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Under the terms of the Creative Commons Attribution 3.0 Unported License.-- Trabajo presentado a la 49th European High Pressure Research Group Conference (EHPRG), celebrada en Mumbai (India) del 25 al 30 de septiembre de 2011.-- et al. ; High-pressure Raman scattering measurements have been carried out in ZnGa2Se4 for both tetragonal defect chalcopyrite and defect stannite structures. Experimental results have been compared with theoretical lattice dynamics ab initio calculations and confirm that both phases exhibit different Raman-active phonons with slightly different pressure dependence. A pressure-induced phase transition to a Raman-inactive phase occurs for both phases; however, the sample with defect chalcopyrite structure requires slightly higher pressures than the sample with defect stannite structure to fully transform into the Raman-inactive phase. On downstroke, the Raman-inactive phase transforms into a phase that could be attributed to a disordered zincblende structure for both original phases; however, the sample with original defect chalcopyrite structure compressed just above 20 GPa, where the transformation to the Raman-inactive phase is not completed, returns on downstroke mainly to its original structure but shows a new peak that does not correspond to the defect chalcopyrite phase. The pressure dependence of the Raman spectra with this new peak and those of the disordered zincblende phase is also reported and discussed. © 2013 AIP Publishing LLC. ; This study was supported by the Spanish government MEC under Grants No. MAT2010-21270-C04-01/03/04, by MALTA Consolider Ingenio 2010 project (CSD2007- 00045), and by the Vicerrectorado de Investigación y Desarrollo of the Universitat Politécnica de Valencia (UPV2011-0914 PAID-05-11 and UPV2011-0966 PAID-06-11). ; Peer Reviewed

et al. ; Order-disorder phase transitions induced by thermal annealing have been studied in the ordered-vacancy compound ZnGa2Se4 by means of Raman scattering and optical absorption measurements. The partially disordered as-grown sample with tetragonal defect stannite (DS) structure and I N42m space group has been subjected to controlled heating and cooling cycles. In situ Raman scattering measurements carried out during the whole annealing cycle show that annealing the sample to 400 °C results in a cation ordering in the sample, leading to the crystallization of the ordered tetragonal defect chalcopyrite (DC) structure with I N4 space group. On decreasing temperature the ordered cation scheme of the DC phase can be retained at ambient conditions. The symmetry of the Raman-active modes in both DS and DC phases is discussed and the similarities and differences between the Raman spectra of the two phases emphasized. The ordered structure of annealed samples is confirmed by optical absorption measurements and ab initio calculations, that show that the direct bandgap of DC-ZnGa2Se4 is larger than that of DS-ZnGa 2Se4. © 2013 IOP Publishing Ltd. ; This study was supported by the Spanish government MEC under grants MAT2010-21270-C04-01/03/04 and MAT2010-19837-C06-06, by MALTA Consolider Ingenio 2010 project (CSD2007-00045), and by the Vicerrectorado de Investigación y Desarrollo of the Universitat Politècnica de Valencia (UPV2011-0914 PAID-05-11 and UPV2011-0966 PAID-06-11). ; Peer Reviewed

A laser melting method has been developed for the synthesis of highly luminescent, long-lasting SrAl2O4:Eu2+, Dy3+ phosphors. The high temperature achieved in high-power density CO2 laser irradiation of mixtures of SrCO3, Al2O3, Eu2O3, and Dy2O3 enabled the one-step, fast synthesis of these phosphors in air at atmospheric pressure. X-ray diffraction, Raman spectroscopy, and scanning electron microscopy characterization studies reveal that the produced materials consist of monoclinic SrAl2O4 grains extensively surrounded by rare-earth ion-enriched grain boundaries. The photoluminescence properties of laser-produced SrAl2O4:Eu2+, Dy3+ materials are discussed. The results reported here suggest that this laser melting method is a promising route for the synthesis of ceramic phosphors. It is presented as an alternative to the conventional sol–gel and solid-state methods, which require the use of high-temperature furnaces, flux additives, and reducing atmospheres. ; The authors acknowledge financial support from the Spanish Ministry of Science and Innovation (MICINN, projects CEN-20072014, SOL-00030930, MAT2010-18519 and MAT2010-19837-C06-06), IMPLASER 99 S.L.L. (http://www.implaser.com), and the regional Government of Aragón (Spain, project PI119/09, and Excellence Research Groups Program T87). ; Peer Reviewed

The first fluorination of the cuspidine-related phases of Ln4(Al2O7□)O2 (where Ln = Sm, Eu, Gd) is reported. A low-temperature reaction with poly(vinyl-idene difluoride) lead to the fluorine being substituted in place of oxygen and inserted into the vacant position between the dialuminate groups. X-ray photoelectron spectroscopy shows the presence of the F 1s photoelectron together with an increase in Al 2p and rare-earth 4d binding energies supporting F incorporation. Energy-dispersive X-ray spectroscopy analyses are consistent with the formula Ln4(Al2O6F2)O2, confirming that substitution of one oxygen by two fluoride atoms has been achieved. Rietveld refinements show an expansion in the cell upon fluorination and confirm that the incorporation of fluoride in the Ln4(Al2O7□)O2 structure results in changes in Al coordination from four to five. Thus, the isolated tetrahedral dialuminate Al2O7 groups are converted to chains of distorted square-based pyramids. These structural results are also discussed based on Raman spectra. ; This research was funded by the Ministerio de Economía, Industria y Competitividad (MAT2016-76739-R) (AEI/FEDER, UE), and Departamento de Educación of the Basque Government (IT-630–13). The authors thank SGIker of UPV/EHU for technical and personnel support. A. Mora´nRuiz thanks UPV/EHU for funding. ; Peer reviewed

This is an Open Access article distributed under the terms of the Creative Commons Attribution License. ; Laser ablation of selected coordination complexes can lead to the production of metal-carbon hybrid materials, whose composition and structure can be tailored by suitably choosing the chemical composition of the irradiated targets. This 'laser chemistry' approach, initially applied by our group to the synthesis of P-containing nanostructured carbon foams (NCFs) from triphenylphosphine-based Au and Cu compounds, is broadened in this study to the production of other metal-NCFs and P-free NCFs. Thus, our results show that P-free coordination compounds and commercial organic precursors can act as efficient carbon source for the growth of NCFs. Physicochemical characterization reveals that NCFs are low-density mesoporous materials with relatively low specific surface areas and thermally stable in air up to around 600°C. Moreover, NCFs disperse well in a variety of solvents and can be successfully chemically processed to enable their handling and provide NCF-containing biocomposite fibers by a wet-chemical spinning process. These promising results may open new and interesting avenues toward the use of NCFs for technological applications. ; This work has been supported by the regional Government of Aragón (Spain, Project PI119/09, and E101 and T87 Research Groups funding) and the Spanish Government and Feder funds through grant MAT2010-19837-C06-06. This work has been funded in part by the European Commission through projects LIFE11/ENV/ES 560 and grant agreement no. 280658. ; Peer Reviewed

8 páginas, 8 figuras. ; Aromatic, triphenylphosphine-containing organometallic compounds, as well as non-aromatic organometallic targets, were irradiated with a Nd:YAG laser to study the role of the metals and ligands used on the structure of the resulting materials. Characterization shows that the composition, metal nanoparticle dilution and crystallite size, and structure of the carbon foams (CFs) produced can be tailored by choosing the metals and ligands of the irradiated targets. The results indicate that precursors containing triphenylphosphine ligands tend to yield larger amounts of ablation products in which graphitic structures are observed in appreciably larger quantities. Electron microscopy reveals that these CFs are multi-component materials that consist of metal nanoparticles embedded in amorphous carbon aggregates, amorphous carbon nanoparticles, and graphitic nanostructures, which can be eventually observed as independent, separate components in the produced soots. The graphitic structures observed can also be produced by laser ablation of triphenylphosphine, indicating that their growth is not promoted by the metals of the chosen aromatic organometallic compounds. ; This work has been supported by the regional Government of Aragón (Spain, Projects PM028/2007 and PI119/09, and Excellence Research Groups funding), MICINN (Spain, Projects TEC2004-05098-C02-02, CTQ2008-06716-C03-01, MAT2004- 01248, MAT2007-64486-C07-02, CEN-20072014), CSIC (Spain, Program I3 2006 8 0I 060), and the European Regional Development Fund (ERDF). ; Peer reviewed

This article belongs to the Special Issue Rational Design and Characterization of Hydrogels to Improve Pharmaceutical and Biomedical Applicability. ; Modifying hydrogels in order to enhance their conductivity is an exciting field with applications in cardio and neuro-regenerative medicine. Therefore, we have designed hybrid alginate hydrogels containing uncoated and protein-coated reduced graphene oxide (rGO). We specifically studied the adsorption of three different proteins, BSA, elastin, and collagen, and the outcomes when these protein-coated rGO nanocomposites are embedded within the hydrogels. Our results demonstrate that BSA, elastin, and collagen are adsorbed onto the rGO surface, through a non-spontaneous phenomenon that fits Langmuir and pseudo-second-order adsorption models. Protein-coated rGOs are able to preclude further adsorption of erythropoietin, but not insulin. Collagen showed better adsorption capacity than BSA and elastin due to its hydrophobic nature, although requiring more energy. Moreover, collagen-coated rGO hybrid alginate hydrogels showed an enhancement in conductivity, showing that it could be a promising conductive scaffold for regenerative medicine. ; This study was financially supported by the Basque Country Government [grant number T907-16]. ; Peer reviewed

This article belongs to the Section Drug Delivery and Controlled Release. ; The use of embedded cells within alginate matrices is a developing technique with great clinical applications in cell-based therapies. However, one feature that needs additional investigation is the improvement of alginate-cells viability, which could be achieved by integrating other materials with alginate to improve its surface properties. In recent years, the field of nanotechnology has shown the many properties of a huge number of materials. Graphene oxide (GO), for instance, seems to be a good choice for improving alginate cell viability and functionality. We previously observed that GO, coated with fetal bovine serum (FBS) within alginate hydrogels, improves the viability of embedded myoblasts. In the current research, we aim to study several proteins, specifically bovine serum albumin (BSA), type I collagen and elastin, to discern their impact on the previously observed improvement on embedded myoblasts within alginate hydrogels containing GO coated with FBS. Thus, we describe the mechanisms of the formation of BSA, collagen and elastin protein layers on the GO surface, showing a high adsorption by BSA and elastin, and a decreasing GO impedance and capacitance. Moreover, we described a better cell viability and protein release from embedded cells within hydrogels containing protein-coated GO. We conclude that these hybrid hydrogels could provide a step forward in regenerative medicine. ; This research was funded by the University of the Basque Country UPV/EHU and the Basque Country Government (Grupos Consolidados, No ref: IT907-16). ; Peer reviewed

Temporary Removal. ; Composite molten salt-ceramic membranes are promising devices for high-temperature CO2 separation. Intensive material properties impact on separation performance as do membrane geometry (thickness) and microstructure (pore volume fraction, size, connectivity, and tortuosity factor). Although controlling pore size is considered somewhat routine, achieving pore alignment and connectivity is still challenging. Here we report the production of the first gas separation membrane using a porous ceramic matrix obtained from a directionally-solidified magnesium-stabilised zirconia (MgSZ) – MgO fibrilar eutectic as the membrane support. MgO was removed from the parent material by acid-etching to create a porous matrix with highly aligned pores with diameters of ~1 μm. X-ray nano-computed tomography of a central portion (~32,000 μm3) of the support identified ~21% porosity, with all pores aligned within 10° and ~76% percolating along the longest sampled length. Employing the matrix as a support for a carbonate molten salt, a high CO2 permeability of 1.41x10-10 mol.m-1.s-1.Pa-1 at 815 °C was achieved, among the highest reported for supported molten-carbonate membranes (typically 10-12 to 10-10 mol.m-1.s-1.Pa-1 at similar temperatures). We suggest that the high permeability is attributable to the excellent pore characteristics resulting from directional solidification, namely a dense array of parallel, micron-scale pores connecting the feed and permeate sides of the membrane. ; The authors acknowledge the financial support from the Spanish Ministerio de Economía y Competitividad and Feder Funds under project MAT2016-77769R. L. Grima acknowledges financial support through grant BES-2017-079683 associated to the aforementioned project. The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement Number 320725 and from the Engineering & Physical Sciences Research Council (EPSRC) via grants EP/M01486X/1, EP/P007767/1 and EP/P009050/1. PRS acknowledges the Royal Academy of Engineering (CiET1718/59). PRS, DJLB, JJB and MDK acknowledge the support of The Faraday Institution (faraday.ac.uk; EP/ S003053/1). G. Mutch was supported by the Royal Academy of Engineering under the Research Fellowship Scheme and would like to thank the EPSRC for his Doctoral Prize Fellowship (EP/M50791X/1) and Newcastle University for a Newcastle University Academic Track (NUAcT) Fellowship. X-Ray CT acquisition and analysis was supported by UCL and EPSRC under EP/N032888/1. We thank the Servicio General de Apoyo a la Investigación-SAI (Universidad de Zaragoza) for technical support in X-ray diffraction and electron microscopy experiments, Rubén Gotor for technical assistance in sample preparation and R. Lahoz for laser-drilling the YSZ plate that serves as the membrane base. ; Peer reviewed

165802-1 165802-11 25 16 ; S Hahn, H., Frank, G., Klingler, W., St�rger, A. D., & St�rger, G. (1955). Untersuchungen �ber tern�re Chalkogenide. VI. �ber Tern�re Chalkogenide des Aluminiums, Galliums und Indiums mit Zink, Cadmium und Quecksilber. Zeitschrift f�r anorganische und allgemeine Chemie, 279(5-6), 241-270. doi:10.1002/zaac.19552790502 Haeuseler, H. (1978). FIR- und Ramanspektren von ternären Chalkogeniden des Galliums und Indiums mit Zink, Cadmium und Quecksilber. Journal of Solid State Chemistry, 26(4), 367-376. doi:10.1016/0022-4596(78)90171-8 Perdew, J. P., Burke, K., & Ernzerhof, M. (1997). Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]. Physical Review Letters, 78(7), 1396-1396. doi:10.1103/physrevlett.78.1396 ; Order-disorder phase transitions induced by thermal annealing have been studied in the ordered-vacancy compound ZnGa2Se4 by means of Raman scattering and optical absorption measurements. The partially disordered as-grown sample with tetragonal defect stannite (DS) structure and I (4) over bar 2m space group has been subjected to controlled heating and cooling cycles. In situ Raman scattering measurements carried out during the whole annealing cycle show that annealing the sample to 400 degrees C results in a cation ordering in the sample, leading to the crystallization of the ordered tetragonal defect chalcopyrite (DC) structure with I (4) over bar space group. On decreasing temperature the ordered cation scheme of the DC phase can be retained at ambient conditions. The symmetry of the Raman-active modes in both DS and DC phases is discussed and the similarities and differences between the Raman spectra of the two phases emphasized. The ordered structure of annealed samples is confirmed by optical absorption measurements and ab initio calculations, that show that the direct bandgap of DC-ZnGa2Se4 is larger than that of DS-ZnGa2Se4. This study was supported by the Spanish government MEC under grants MAT2010-21270-C04-01/03/04 and ...

Order-disorder phase transitions induced by thermal annealing have been studied in the ordered-vacancy compound ZnGa2Se4 by means of Raman scattering and optical absorption measurements. The partially disordered as-grown sample with tetragonal defect stannite (DS) structure and I (4) over bar 2m space group has been subjected to controlled heating and cooling cycles. In situ Raman scattering measurements carried out during the whole annealing cycle show that annealing the sample to 400 degrees C results in a cation ordering in the sample, leading to the crystallization of the ordered tetragonal defect chalcopyrite (DC) structure with I (4) over bar space group. On decreasing temperature the ordered cation scheme of the DC phase can be retained at ambient conditions. The symmetry of the Raman-active modes in both DS and DC phases is discussed and the similarities and differences between the Raman spectra of the two phases emphasized. The ordered structure of annealed samples is confirmed by optical absorption measurements and ab initio calculations, that show that the direct bandgap of DC-ZnGa2Se4 is larger than that of DS-ZnGa2Se4. ; This study was supported by the Spanish government MEC under grants MAT2010-21270-C04-01/03/04 and MAT2010-19837-C06-06, by MALTA Consolider Ingenio 2010 project (CSD2007-00045), and by the Vicerrectorado de Investigacion y Desarrollo of the Universitat Politecnica de Valencia (UPV2011-0914 PAID-05-11 and UPV2011-0966 PAID-06-11). EP-G, AM, and PR-H acknowledge computing time provided by Red Espanola de Supercomputacion (RES) and MALTA-Cluster. Finally, the authors would also like to acknowledge M C Moron for stimulating discussions and revision of the present manuscript. ; Vilaplana Cerda, RI.; Gomis Hilario, O.; Pérez-González, E.; Ortiz, HM.; Manjón Herrera, FJ.; Rodríguez-Hernández, P.; Muñoz, A. (2013). Thermally-activated cation ordering in ZnGa2Se4 single crystals studied by Raman scattering, optical absorption, and ab initio calculations. Journal of Physics: Condensed ...