Simulaciones de Monte Carlo-Metropolis del almacenamiento de hidrógeno en COFs (Covalent Organic Frameworks)

La reducción de la emisión de los gases de efecto invernadero es uno de los temas que más preocupa a la sociedad en este siglo. Ante esta situación, el vehículo de hidrógeno se erige como una propuesta que puede convertirse en una opción de presente y futuro. Uno de los principales problemas que presenta el vehículo de hidrógeno es el almacenamiento de este gas. Una de las formas que está ofreciendo resultados más prometedores es el almacenamiento en materiales nanoporosos mediante fisisorción. En concreto, el uso de los COFs como material es una de las opciones más atractivas, gracias a sus grandes cualidades de porosidad, lo que contribuye al almacenamiento del hidrógeno. En este trabajo, se estudia el material COF-102, calculando mediante simulaciones de Monte Carlo la capacidad de almacenamiento de este, a la temperatura de 77 K y a bajas y medias presiones. Los resultados obtenidos se compararon con datos experimentales y simulados obtenidos en otras simulaciones.Reducing the emission of greenhouse gases is one of the issues that most concerns society in this century. In this situation, the hydrogen vehicle stands as a proposal that can become an option for the present and the future. One of the main problems that the hydrogen vehicle presents is the storage of this gas. One of the ways that is o ering the most promising results is storage in nanoporous materials by physisorption. Speci cally, the use of COFs as a material is one of the most attractive options, due to its great porosity qualities, which contribute to the storage of hydrogen. In this work, COF-102 material is studied. Its storage capacity through Monte Carlo simulations was calculated, at a temperature of 77 K and at low and medium pressures. The results obtained were compared with experimental and simulated data obtained in other simulations.Grado en Físic

Fingolimod phosphate protection against mitochondrial damage in neuronal cells

Background: Major role of oxidative stress in the pathogenesis of neurodegenerative diseases have been suggested, being mitochondria one of the main sources of ROS. Aim: In the present work, we have studied the antioxidant effect of fingolimod phosphate (FP) on neuronal mitochondrial function and morphology using a model of mitochondrial oxidative damage induced by menadione (Vitk3). Methods: SN4741 neuronal cells were grown (70-80% confluence) and used as control (non-treated cells) or treated cells with Vitk3 15 µM alone or in presence of FP 50 nM during 4 hours. Mitochondrial membrane potential (MMP), cytochrome c oxidase (COX) activity, mitochondrial oxygen consumption rate (OCR), mitochondrial distribution (MTG) and morphology (EM) were analysed. Statistical differences were determined using one-way ANOVA. Results: Vitk3 incubation produces a dramatical decrease in MMP compared to control (43.7 %); this can be almost totally reverted by the co-incubation of Vitk3 in presence of FP (p<0.05). A 20.7 % decrease in COX activity has been found after Vitk3 incubation, again this effect was counteracted when Vitk3 and FP are combined, restoring COX activity to control levels (p<0.05). Vitk3 incubation triggers initially an increase in OCR, decreasing dramatically (61%) after 4 hours. In experiments co-incubating Vitk3 in presence of FP, the OCR decrease found was reduced to only 17% (p<0.05). In experiments with MitoTracker™ Green, we found a change in the network pattern distribution after Vitk3 administration that partially disappears when co-incubated in presence of FP. Almost all the mitochondria treated with Vitk3 show ultrastructural alterations at the electron microscopy level while normal mitochondria can be found when Vitk3 and FP are combined. Conclusion: FP protects against the mitochondrial damage induced by Vitk3, as seen by the results obtained in mitochondrial functional markers, distribution and morphology.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. PS13/14: Study of the non-immunological mechanisms of action of Gilenya (Fingolimod) as therapeutic tool in Multiple Sclerosis and/or other neurodegenerative diseases. Novartis Farmacéutica S.A

Análisis de la vulnerabilidad sísmica del pabellón “C” en la institución educativa Mariscal Toribio de Luzuriaga Independencia Huaraz - 2018

El presente trabajo tiene como objetivo “Analizar la Vulnerabilidad Sísmica del Pabellón C de la institución educativa Mariscal Toribio de Luzuriaga IndependenciaHuaraz-2018,” con la finalidad de fomentar acciones de mitigación ante un evento sísmico, de tal forma que no ponga en peligro la vida de los estudiantes ni el personal que allí labora, de conformidad al Reglamento Nacional de Edificaciones (E-030 Diseño sismo resistente). El tipo de investigación es descriptiva, no experimental, transversal correlacional teniendo como población la institución educativa Mariscal Toribio de Luzuriaga y como objeto de estudio el pabellón C de la institución mencionada. Con tal fin se realizaron diferentes estudios tales como: Estudio de campo aplicando la ficha técnica para determinar las características de la edificación, laboratorio de suelos para determinar el tipo de suelo y capacidad portante adicionalmente se realizó un modelamiento matemático en el programa Etabs v.17 para determinar el comportamiento de los elementos estructurales ante un evento sísmico. Adicionalmente a ello se desarrolló planos arquitectónicos de la edificación que consta de dos niveles, la cual tiene dos accesos al segundo nivel con escalera en ambos extremos de la estructura, la cual será de mucha utilidad para la institución, para fines, así como señalizaciones de evacuación, entre otros. Obteniendo como resultado en la evaluación un pésimo desempeño sísmico por lo que no cumple con lo establecido en la norma E-030, así como las derivas máximas, las irregularidades, y columnas cortas, llegando a la conclusión que la edificación presenta una vulnerabilidad alta. Finalmente se brinda los resultados obtenidos en los diferentes estudios de análisis realizados y las recomendaciones correspondientes

Electrochemical vs. chemical promotion in the H2 production catalytic reactions

The addition of electronic promoters chemically (chemical promotion) or electrochemically (electrochemical promotion or EPOC) induces very significant and similar effects on catalytic hydrogen production reactions such as CH4 and CH3OH conversion reactions, water-gas shift or ammonia decomposition. Both kinds of promotional phenomena follow the same general mechanism but the usefulness of the latter is highlighted. In this paper, the most important and recent contributions of the electrochemical promotion in different hydrogen production reactions are reviewed and compared to those based on conventional chemical promotion methods, mostly focusing on alkali promoters. The functional similarities and operational differences between both promotion ways are pointed out, and their impact on the hydrogen production technology is discussed. By this way the possibility of in-situ controlling the promoter coverage on the catalyst under working conditions and the in-situ catalyst regeneration from carbon deposition, among other novel contributions, lead EPOC to new opportunities for both: development of tailored effective catalysts and operation of hydrogen catalytic processes.La adición de promotores electrónicos químicamente (promoción química) o electroquímicamente (promoción electroquímica o EPOC) induce efectos muy significativos y similares en las reacciones catalíticas de producción de hidrógeno , como las reacciones de conversión de CH 4 y CH 3 OH, el desplazamiento agua-gas o la descomposición del amoníaco .. Ambos tipos de fenómenos promocionales siguen el mismo mecanismo general pero se destaca la utilidad del último. En este trabajo se revisan las contribuciones más importantes y recientes de la promoción electroquímica en diferentes reacciones de producción de hidrógeno y se comparan con aquellas basadas en métodos de promoción química convencionales, centrándose principalmente en promotores alcalinos. Se señalan las similitudes funcionales y las diferencias operativas entre ambas formas de promoción y se discute su impacto en la tecnología de producción de hidrógeno. De esta manera, la posibilidad de controlar in situ la cobertura del promotor sobre el catalizador en condiciones de trabajo y la regeneración in situ del catalizador a partir de la deposición de carbono ., entre otras contribuciones novedosas, llevan a EPOC a nuevas oportunidades para ambos: desarrollo de catalizadores efectivos personalizados y operación de procesos catalíticos de hidrógeno

A phase II trial of weekly nab-paclitaxel for progressive and symptomatic desmoid tumors

Desmoid tumors; Phase II trial; PaclitaxelTumores desmoides; Ensayo de fase II; PaclitaxelTumors desmoides; Assaig de fase II; PaclitaxelDesmoid fibromatosis (DF) are mesenchymal neoplasms, with potential aggressive course and relevant clinical impact. New systemic therapy modalities are needed in this symptomatic/progressive population. In this multicenter, phase II trial (NCT03275818), patients with symptomatic/progressing DF received three cycles of weekly nab-paclitaxel. Brief pain inventory short form (BPI-SF) was collected at baseline and in every visit. MRI was performed every 3 months. Primary composite endpoint was RECIST 1.1 overall response rate (ORR) and/or clinical response (improvement ≥ 2 points in BPI-SF). If 40% of patients achieved clinical/radiological response, further investigation would be warranted. Toxicity, progression-free survival (PFS), pattern of response and its correlation with clinical best response and BPI, variation of physical function, and analgesic consumption were secondary endpoints. The translational research reported was not a pre-specified secondary outcome. Forty eligible patients started therapy, being 35 radiologically and clinically evaluable. The study achieved its primary endpoint, as 7(20%) patients obtained RECIST partial response, whereas 31(89%) experienced pain reduction of ≥2 points in BPI-SF worst pain. Therapy was well tolerated. With a median follow-up of 30(14–44) months, median 12 and 24-months PFS rates were 91%(CI 95%, 82–100) and 84%(CI 95%, 71–97). For clinical progression, 12 and 24-months PFS rates were 85% (CI 95%, 73–97) and 74% (CI 95%, 58–90) respectively. Short course of nab-paclitaxel is active, safe and achieves quick and durable responses in progressing/symptomatic DF patients.The authors would like to thank the Spanish group for Research on Sarcomas (GEIS) for supporting the study and BMS/ Celgene (study ID AX-CL-GEIS-007345) for providing drug supply. The sponsor (GEIS) has been in charge of study design, data collection, analysis and manuscript writing. The authors also thank the donors and the University Hospital Virgen del Rocío for participating in patient recruitment. The authors would like to thank Araceli Rodriguez Morales and Gabriela Golab for Data Management. David S. Moura is recipient of a Sara Borrell postdoctoral fellowship funded by the National Institute of Health Carlos III (ISCIII) (CD20/00155). The authors would also like to thank SELNET project. SELNET has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No. 825806

Guest Induced Strong Cooperative One- and Two-Step Spin Transitions in Highly Porous Iron(II) Hofmann-Type Metal-Organic Frameworks

[EN] The synthesis, crystal structure, magnetic, calorimetric, and Mo¿ ssbauer studies of a series of new Hofmann-type spin crossover (SCO) metal¿organic frameworks (MOFs) is reported. The new SCO-MOFs arise from self-assembly of FeII, bis(4-pyridyl)butadiyne (bpb), and [Ag(CN)2] ¿ or [MII(CN)4] 2¿ (MII = Ni, Pd). Interpenetration of four identical 3D networks with ¿-Po topology are obtained for {Fe(bpb)[AgI (CN)2]2} due to the length of the rod-like bismonodentate bpb and [Ag(CN)2] ¿ ligands. The four networks are tightly packed and organized in two subsets orthogonally interpenetrated, while the networks in each subset display parallel interpenetration. This nonporous material undergoes a very incomplete SCO, which is rationalized from its intricate structure. In contrast, the single network Hofmann-type MOFs {Fe(bpb)[MII(CN)4]}·nGuest (MII = Ni, Pd) feature enhanced porosity and display complete one-step or two-step cooperative SCO behaviors when the pores are filled with two molecules of nitrobenzene or naphthalene that interact strongly with the pyridyl and cyano moieties of the bpb ligands via ¿¿¿ stacking. The lack of these guest molecules favors stabilization of the high-spin state in the whole range of temperatures. However, application of hydrostatic pressure induces one- and two-step SCO.We thank the Spanish Ministerio de Economia y Competitividad (MINECO) and FEDER funds (CTQ2013-46275-P and CTQ2016-78341-P and Unidad de Excelencia Maria de Maeztu MDM-2015-0538) and Generalitat Valenciana (PROMETEO/2016/147). L.P.-L. and F.J.V.-M. thank, respectively, the Universidad de Valencia and MINECO for a predoctoral FPI grant.Piñeiro-López, L.; Valverde-Muñoz, FJ.; Seredyuk, M.; Muñoz Roca, MDC.; Haukka, M.; Real, JA. (2017). Guest Induced Strong Cooperative One- and Two-Step Spin Transitions in Highly Porous Iron(II) Hofmann-Type Metal-Organic Frameworks. Inorganic Chemistry. 56(12):7038-7047. https://doi.org/10.1021/acs.inorgchem.7b00639S70387047561

Self-limited autoimmune disease related to transient donor B cell activation in mice neonatally injected with semi-allogeneic F1 cells

BALB/c mice injected at birth with 108 semi-allogeneic (C57BL/6 x BALB.IgHb)F1 spleen cells develop a lupus-like syndrome in which autoantibodles bear exclusively the donor allotype. We have analyzed the evolution of donor B cell chimerism and the autoimmune manifestations during the first year of life in these mice. Anti-DNA, -histone, and -cardiolipln IgG antibodies as well as circulating immune complexes appeared in the second week of life, reached the highest values around the sixth week, and then progressively dropped to normal values after the sixth month in most mice. The kinetics of the evolution of the autoimmune manifestations, as well as the kinetics of serum donor Ig allotype, were parallel to the kinetics of donor B cell chimerism, which was particularly prominent in the spleens in early weeks of life, and progressively decreased after remission of the autoimmune syndrome. Membrane-proliferative glomerulonephritls, which was followed as the more representative histological abnormality in this model, was particularly evident after 10 weeks of life, but disappeared by the end of the follow-up. Interestingly, when mice with a self-limited disease were re-injected with 108 F1 spleen cells i.v., a flare in the serologlcal manifestations was observed. In these re-injected mice a predominance of anti-DNA, lgG1 antibodies bearing exclusively the donor allotype was also observed, as in the early weeks of life. These results emphasize the central role of donor B cell chimerism in the development and in the self-limitation of the autoimmune disease in parental mice neonatally injected with F1 cells and Indicate that the capacity to react with F1 cells, to generate a renewed burst of symptoms, persists in these mice after the disappearance of autoimmune finding

Metal-Controlled Magnetoresistance at Room Temperature in Single-Molecule Devices

The appropriate choice of the transition metal complex and metal surface electronic structure opens the possibility to control the spin of the charge carriers through the resulting hybrid molecule/metal spinterface in a single molecule electrical contact at room temperature. The single molecule conductance of a Au/molecule/Ni junction can be switched by flipping the magnetization direction of the ferromagnetic electrode. The requirements of the molecule include not just the presence of unpaired electrons: the electronic configuration of the metal center has to provide occupied or empty orbitals that strongly interact with the junction metal electrodes and that are close in energy to their Fermi levels for one of the electronic spins only. The key ingredient for the metal surface is to provide an efficient spin texture induced by the spin orbit coupling in the topological surface states that results in an efficient spin-dependent interaction with the orbitals of the molecule. The strong magnetoresistance effect found in this kind of single-molecule wire opens a new approach for the design of room-temperature nanoscale devices based on spin-polarized currents controlled at molecular level

Electrochemical promotion of a dispersed Ni catalyst for H2 production via partial oxidation of methanol

This study reports the electrochemical promotion (EPOC) of Ni particles dispersed in a diamond-like carbon (DLC) matrix. A Ni-DLC (Ni/C molar ratio of 0.1) catalyst film was prepared on a K-βAl2O3 (K+-conductor) solid electrolyte by cathodic arc deposition (CAD). This physical vapour deposition (PVD) technique allows to decrease the metal loading used in the solid electrolyte cell and to electrochemically activate dispersed Ni particles in the methanol partial oxidation (POM) reaction by in-situ controlling the coverage of K+ ions electrochemically transferred to the catalyst surface. As compared with a pure Ni layer prepared by the same technique, the Ni-DLC catalyst film shows a higher specific activity and an improved oxidation resistance under EPOC working reaction conditions. The possibility of electrochemically activate (with a negligible energy consumption) dispersed particles of a non-noble metal catalyst (closely related to commercially catalyst formulations) is of great interest for a further commercialization step of the EPOC phenomena in H2 production reactions and in other catalytic systems.Este estudio informa sobre la promoción electroquímica (EPOC) de partículas de Ni dispersas en una matriz de carbono tipo diamante (DLC). Se preparó una película catalizadora de Ni-DLC (relación molar Ni/C de 0,1) sobre un electrolito sólido de K-βAl2O3 (conductor de K+) mediante deposición por arco catódico (CAD). Esta técnica de deposición física de vapor (PVD) permite disminuir la carga metálica utilizada en la celda de electrolito sólido y activar electroquímicamente las partículas de Ni dispersas en la reacción de oxidación parcial del metanol (POM) mediante el control in situ de la cobertura de iones K+ transferidos electroquímicamente a la superficie del catalizador. En comparación con una capa de Ni pura preparada mediante la misma técnica, la película catalizadora de Ni-DLC muestra una mayor actividad específica y una mejor resistencia a la oxidación en condiciones de reacción de trabajo EPOC. La posibilidad de activar electroquímicamente (con un consumo de energía insignificante) partículas dispersas de un catalizador de metal no noble (estrechamente relacionado con las formulaciones de los catalizadores comerciales) es de gran interés para un posterior paso de comercialización del fenómeno EPOC en reacciones de producción de H2 y en otros sistemas catalíticos