Electrocatalytic behavior of tetrathiafulvalene (TTF) and extended tetrathiafulvalene (exTTF) [FeFe] hydrogenase mimics

TTF- and exTTF-containing [(μ-S2)Fe2(CO)6] complexes have been prepared by the photochemical reaction of TTF or exTTF and [(μ-S2)Fe2(CO)6]. These complexes are able to interact with PAHs. In the absence of air and in acid media an electrocatalytic dihydrogen evolution reaction (HER) occurs, similarly to analogous [(μ-S2)Fe2(CO)6] complexes. However, in the presence of air, the TTF and exTTF organic moieties strongly influence the electrochemistry of these systems. The reported data may be valuable in the design of [FeFe] hydrogenase mimics able to combine the HER properties of the [FeFe] cores with the unique TTF propertie

Phosphite Bearing [(μ-ADT)RFe2(CO)6] (ADT = Azadithiolate) Moieties: A Tool for the Building of Multimetallic [FeFe]-Hydrogenase Mimics

A new phosphite ligand having three [(μ-ADT)RFe2(CO)6] (R= p-HOC6H4) moieties (2) has been prepared in good yield by the reaction of complex [(μ-ADT)RFe2(CO)6] (R= p-HOC6H4) 1a with PCl3. Coordination of this phosphite to [PdCl2(MeCN)2] or [PtCl2(DMSO)2] forms heterometallic square planar complexes 5 (C84H48Cl2Fe12N6O42P2MS12) (M = Pt, Pd) in excellent yields. Three-legged piano stool complexes 6 (C52H39Cl2Fe6N3O21PMS6) (M = Rh, Ir) were obtained by the reaction of phosphite 2 with [MCl2Cp*]2(M = Rh, Ir) in good yields. The formation of complexes 5 and 6 demonstrates the versatility of this new ligand for forming different heteropolymetallic complexes under mild reaction conditions. Moreover, the open-chain derivatives [(μ-ADT)RFe2(CO)6] (R= HOCH2CH2, o-HOC6H4) (1b and 1c, respectively) form cyclic complexes 4 by spontaneous intramolecular CO substitution by the P atom in one of the three [FeFe] fragments. The electrocatalytic behavior of complexes 2 and 4 upon the addition of AcOH is similar to that of related [(μ-ADT)Fe2(CO)6] derivatives. The successive additions of AcOH cause an increase in the current intensity in the wave at about -1.80 V for heteropolymetallic complexes 5 and 6. However, the appearance of a new wave around -1.40 V in complexes 5 points to an acid-promoted side reaction in the electrochemical proces

Osmium Catalysts for Acceptorless and Base-Free Dehydrogenation of Alcohols and Amines: Unusual Coordination Modes of a BPI Anion

A novel type of catalyst precursors for the dehydrogenation of hydrogen carriers based on organic liquids has been discovered. Complexes OsH6(PiPr3)2 (1) and OsH(OH)(CO)(PiPr3)2 (2) react with 1,3-bis(6'-methyl-2'-pyridylimino)isoindoline (HBMePI) to give OsH3{¿2-Npy,Nimine-(BMePI)}(PiPr3)2 (3) and OsH{¿2-Npy,Nimine-(BMePI)}(CO)(PiPr3)2 (4). The unprecedented ¿2-Npy,Nimine coordination mode of BMePI is thermodynamically preferred with Os(IV) and Os(II) metal fragments and allows for preparation of BMePI-based dinuclear metal cations. Treatment of OsH2Cl2(PiPr3)2 (5) with 0.5 equiv of HBMePI in the presence of KOtBu affords the chloride salt of the bis(osmium(IV)) dinuclear cation [{OsH3(PiPr3)2}2{µ-(¿2-Npy,Nimine)2-BMePI}]+ (6). Related homoleptic bis(osmium(II)) complexes have been also synthesized. Complex 4 reacts with the bis(solvento) [OsH(CO){¿1-O-[OCMe2]2}(PiPr3)2]BF4 to give [{OsH(CO)(PiPr3)2}2{µ-(¿2-Npy,Nimine)2-BMePI}]BF4 (7), whereas the addition of 0.5 equiv of HBMePI to {OsCl(¿6-C6H6)}2(µ–Cl)2 (8) affords [{OsCl(¿6-C6H6)}2{µ-(¿2-Npy,Nimine)2-BMePI}]Cl (9). The reactions of 4 with 8 and {OsCl(¿6-p-cymene)}2(µ–Cl)2 (10) lead to the heteroleptic cations [(PiPr3)2(CO)HOs{µ-(¿2-Npy,Nimine)2-BMePI}OsCl(¿6-arene)]+ (arene = C6H6 (11), p-cymene (12)). The electronic structrure and electrochemical properties of the dinuclear complexes were also studied. Complexes 3 and 4 are efficient catalyst precursors for the acceptorless and base-free dehydrogenation of secondary and primary alcohols and cyclic and lineal amines. The primary alcohols afford aldehydes. The amount of H2 released per gram of heterocycle depends upon the presence of a methyl group adjacent to the nitrogen atom, the position of the nitrogen atom in the heterocycle, and the size of the heterocycle

Chemoselectivity on the synthesis of iridacycles: A theoretical and experimental study

The selective synthesis of a spirobifluorene-iridacyclopentadiene complex has been achieved through the corresponding methoxyalkenylcarbeneiridium complex. The chemoselectivity of the Csingle bondH bond activation over the precursor has been studied via DFT calculations on the relative energies of the E and Z isomers of several examples and compared with experimental results. The data suggest that the steric effect of the substituents has more influence than their electronic character on the structure of the resulting iridacycle compounds.Xunta de Galicia | Ref. ED431F 2016/005Xunta de Galicia | Ref. GRC2015/017Unión Europea-FEDER (Interreg V-A—España-Portugal) | Ref. 0245_IBEROS_1_

La participación de alumnos en Comunidades de Aprendizaje

Nuestro objetivo es dar a conocer la actividad “Prácticas de Intervención Psicoeducativa en Comunidades de Aprendizaje” que ha sido ofrecida en el curso 2013-14 de manera interdepartamental, con la participación de profesores de los Departamentos de Psicología Evolutiva y de la Educación y de Didáctica y Organización Educativa, de la Universidad de Sevilla. Se propuso para todos los alumnos de la Universidad como actividad de libre configuración, de reconocimiento de créditos o de voluntariado para los que no optasen por ninguna de las dos posibilidades primeras. La participación en Grupos Interactivos, Tertulias Dialógicas o en otras actividades llevadas a cabo por los estudiantes en los centros que forman parte de la Red de Comunidades de Aprendizaje de Sevilla está siendo gratificante personalmente para ellos y muy productiva desde un punto de vista académico para implicar a los estudiantes en actuaciones educativas de éxito y de superación del fracaso escolar.Our aim is to publicize the internships “Intervention in Educational Learning Communities” that has been offered in the academic year 2013-2014 with the participation of professors from the Departments of Psychology and Education and Teaching and Educational Organization, University of Seville. It has been offered to all university students and they will earn free-elected credits, recognition of credits or, at least, volunteerism for those who do not select the previous two options. The collaboration in Interactive Groups, Discussion Groups or other activities developed by the students in schools that are taken part in the Learning Community Network of Seville has being personally rewarded for them and really productive from the academic perspective. With this programme, students have been involved in successful practical experiences, overcoming school failure

El impulso del emprendimiento como competencia transversal en los estudiantes del Grado de Trabajo Social

Este proyecto está realizado por un grupo de profesores consolidado en docencia e investigación que apuesta por la innovación desde 2004, formado por profesores de la Facultad de Trabajo Social (UCM) y de distintas universidades nacionales que se preocupan por desarrollar planes de innovación que implementen la formación de los estudiantes con el fin de proporcionarles en su inserción laboral. El emprendimiento es parte de la competencia transversal “iniciativa y espíritu emprendedor” desarrollada especialmente en las asignaturas de Practicum (donde debe realizarse un Proyecto Social) y especialmente en el Trabajo Fin de Grado (TFG), ayudando a configurar el perfil profesional del alumnado. En la historia de la disciplina del Trabajo Social existen referentes que vinculan a la universidad como centro de la innovación y progreso de la humanidad. En este sentido sea motivado a la innovación y la creatividad en los estudiantes. La universidad se encuentra en una posición muy aventajada para promover las competencias relacionadas con la innovación y el espíritu empresarial. Estas competencias deben favorecer el emprendimiento social relacionado con el desarrollo social y humano, para la realización de una sociedad más equitativa y participativa desde distintas iniciativas que motiven la participación y la cooperación en esta sociedad desde sus instituciones. La responsabilidad social de la universidad, puede encontrase en esta función ya que se ha potenciado la adquisición de competencias profesionales. Entre algunos resultados próximos se resalta la presentación a los estudiantes de buenas prácticas realizadas desde la universidad para intervenir en la realidad social con el fin de incentivar la generación de nuevas experiencias. Además se destaca el hecho de que 5 estudiantes han terminado con un contrato de trabajo en su centro de practicas externas

Red de Empleabilidad y Emprendimiento en los estudiantes del Grado de Trabajo Social

Este proyecto sigue las líneas definidas en el Proyecto de Innovación y Mejora de la Calidad Docente de la Convocatoria 2016/2017, con el nº 109, con el tema: “El impulso del emprendimiento como competencia transversal en los estudiantes del Grado de Trabajo Social”, premiado en la VII EDICIÓN de PREMIOS EMPRENDEDOR UNIVERSITARIO UCM, en la 4ª modalidad de Premio Innova docente. Al mismo tiempo se ha implementado con el inicio de la experiencia del Proyecto de Aprendizaje Servicio “UCM_MEDIMAYOR_ ALUMNI”, de formación en mediación a un grupo de mayores pertenecientes al Centro de Día Peñagrande del Ayuntamiento de Madrid. La responsabilidad social de la universidad, puede encontrase en esta función ya que se ha potenciado la adquisición de competencias profesionales

Darunavir/cobicistat/emtricitabine/tenofovir alafenamide versus dolutegravir /abacavir/lamivudine in antiretroviral-naïve adults (SYMTRI): a multicenter randomized open-label study (PReEC/RIS-57)

D/C/F/TAF is the reference for combination therapy based on protease inhibitors but has not been compared with regimens containing integrase inhibitors as initial ART. We could not demonstrate D/C/F/TAF noninferiority relative to DTG/ABC/3TC, although both regimens were similarly well tolerated. Background Darunavir/cobicistat/emtricitabine/tenofovir alafenamide (D/C/F/TAF) is the reference for combination therapy based on protease inhibitors due to its efficacy, tolerability, and convenience. Head-to-head randomized comparisons between D/C/F/TAF and combination therapy based on integrase inhibitors in antiretroviral-naive patients are lacking. Methods Adult (>18 years old) human immunodeficiency virus-infected antiretroviral-naive patients (HLA-B*5701 negative and hepatitis B virus negative), with viral load (VL) >= 500 c/mL, were centrally randomized to initiate D/C/F/TAF or dolutegravir/abacavir/lamivudine (DTG/3TC/ABC) after stratifying by VL and CD4 count. Clinical and analytical assessments were performed at weeks 0, 4, 12, 24, and 48. The primary endpoint was VL 100 000 copies/mL, and 13% had <200 CD4 cells/mu L. Median weight was 73 kg and median body mass index was 24 kg/m(2). At 48 weeks, 79% (D/C/F/TAF) versus 82% (DTG/3TC/ABC) had VL <50 c/mL (difference, -2.4%; 95% confidence interval [CI], -11.3 to 6.6). Eight percent versus four percent experienced virologic failure but no resistance-associated mutations emerged. Four percent versus six percent had drug discontinuation due to adverse events. In the per-protocol analysis, 94% versus 96% of patients had VL <50 c/mL (difference, -2%; 95% CI, -8.1 to 3.5). There were no differences in CD4 cell count or weight changes. Conclusions We could not demonstrate the noninferiority of D/C/F/TAF relative to DTG/ABC/3TC as initial antiretroviral therapy, although both regimens were similarly well tolerated

Neuroblastoma RAS viral oncogene homolog (N-RAS) deficiency aggravates liver injury and fibrosis.

Progressive hepatic damage and fibrosis are major features of chronic liver diseases of different etiology, yet the underlying molecular mechanisms remain to be fully defined. N-RAS, a member of the RAS family of small guanine nucleotide-binding proteins also encompassing the highly homologous H-RAS and K-RAS isoforms, was previously reported to modulate cell death and renal fibrosis; however, its role in liver damage and fibrogenesis remains unknown. Here, we approached this question by using N-RAS deficient (N-RAS-/-) mice and two experimental models of liver injury and fibrosis, namely carbon tetrachloride (CCl4) intoxication and bile duct ligation (BDL). In wild-type (N-RAS+/+) mice both hepatotoxic procedures augmented N-RAS expression in the liver. Compared to N-RAS+/+ counterparts, N-RAS-/- mice subjected to either CCl4 or BDL showed exacerbated liver injury and fibrosis, which was associated with enhanced hepatic stellate cell (HSC) activation and leukocyte infiltration in the damaged liver. At the molecular level, after CCl4 or BDL, N-RAS-/- livers exhibited augmented expression of necroptotic death markers along with JNK1/2 hyperactivation. In line with this, N-RAS ablation in a human hepatocytic cell line resulted in enhanced activation of JNK and necroptosis mediators in response to cell death stimuli. Of note, loss of hepatic N-RAS expression was characteristic of chronic liver disease patients with fibrosis. Collectively, our study unveils a novel role for N-RAS as a negative controller of the progression of liver injury and fibrogenesis, by critically downregulating signaling pathways leading to hepatocyte necroptosis. Furthermore, it suggests that N-RAS may be of potential clinical value as prognostic biomarker of progressive fibrotic liver damage, or as a novel therapeutic target for the treatment of chronic liver disease

APICAMPUS, a project on Urban beekeeping developed at the University of Malaga

Urban beekeeping has ourished in the last years, with many institutions interested in creating colonies on their roofs. Bees and other animal pollinators contribute to increase food production, making bees essential for agriculture and plant life, in general. And, as bee populations decline, the need for secondary sources of pollinators for agricultural production grows. The Vice-rectorate of Smart-Campus of the University of Malaga focuses on two fundamen tal aspects: understanding the UMA campus as a Smart City in itself and marking new lines of action at the academic level that will make the UMA an international benchmark in Sustainability. Framed in the program above mentioned, APICAMPUS is a pilot and interdisciplinary project that involves researchers and students belonging to 4 departments of 2 university faculties together with Bee Garden Malaga, a multi-disciplinary environmental company with thematic areas on beekeeping. The project aims to promote the development of beekeeping in urban environments, raising awareness about the importance of the bees as pollinating insects, as well as the use of the beehive products. For the above mentioned, two beehives Langstroth type, were installed at the roof of the Faculty of Science, a traditional wooden one, and another made of polystyrene. The main interest of this project lies in the monitoring of the hives by means of temperature and humidity sensors, electronic scales for weight control, video cameras located inside and outside of them, together with the use of bee-marking systems. Additionally, analysis for characterizing and study the origin and the properties of the beehive products will be carried out, as well as field monitoring to highlight the situation of pollinators at the University Campus of Teatinos. Although the samplings have barely begun, this communication intends to be the offcial presentation of the project APICAMPUS to the scientific community.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech