2]Jorge M, Fischer M, Gomes JRB, Siquet C, Santos JC, RodriguesAE,Industrial and Engineering Chemistry Research, 2014,inpress.DOI:10.1021/ie500310c COMBINING QUANTUM MECHANICS WITH MOLECULAR SIMULATION FOR PREDICTING ADSORPTION IN MOFS WITH UNSATURATED METAL SITES Jorge M1, Fischer M2, Gomes JRB3 Figure 2.Comparisonbetweenexperimental(points)andsimulated(lines)adsorptionisotherms forpropyleneonCuBTCat severaltemperatures. Figure 1.OntheleftitisshownthegeometryusedfortheDFTcalculationsofethyleneadsorbingontoaCu2(btc)4cluster(btc=benzene-tricarboxylate)whileontherightitisshownatypicalsnapshotfromtheGCMCsimulationsonpropyleneadsorptioninCuBTC. ColorcodingisgreenforCintheframework,purpleforCinthesorbate,whiteforH,redforO,andyellowforCu.