Structural and dielectric properties of Cobaltacarborane Composite Polybenzimidazole Membranes as solid polymer electrolytes at high temperature

[EN] The conductivity of a series of composite membranes, based on polybenzimidazole (PBI) containing the metallacarborane salt M[Co(C2B9H11)(2)], M[COSANE] and tetraphenylborate, M[B(C6H5)(4)], M[TPB] both anions having the same number of atoms and the same negative charge, has been investigated. Different cations (M = H+, Li+ and Na+) have been studied and the composite membranes have been characterized by water uptake, swelling ratios, ATR FT-IR, thermogravimetric analysis and electrochemical impedance spectroscopy to explore the dielectric response and ion dynamics in composite membranes. Our results show that conductivity increases with increasing temperature and it is higher for H+ than for Li+ and Na+ for all temperatures under study. The mobility of Li+ is greater in [COSANE](-) than in [TPB](-) composite PBI@membranes while for Na+ it is the opposite. The temperature dependence of the conductivity of the composite was followed by a typical Arrhenius behaviour with two different regions: (1) between 20 and 100 degrees C, and (2) between 100 and 150 degrees C. Using the analysis of electrode polarization (EP) based on the Thrukhan theory we have calculated the ionic diffusion coefficients and the density of carriers. From the double logarithmic plot of the imaginary part of the conductivity (sigma '') versus frequency in the entire range of temperatures studied we have determined for each sample at each temperature, the frequency values of the onset (f(ON)) and full development of electrode polarization (f(MAX)), respectively, which permit us to calculate static permittivity.We gratefully acknowledge Spanish Ministerio de Economia y Competitividad (MINECO) for financial support by the ENE/2015-69203-R project and CTQ2016-75150-R project, and Generalitat de Catalunya (2014/SGR/149). I. Fuentes is enrolled in the PhD program of the UAB. The authors acknowledge Dr Oscar Sahuquillo for technical assistance in TGA.Fuentes, I.; Andrio Balado, A.; Garcia Bernabe, A.; Escorihuela Fuentes, J.; Viñas, C.; Teixidor, F.; Compañ Moreno, V. (2018). Structural and dielectric properties of Cobaltacarborane Composite Polybenzimidazole Membranes as solid polymer electrolytes at high temperature. Physical Chemistry Chemical Physics. 20(15):10173-10185. https://doi.org/10.1039/c8cp00372fS10173101852015I. E. A. Statistics, IEA, Paris, France, 2016Li, W., Dahn, J. R., & Wainwright, D. S. (1994). Rechargeable Lithium Batteries with Aqueous Electrolytes. Science, 264(5162), 1115-1118. doi:10.1126/science.264.5162.1115Lee, H., Yanilmaz, M., Toprakci, O., Fu, K., & Zhang, X. (2014). A review of recent developments in membrane separators for rechargeable lithium-ion batteries. Energy Environ. Sci., 7(12), 3857-3886. doi:10.1039/c4ee01432dAnothumakkool, B., Torris A. T., A., Veeliyath, S., Vijayakumar, V., Badiger, M. V., & Kurungot, S. (2016). High-Performance Flexible Solid-State Supercapacitor with an Extended Nanoregime Interface through in Situ Polymer Electrolyte Generation. ACS Applied Materials & Interfaces, 8(2), 1233-1241. doi:10.1021/acsami.5b09677Huang, C., Zhang, J., Snaith, H. J., & Grant, P. S. (2016). Engineering the Membrane/Electrode Interface To Improve the Performance of Solid-State Supercapacitors. ACS Applied Materials & Interfaces, 8(32), 20756-20765. doi:10.1021/acsami.6b05789Wang, Y., Chen, K. S., Mishler, J., Cho, S. C., & Adroher, X. C. (2011). A review of polymer electrolyte membrane fuel cells: Technology, applications, and needs on fundamental research. Applied Energy, 88(4), 981-1007. doi:10.1016/j.apenergy.2010.09.030Kraytsberg, A., & Ein-Eli, Y. (2014). Review of Advanced Materials for Proton Exchange Membrane Fuel Cells. Energy & Fuels, 28(12), 7303-7330. doi:10.1021/ef501977kLufrano, F., Baglio, V., Staiti, P., Antonucci, V., & Arico’, A. S. (2013). Performance analysis of polymer electrolyte membranes for direct methanol fuel cells. Journal of Power Sources, 243, 519-534. doi:10.1016/j.jpowsour.2013.05.180Awang, N., Ismail, A. F., Jaafar, J., Matsuura, T., Junoh, H., Othman, M. H. D., & Rahman, M. A. (2015). Functionalization of polymeric materials as a high performance membrane for direct methanol fuel cell: A review. Reactive and Functional Polymers, 86, 248-258. doi:10.1016/j.reactfunctpolym.2014.09.019Nunes, S. (2002). Inorganic modification of proton conductive polymer membranes for direct methanol fuel cells. Journal of Membrane Science, 203(1-2), 215-225. doi:10.1016/s0376-7388(02)00009-1Jung, D. H., Cho, S. Y., Peck, D. H., Shin, D. R., & Kim, J. S. (2003). Preparation and performance of a Nafion®/montmorillonite nanocomposite membrane for direct methanol fuel cell. Journal of Power Sources, 118(1-2), 205-211. doi:10.1016/s0378-7753(03)00095-8Song, M.-K., Park, S.-B., Kim, Y.-T., Kim, K.-H., Min, S.-K., & Rhee, H.-W. (2004). Characterization of polymer-layered silicate nanocomposite membranes for direct methanol fuel cells. Electrochimica Acta, 50(2-3), 639-643. doi:10.1016/j.electacta.2003.12.078GAOWEN, Z., & ZHENTAO, Z. (2005). Organic/inorganic composite membranes for application in DMFC. Journal of Membrane Science, 261(1-2), 107-113. doi:10.1016/j.memsci.2005.03.036Hande, V. R., Rath, S. K., Rao, S., & Patri, M. (2011). Cross-linked sulfonated poly (ether ether ketone) (SPEEK)/reactive organoclay nanocomposite proton exchange membranes (PEM). Journal of Membrane Science, 372(1-2), 40-48. doi:10.1016/j.memsci.2011.01.042Shimizu, G. K. H. (2005). Assembly of metal ions and ligands with adaptable coordinative tendencies as a route to functional metal-organic solids. Journal of Solid State Chemistry, 178(8), 2519-2526. doi:10.1016/j.jssc.2005.07.003Li, Q., He, R., Jensen, J. O., & Bjerrum, N. J. (2003). Approaches and Recent Development of Polymer Electrolyte Membranes for Fuel Cells Operating above 100 °C. Chemistry of Materials, 15(26), 4896-4915. doi:10.1021/cm0310519Hurd, J. A., Vaidhyanathan, R., Thangadurai, V., Ratcliffe, C. I., Moudrakovski, I. L., & Shimizu, G. K. H. (2009). Anhydrous proton conduction at 150 °C in a crystalline metal–organic framework. Nature Chemistry, 1(9), 705-710. doi:10.1038/nchem.402Araya, S. S., Zhou, F., Liso, V., Sahlin, S. L., Vang, J. R., Thomas, S., … Kær, S. K. (2016). A comprehensive review of PBI-based high temperature PEM fuel cells. International Journal of Hydrogen Energy, 41(46), 21310-21344. doi:10.1016/j.ijhydene.2016.09.024González-Cardoso, P., Stoica, A.-I., Farràs, P., Pepiol, A., Viñas, C., & Teixidor, F. (2010). Additive Tuning of Redox Potential in Metallacarboranes by Sequential Halogen Substitution. Chemistry - A European Journal, 16(22), 6660-6665. doi:10.1002/chem.200902558Pepiol, A., Teixidor, F., Sillanpää, R., Lupu, M., & Viñas, C. (2011). Stepwise Sequential Redox Potential Modulation Possible on a Single Platform. Angewandte Chemie International Edition, 50(52), 12491-12495. doi:10.1002/anie.201105668Tarrés, M., Arderiu, V. S., Zaulet, A., Viñas, C., Fabrizi de Biani, F., & Teixidor, F. (2015). How to get the desired reduction voltage in a single framework! Metallacarborane as an optimal probe for sequential voltage tuning. Dalton Transactions, 44(26), 11690-11695. doi:10.1039/c5dt01464fOlid, D., Núñez, R., Viñas, C., & Teixidor, F. (2013). Methods to produce B–C, B–P, B–N and B–S bonds in boron clusters. Chemical Society Reviews, 42(8), 3318. doi:10.1039/c2cs35441aBauduin, P., Prevost, S., Farràs, P., Teixidor, F., Diat, O., & Zemb, T. (2011). A Theta-Shaped Amphiphilic Cobaltabisdicarbollide Anion: Transition From Monolayer Vesicles to Micelles. Angewandte Chemie International Edition, 50(23), 5298-5300. doi:10.1002/anie.201100410Brusselle, D., Bauduin, P., Girard, L., Zaulet, A., Viñas, C., Teixidor, F., … Diat, O. (2013). Lyotropic Lamellar Phase Formed from Monolayered θ-Shaped Carborane-Cage Amphiphiles. Angewandte Chemie International Edition, 52(46), 12114-12118. doi:10.1002/anie.201307357Gassin, P.-M., Girard, L., Martin-Gassin, G., Brusselle, D., Jonchère, A., Diat, O., … Bauduin, P. (2015). Surface Activity and Molecular Organization of Metallacarboranes at the Air–Water Interface Revealed by Nonlinear Optics. Langmuir, 31(8), 2297-2303. doi:10.1021/acs.langmuir.5b00125Ďorďovič, V., Tošner, Z., Uchman, M., Zhigunov, A., Reza, M., Ruokolainen, J., … Matějíček, P. (2016). Stealth Amphiphiles: Self-Assembly of Polyhedral Boron Clusters. Langmuir, 32(26), 6713-6722. doi:10.1021/acs.langmuir.6b01995Uchman, M., Ďorďovič, V., Tošner, Z., & Matějíček, P. (2015). Classical Amphiphilic Behavior of Nonclassical Amphiphiles: A Comparison of Metallacarborane Self-Assembly with SDS Micellization. Angewandte Chemie International Edition, 54(47), 14113-14117. doi:10.1002/anie.201506545Núñez, R., Romero, I., Teixidor, F., & Viñas, C. (2016). Icosahedral boron clusters: a perfect tool for the enhancement of polymer features. Chemical Society Reviews, 45(19), 5147-5173. doi:10.1039/c6cs00159aNúñez, R., Tarrés, M., Ferrer-Ugalde, A., de Biani, F. F., & Teixidor, F. (2016). Electrochemistry and Photoluminescence of Icosahedral Carboranes, Boranes, Metallacarboranes, and Their Derivatives. Chemical Reviews, 116(23), 14307-14378. doi:10.1021/acs.chemrev.6b00198Masalles, C., Borrós, S., Viñas, C., & Teixidor, F. (2000). Are Low-Coordinating Anions of Interest as Doping Agents in Organic Conducting Polymers? Advanced Materials, 12(16), 1199-1202. doi:10.1002/1521-4095(200008)12:163.0.co;2-wMasalles, C., Borrós, S., Viñas, C., & Teixidor, F. (2002). Surface Layer Formation on Polypyrrole Films. Advanced Materials, 14(6), 449-452. doi:10.1002/1521-4095(20020318)14:63.0.co;2-4Fabre, B., Clark, J. C., & Vicente, M. G. H. (2006). Synthesis and Electrochemistry of Carboranylpyrroles. Toward the Preparation of Electrochemically and Thermally Resistant Conjugated Polymers. Macromolecules, 39(1), 112-119. doi:10.1021/ma051508vHao, E., Fabre, B., Fronczek, F. R., & Vicente, M. G. H. (2007). Syntheses and Electropolymerization of Carboranyl-Functionalized Pyrroles and Thiophenes. Chemistry of Materials, 19(25), 6195-6205. doi:10.1021/cm701935nMasalles, C., Teixidor, F., Borrós, S., & Viñas, C. (2002). Cobaltabisdicarbollide anion [Co(C2B9H11)2]− as doping agent on intelligent membranes for ion capture. Journal of Organometallic Chemistry, 657(1-2), 239-246. doi:10.1016/s0022-328x(02)01432-8Masalles, C., Llop, J., Viñas, C., & Teixidor, F. (2002). Extraordinary Overoxidation Resistance Increase in Self-Doped Polypyrroles by Using Non-conventional Low Charge-Density Anions. Advanced Materials, 14(11), 826. doi:10.1002/1521-4095(20020605)14:113.0.co;2-cFuentes, I., Andrio, A., Teixidor, F., Viñas, C., & Compañ, V. (2017). Enhanced conductivity of sodium versus lithium salts measured by impedance spectroscopy. Sodium cobaltacarboranes as electrolytes of choice. Physical Chemistry Chemical Physics, 19(23), 15177-15186. doi:10.1039/c7cp02526bMauritz, K. A., & Moore, R. B. (2004). State of Understanding of Nafion. Chemical Reviews, 104(10), 4535-4586. doi:10.1021/cr0207123Alberti, G., Narducci, R., & Sganappa, M. (2008). Effects of hydrothermal/thermal treatments on the water-uptake of Nafion membranes and relations with changes of conformation, counter-elastic force and tensile modulus of the matrix. Journal of Power Sources, 178(2), 575-583. doi:10.1016/j.jpowsour.2007.09.034Sukumar, P. R., Wu, W., Markova, D., Ünsal, Ö., Klapper, M., & Müllen, K. (2007). Functionalized Poly(benzimidazole)s as Membrane Materials for Fuel Cells. Macromolecular Chemistry and Physics, 208(19–20), 2258-2267. doi:10.1002/macp.200700390Pu, H., Liu, L., Chang, Z., & Yuan, J. (2009). Organic/inorganic composite membranes based on polybenzimidazole and nano-SiO2. Electrochimica Acta, 54(28), 7536-7541. doi:10.1016/j.electacta.2009.08.011Singha, S., & Jana, T. (2014). Structure and Properties of Polybenzimidazole/Silica Nanocomposite Electrolyte Membrane: Influence of Organic/Inorganic Interface. ACS Applied Materials & Interfaces, 6(23), 21286-21296. doi:10.1021/am506260jKutcherlapati, S. R., Koyilapu, R., & Jana, T. (2017). Poly(N -vinyl imidazole) grafted silica nanofillers: Synthesis by RAFT polymerization and nanocomposites with polybenzimidazole. Journal of Polymer Science Part A: Polymer Chemistry, 56(4), 365-375. doi:10.1002/pola.28917Maity, S., Singha, S., & Jana, T. (2015). Low acid leaching PEM for fuel cell based on polybenzimidazole nanocomposites with protic ionic liquid modified silica. Polymer, 66, 76-85. doi:10.1016/j.polymer.2015.03.040Reyes-Rodriguez, J. L., Escorihuela, J., García-Bernabé, A., Giménez, E., Solorza-Feria, O., & Compañ, V. (2017). Proton conducting electrospun sulfonated polyether ether ketone graphene oxide composite membranes. RSC Advances, 7(84), 53481-53491. doi:10.1039/c7ra10484gDyre, J. C., & Schrøder, T. B. (2000). Universality of ac conduction in disordered solids. Reviews of Modern Physics, 72(3), 873-892. doi:10.1103/revmodphys.72.873Roling, B., Martiny, C., & Brückner, S. (2001). Ion transport in glass: Influence of glassy structure on spatial extent of nonrandom ion hopping. Physical Review B, 63(21). doi:10.1103/physrevb.63.214203Serghei, A., Tress, M., Sangoro, J. R., & Kremer, F. (2009). Electrode polarization and charge transport at solid interfaces. Physical Review B, 80(18). doi:10.1103/physrevb.80.184301Pu, H., Lou, L., Guan, Y., Chang, Z., & Wan, D. (2012). Proton exchange membranes based on semi-interpenetrating polymer networks of polybenzimidazole and perfluorosulfonic acid polymer with hollow silica spheres as micro-reservoir. Journal of Membrane Science, 415-416, 496-503. doi:10.1016/j.memsci.2012.05.036Tominaka, S., & Cheetham, A. K. (2014). Intrinsic and extrinsic proton conductivity in metal-organic frameworks. RSC Adv., 4(97), 54382-54387. doi:10.1039/c4ra11473fBarbosa, P., Rosero-Navarro, N. C., Shi, F.-N., & Figueiredo, F. M. L. (2015). Protonic Conductivity of Nanocrystalline Zeolitic Imidazolate Framework 8. Electrochimica Acta, 153, 19-27. doi:10.1016/j.electacta.2014.11.093Krause, C., Sangoro, J. R., Iacob, C., & Kremer, F. (2010). Charge Transport and Dipolar Relaxations in Imidazolium-Based Ionic Liquids. The Journal of Physical Chemistry B, 114(1), 382-386. doi:10.1021/jp908519uRivera, A., & Rössler, E. A. (2006). Evidence of secondary relaxations in the dielectric spectra of ionic liquids. Physical Review B, 73(21). doi:10.1103/physrevb.73.212201Maity, S., & Jana, T. (2014). Polybenzimidazole Block Copolymers for Fuel Cell: Synthesis and Studies of Block Length Effects on Nanophase Separation, Mechanical Properties, and Proton Conductivity of PEM. ACS Applied Materials & Interfaces, 6(9), 6851-6864. doi:10.1021/am500668cChuang, S.-W., Hsu, S. L.-C., & Hsu, C.-L. (2007). Synthesis and properties of fluorine-containing polybenzimidazole/montmorillonite nanocomposite membranes for direct methanol fuel cell applications. Journal of Power Sources, 168(1), 172-177. doi:10.1016/j.jpowsour.2007.03.021Mustarelli, P., Quartarone, E., Grandi, S., Carollo, A., & Magistris, A. (2008). Polybenzimidazole-Based Membranes as a Real Alternative to Nafion for Fuel Cells Operating at Low Temperature. Advanced Materials, 20(7), 1339-1343. doi:10.1002/adma.200701767Lobato, J., Cañizares, P., Rodrigo, M. A., Úbeda, D., & Pinar, F. J. (2011). Enhancement of the fuel cell performance of a high temperature proton exchange membrane fuel cell running with titanium composite polybenzimidazole-based membranes. Journal of Power Sources, 196(20), 8265-8271. doi:10.1016/j.jpowsour.2011.06.011Sørensen, T. S., & Compañ, V. (1995). Complex permittivity of a conducting, dielectric layer containing arbitrary binary Nernst–Planck electrolytes with applications to polymer films and cellulose acetate membranes. J. Chem. Soc., Faraday Trans., 91(23), 4235-4250. doi:10.1039/ft9959104235Sørensen, T. S., Compañ, V., & Diaz-Calleja, R. (1996). Complex permittivity of a film of poly[4-(acryloxy)phenyl-(4-chlorophenyl)methanone] containing free ion impurities and the separation of the contributions from interfacial polarization, Maxwell–Wagner–Sillars effects and dielectric relaxations of the polymer chains. J. Chem. Soc., Faraday Trans., 92(11), 1947-1957. doi:10.1039/ft9969201947Munar, A., Andrio, A., Iserte, R., & Compañ, V. (2011). Ionic conductivity and diffusion coefficients of lithium salt polymer electrolytes measured with dielectric spectroscopy. Journal of Non-Crystalline Solids, 357(16-17), 3064-3069. doi:10.1016/j.jnoncrysol.2011.04.012Macdonald, J. R. (1953). Theory of ac Space-Charge Polarization Effects in Photoconductors, Semiconductors, and Electrolytes. Physical Review, 92(1), 4-17. doi:10.1103/physrev.92.4Coelho, R. (1983). Sur la relaxation d’une charge d’espace. Revue de Physique Appliquée, 18(3), 137-146. doi:10.1051/rphysap:01983001803013700Klein, R. J., Zhang, S., Dou, S., Jones, B. H., Colby, R. H., & Runt, J. (2006). Modeling electrode polarization in dielectric spectroscopy: Ion mobility and mobile ion concentration of single-ion polymer electrolytes. The Journal of Chemical Physics, 124(14), 144903. doi:10.1063/1.2186638Coelho, R. (1991). On the static permittivity of dipolar and conductive media — an educational approach. Journal of Non-Crystalline Solids, 131-133, 1136-1139. doi:10.1016/0022-3093(91)90740-wJönsson, M., Welch, K., Hamp, S., & Strømme, M. (2006). Bacteria Counting with Impedance Spectroscopy in a Micro Probe Station. The Journal of Physical Chemistry B, 110(20), 10165-10169. doi:10.1021/jp060148qBandara, T. M. W. J., Dissanayake, M. A. K. L., Albinsson, I., & Mellander, B.-E. (2011). Mobile charge carrier concentration and mobility of a polymer electrolyte containing PEO and Pr4N+I− using electrical and dielectric measurements. Solid State Ionics, 189(1), 63-68. doi:10.1016/j.ssi.2011.03.004Pasini Cabello, S. D., Mollá, S., Ochoa, N. A., Marchese, J., Giménez, E., & Compañ, V. (2014). New bio-polymeric membranes composed of alginate-carrageenan to be applied as polymer electrolyte membranes for DMFC. Journal of Power Sources, 265, 345-355. doi:10.1016/j.jpowsour.2014.04.093García-Bernabé, A., Rivera, A., Granados, A., Luis, S. V., & Compañ, V. (2016). Ionic transport on composite polymers containing covalently attached and absorbed ionic liquid fragments. Electrochimica Acta, 213, 887-897. doi:10.1016/j.electacta.2016.08.018Compañ, V., Molla, S., García Verdugo, E., Luis, S. V., & Burguete, M. I. (2012). Synthesis and characterization of the conductivity and polarization processes in supported ionic liquid-like phases (SILLPs). Journal of Non-Crystalline Solids, 358(9), 1228-1237. doi:10.1016/j.jnoncrysol.2012.02.02

Improved Carbohydrate Metabolism After Bariatric Surgery Raises Antioxidized LDL Antibody Levels in Morbidly Obese Patients

OBJECTIVE—Antioxidized LDL (anti-oxLDL) antibodies have recently been suggested to be protective against the development of diabetes. We measured the changes in anti-oxLDL antibody levels in the inverse situation of improvement in carbohydrate metabolism

What to consider when pseudohypoparathyroidism is ruled out: IPPSD and differential diagnosis

Background: Pseudohypoparathyroidism (PHP) is a rare disease whose phenotypic features are rather difficult to identify in some cases. Thus, although these patients may present with the Albright''s hereditary osteodystrophy (AHO) phenotype, which is characterized by small stature, obesity with a rounded face, subcutaneous ossifications, mental retardation and brachydactyly, its manifestations are somewhat variable. Indeed, some of them present with a complete phenotype, whereas others show only subtle manifestations. In addition, the features of the AHO phenotype are not specific to it and a similar phenotype is also commonly observed in other syndromes. Brachydactyly type E (BDE) is the most specific and objective feature of the AHO phenotype, and several genes have been associated with syndromic BDE in the past few years. Moreover, these syndromes have a skeletal and endocrinological phenotype that overlaps with AHO/PHP. In light of the above, we have developed an algorithm to aid in genetic testing of patients with clinical features of AHO but with no causative molecular defect at the GNAS locus. Starting with the feature of brachydactyly, this algorithm allows the differential diagnosis to be broadened and, with the addition of other clinical features, can guide genetic testing. Methods: We reviewed our series of patients (n = 23) with a clinical diagnosis of AHO and with brachydactyly type E or similar pattern, who were negative for GNAS anomalies, and classify them according to the diagnosis algorithm to finally propose and analyse the most probable gene(s) in each case. Results: A review of the clinical data for our series of patients, and subsequent analysis of the candidate gene(s), allowed detection of the underlying molecular defect in 12 out of 23 patients: five patients harboured a mutation in PRKAR1A, one in PDE4D, four in TRPS1 and two in PTHLH. Conclusions: This study confirmed that the screening of other genes implicated in syndromes with BDE and AHO or a similar phenotype is very helpful for establishing a correct genetic diagnosis for those patients who have been misdiagnosed with "AHO-like phenotype" with an unknown genetic cause, and also for better describing the characteristic and differential features of these less common syndromes

Antifungal activity of amphotericin B conjugated to nanosized magnetite in the treatment of paracoccidioidomycosis

This study reports on in vitro and in vivo tests that sought to assess the antifungal activity of a newly developed magnetic carrier system comprising amphotericin B loaded onto the surface of pre-coated (with a double-layer of lauric acid) magnetite nanoparticles. The in vitro tests compared two drugs; i.e., this newly developed form and free amphotericin B. We found that this nanocomplex exhibited antifungal activity without cytotoxicity to human urinary cells and with low cytotoxicity to peritoneal macrophages. We also evaluated the efficacy of the nanocomplex in experimental paracoccidioidomycosis. BALB/c mice were intratracheally infected with Paracoccidioides brasiliensis and treated with the compound for 30 or 60 days beginning the day after infection. The newly developed amphotericin B coupled with magnetic nanoparticles was effective against experimental paracoccidioidomycosis, and it did not induce clinical, biochemical or histopathological alterations. The nanocomplex also did not induce genotoxic effects in bone marrow cells. Therefore, it is reasonable to believe that amphotericin B coupled to magnetic nanoparticles and stabilized with bilayer lauric acid is a promising nanotool for the treatment of the experimental paracoccidioidomycosis because it exhibited antifungal activity that was similar to that of free amphotericin B, did not induce adverse effects in therapeutic doses and allowed for a reduction in the number of applications

Lattice dynamics study of HgGa2Se4 at high pressures

We report on Raman scattering measurements in mercury digallium selenide (HgGa2Se4) up to 25 GPa. We also performed, for the low-pressure defect-chalcopyrite structure, lattice-dynamics ab initio calculations at high pressures which agree with experiments. Measurements evidence that the semiconductor HgGa2Se4 exhibits a pressure-induced phase transition above 19 GPa to a previously undetected structure. This transition is followed by a transformation to a Raman-inactive phase above 23.4 GPa. On downstroke from 25 GPa until 2.5 GPa, a broad Raman spectrum was observed, which has been attributed to a fourth phase, and whose pressure dependence was followed during a second upstroke. Candidate structures for the three phases detected under compression are proposed. Finally, we also report and discuss the decomposition of the sample by laser heating at pressures close to 19 GPa. As possible products of decomposition, we have identified at least the formation of trigonal selenium nanoclusters and cinnabar-type HgSe.This study was supported by the Spanish government MEC under Grant No. MAT2010-21270-004-01/03/04, by MALTA Consolider Ingenio 2010 project (CSD2007-00045), by Generalitat Valenciana through project GVA-ACOMP-2013-012, and by the Vicerrectorado de Investigacion y Desarrollo of the Universidad Politecnica de Valencia (UPV2011-0966 and UPV2011-0914). E.P.-G., J.L.-S., A.M., and P.R.-H. acknowledge computing time provided by Red Espanola de Super-computacion (RES) and MALTA-Cluster.Vilaplana Cerda, RI.; Gomis Hilario, O.; Manjón Herrera, FJ.; Ortiz, HM.; Pérez González, E.; López Solano, J.; Rodríguez Hernández, P.... (2013). Lattice dynamics study of HgGa2Se4 at high pressures. Journal of Physical Chemistry C. 117(30):15773-15781. https://doi.org/10.1021/jp402493rS15773157811173

Updated Iberian archeomagnetic catalogue: new full vector paleosecular variation curve for the last three millennia

In this work, we present 16 directional and 27 intensity high‐quality values from Iberia. Moreover, we have updated the Iberian archeomagnetic catalogue published more than 10 years ago with a considerable increase in the database. This has led to a notable improvement of both temporal and spatial data distribution. A full vector paleosecular variation curve from 1000 BC to 1900 AD has been developed using high‐quality data within a radius of 900 km from Madrid. A hierarchical bootstrap method has been followed for the computation of the curves. The most remarkable feature of the new curves is a notable intensity maximum of about 80 μT around 600 BC, which has not been previously reported for the Iberian Peninsula. We have also analyzed the evolution of the paleofield in Europe for the last three thousand years and conclude that the high maximum intensity values observed around 600 BC in the Iberian Peninsula could respond to the same feature as the Levantine Iron Age Anomaly, after travelling westward through Europe

Clinical phenotypes of acute heart failure based on signs and symptoms of perfusion and congestion at emergency department presentation and their relationship with patient management and outcomes

Objective To compare the clinical characteristics and outcomes of patients with acute heart failure (AHF) according to clinical profiles based on congestion and perfusion determined in the emergency department (ED). Methods and results Overall, 11 261 unselected AHF patients from 41 Spanish EDs were classified according to perfusion (normoperfusion = warm; hypoperfusion = cold) and congestion (not = dry; yes = wet). Baseline and decompensation characteristics were recorded as were the main wards to which patients were admitted. The primary outcome was 1-year all-cause mortality; secondary outcomes were need for hospitalisation during the index AHF event, in-hospital all-cause mortality, prolonged hospitalisation, 7-day post-discharge ED revisit for AHF and 30-day post-discharge rehospitalisation for AHF. A total of 8558 patients (76.0%) were warm+ wet, 1929 (17.1%) cold+ wet, 675 (6.0%) warm+ dry, and 99 (0.9%) cold+ dry; hypoperfused (cold) patients were more frequently admitted to intensive care units and geriatrics departments, and warm+ wet patients were discharged home without admission. The four phenotypes differed in most of the baseline and decompensation characteristics. The 1-year mortality was 30.8%, and compared to warm+ dry, the adjusted hazard ratios were significantly increased for cold+ wet (1.660; 95% confidence interval 1.400-1.968) and cold+ dry (1.672; 95% confidence interval 1.189-2.351). Hypoperfused (cold) phenotypes also showed higher rates of index episode hospitalisation and in-hospital mortality, while congestive (wet) phenotypes had a higher risk of prolonged hospitalisation but decreased risk of rehospitalisation. No differences were observed among phenotypes in ED revisit risk. Conclusions Bedside clinical evaluation of congestion and perfusion of AHF patients upon ED arrival and classification according to phenotypic profiles proposed by the latest European Society of Cardiology guidelines provide useful complementary information and help to rapidly predict patient outcomes shortly after ED patient arrival

Spoken term detection ALBAYZIN 2014 evaluation: overview, systems, results, and discussion

The electronic version of this article is the complete one and can be found online at: http://dx.doi.org/10.1186/s13636-015-0063-8Spoken term detection (STD) aims at retrieving data from a speech repository given a textual representation of the search term. Nowadays, it is receiving much interest due to the large volume of multimedia information. STD differs from automatic speech recognition (ASR) in that ASR is interested in all the terms/words that appear in the speech data, whereas STD focuses on a selected list of search terms that must be detected within the speech data. This paper presents the systems submitted to the STD ALBAYZIN 2014 evaluation, held as a part of the ALBAYZIN 2014 evaluation campaign within the context of the IberSPEECH 2014 conference. This is the first STD evaluation that deals with Spanish language. The evaluation consists of retrieving the speech files that contain the search terms, indicating their start and end times within the appropriate speech file, along with a score value that reflects the confidence given to the detection of the search term. The evaluation is conducted on a Spanish spontaneous speech database, which comprises a set of talks from workshops and amounts to about 7 h of speech. We present the database, the evaluation metrics, the systems submitted to the evaluation, the results, and a detailed discussion. Four different research groups took part in the evaluation. Evaluation results show reasonable performance for moderate out-of-vocabulary term rate. This paper compares the systems submitted to the evaluation and makes a deep analysis based on some search term properties (term length, in-vocabulary/out-of-vocabulary terms, single-word/multi-word terms, and in-language/foreign terms).This work has been partly supported by project CMC-V2 (TEC2012-37585-C02-01) from the Spanish Ministry of Economy and Competitiveness. This research was also funded by the European Regional Development Fund, the Galician Regional Government (GRC2014/024, “Consolidation of Research Units: AtlantTIC Project” CN2012/160)

A comprehensive characterization of the caspase gene family in insects from the order Lepidoptera

<p>Abstract</p> <p>Background</p> <p>The cell suicide pathway of apoptosis is a necessary event in the life of multicellular organisms. It is involved in many biological processes ranging from development to the immune response. Evolutionarily conserved proteases, called caspases, play a central role in regulating apoptosis. Reception of death stimuli triggers the activation of initiator caspases, which in turn activate the effector caspases. In Lepidoptera, apoptosis is crucial in processes such as metamorphosis or defending against baculovirus infection. The discovery of p35, a baculovirus protein inhibiting caspase activity, has led to the characterization of the first lepidopteran caspase, Sf-Caspase-1. Studies on Sf-Caspase-1 mode of activation suggested that apoptosis in Lepidoptera requires a cascade of caspase activation, as demonstrated in many other species.</p> <p>Results</p> <p>In order to get insights into this gene family in Lepidoptera, we performed an extensive survey of lepidopteran-derived EST datasets. We identified 66 sequences distributed among 27 species encoding putative caspases. Phylogenetic analyses showed that Lepidoptera possess at least 5 caspases, for which we propose a unified nomenclature. According to homology to their <it>Drosophila </it>counterparts and their primary structure, we determined that Lep-Caspase-1, -2 and -3 are putative effector caspases, whereas Lep-Caspase-5 and -6 are putative initiators. The likely function of Lep-Caspase-4 remains unclear. Lep-Caspase-2 is absent from the silkworm genome and appears to be noctuid-specific, and to have arisen from a tandem duplication of the Caspase-1 gene. In the tobacco hawkmoth, 3 distinct transcripts encoding putative Caspase-4 were identified, suggesting at least 2 duplication events in this species.</p> <p>Conclusions</p> <p>The basic repertoire of five major types of caspases shared among Lepidoptera seems to be smaller than for most other groups studied to date, but gene duplication still plays a role in lineage-specific increases in diversity, just as in Diptera and mammals.</p