Molecular hydrogen and water activation by transition metal frustrated Lewis pairs containing ruthenium or osmium components: catalytic hydrogenation assays

The transition metal frustrated Lewis pair compounds [(Cym)M(κ3S,P,N-HL1)][SbF6] (Cym = η6-p-MeC6H4iPr; H2L1 = N-(p-tolyl)-N′-(2-diphenylphosphanoethyl)thiourea; M = Ru (5), Os (6)) have been prepared from the corresponding dimer [{(Cym)MCl}2(μ-Cl)2] and H2L1 by successive chloride abstraction with NaSbF6 and AgSbF6 and NH deprotonation with NaHCO3. Complexes 5 and 6 and the previously reported phosphano–guanidino compounds [(Cym)M(κ3P,N,N′-HL2)][SbF6] [H2L2 = N,N′-bis(p-tolyl)-N′′-(2-diphenylphosphanoethyl) guanidine; M = Ru (7), Os (8)] and pyridinyl–guanidino compounds [(Cym)M(κ3N,N′,N′′-HL3)][SbF6] [H2L3 = N,N′-bis(p-tolyl)-N′′-(2-pyridinylmethyl) guanidine; M = Ru (9), Os (10)] heterolytically activate H2 in a reversible manner affording the hydrido complexes [(Cym)MH(H2L)][SbF6] (H2L = H2L1; M = Ru (11), Os (12); H2L = H2L2; M = Ru (13), Os (14); H2L = H2L3; M = Ru (15), Os (16)). DFT calculations carried out on the hydrogenation of complex 7 support an FLP mechanism for the process. Heating 9 and 10 in methanol yields the orthometalated complexes [(Cym)M(κ3N,N′,C-H2L3-H)][SbF6] (M = Ru (17), Os (18)). The phosphano–guanidino complex 7 activates deuterated water in a reversible fashion, resulting in the gradual deuteration of the three cymene methyl protons through sequential C(sp3)–H bond activation. From DFT calculations, a metal–ligand cooperative reversible mechanism that involves the O–H bond activation and the formation of an intermediate methylene cyclohexenyl complex has been proposed. Complexes 5–10 catalyse the hydrogenation of the C[double bond, length as m-dash]C double bond of styrene and a range of acrylates, the C[double bond, length as m-dash]O bond of acetophenone and the C[double bond, length as m-dash]N bond of N-benzylideneaniline and quinoline. The C[double bond, length as m-dash]C double bond of methyl acrylate adds to catalyst 9, affording complex 19 in which a new ligand exhibiting a fac κ3N,N′,C coordination mode has been incorporated

Clinical rating scale for pantothenate kinase-associated neurodegeneration: A pilot study

Pantothenate kinase-associated neurodegeneration is a progressive neurological disorder occurring in both childhood and adulthood. The objective of this study was to design and pilot-test a disease-specific clinical rating scale for the assessment of patients with pantothenate kinase-associated neurodegeneration.info:eu-repo/semantics/publishedVersio

Circulating microRNAs in sera correlate with soluble biomarkers of immune activation but do not predict mortality in ART treated individuals with HIV-1 infection: A case control study

Introduction: The use of anti-retroviral therapy (ART) has dramatically reduced HIV-1 associated morbidity and mortality. However, HIV-1 infected individuals have increased rates of morbidity and mortality compared to the non-HIV-1 infected population and this appears to be related to end-organ diseases collectively referred to as Serious Non-AIDS Events (SNAEs). Circulating miRNAs are reported as promising biomarkers for a number of human disease conditions including those that constitute SNAEs. Our study sought to investigate the potential of selected miRNAs in predicting mortality in HIV-1 infected ART treated individuals. Materials and Methods: A set of miRNAs was chosen based on published associations with human disease conditions that constitute SNAEs. This case: control study compared 126 cases (individuals who died whilst on therapy), and 247 matched controls (individuals who remained alive). Cases and controls were ART treated participants of two pivotal HIV-1 trials. The relative abundance of each miRNA in serum was measured, by RTqPCR. Associations with mortality (all-cause, cardiovascular and malignancy) were assessed by logistic regression analysis. Correlations between miRNAs and CD4+ T cell count, hs-CRP, IL-6 and D-dimer were also assessed. Results: None of the selected miRNAs was associated with all-cause, cardiovascular or malignancy mortality. The levels of three miRNAs (miRs -21, -122 and -200a) correlated with IL-6 while miR-21 also correlated with D-dimer. Additionally, the abundance of miRs -31, -150 and -223, correlated with baseline CD4+ T cell count while the same three miRNAs plus miR- 145 correlated with nadir CD4+ T cell count. Discussion: No associations with mortality were found with any circulating miRNA studied. These results cast doubt onto the effectiveness of circulating miRNA as early predictors of mortality or the major underlying diseases that contribute to mortality in participants treated for HIV-1 infection

TFG 2013/2014

Amb aquesta publicació, EINA, Centre universitari de Disseny i Art adscrit a la Universitat Autònoma de Barcelona, dóna a conèixer el recull dels Treballs de Fi de Grau presentats durant el curs 2013-2014. Voldríem que un recull com aquest donés una idea més precisa de la tasca que es realitza a EINA per tal de formar nous dissenyadors amb capacitat de respondre professionalment i intel·lectualment a les necessitats i exigències de la nostra societat. El treball formatiu s’orienta a oferir resultats que responguin tant a paràmetres de rigor acadèmic i capacitat d’anàlisi del context com a l’experimentació i la creació de nous llenguatges, tot fomentant el potencial innovador del disseny.Con esta publicación, EINA, Centro universitario de diseño y arte adscrito a la Universidad Autónoma de Barcelona, da a conocer la recopilación de los Trabajos de Fin de Grado presentados durante el curso 2013-2014. Querríamos que una recopilación como ésta diera una idea más precisa del trabajo que se realiza en EINA para formar nuevos diseñadores con capacidad de responder profesional e intelectualmente a las necesidades y exigencias de nuestra sociedad. El trabajo formativo se orienta a ofrecer resultados que respondan tanto a parámetros de rigor académico y capacidad de análisis, como a la experimentación y la creación de nuevos lenguajes, al tiempo que se fomenta el potencial innovador del diseño.With this publication, EINA, University School of Design and Art, affiliated to the Autonomous University of Barcelona, brings to the public eye the Final Degree Projects presented during the 2013-2014 academic year. Our hope is that this volume might offer a more precise idea of the task performed by EINA in training new designers, able to speak both professionally and intellectually to the needs and demands of our society. The educational task is oriented towards results that might respond to the parameters of academic rigour and the capacity for contextual analysis, as well as to considerations of experimentation and the creation of new languages, all the while reinforcing design’s innovative potential

Structural differences in enantiopure and racemate organometallic complexes. Application to [(η5-C5Me5)RhCl(PN)]+n complexes

Resumen del trabajo presentado al 30th European Crystallographic Meeting, celebrado del 28 de agosto al 1 de septiembre de 2016 en Switzerland.The use of metal-based catalysts is one of the most powerful strategies for synthesizing enantioenriched compounds by asymmetric catalysis. Our lab is focused in the development and structural characterization of different types of coordination complexes, based on 2nd and 3rd row late transition metals, and in their potential application as homogeneous catalyst precursors, trying to establish a clear correspondence between specific structural parameters and chemical and catalytic activity. This approach usually relies on organometallic complexes where the metal atoms are stereogenic centers. The asymmetric environment around the metal, i.e., the catalyst pocket in which catalysis occurs, may control the achieved enantioselectivity. Therefore, the synthesis, isolation and the detailed structural characterization of enantiopure catalysts are primary goals in this research line.  Peer Reviewe

HEMATOMA SUBDURAL CRÓNICO EN PACIENTE CON QUISTE ARACNOIDEO GIGANTE

Varón  de  38  años  atendido  en  Urgencias  por  cefalea.  Refiere   traumatismo craneoencefálico 6 meses antes. Asintomático en todo ese tiempo, acude por presentar cefalea holocraneal e inestabilidad de horas de evolución sin nuevo evento traumático. A su llegada, Glasgow 4-5-6, sin signos de focalidad neurológica. Se realiza tomografía computarizada (TC) craneal (Figura 1) objetivando amplio hematoma subdural crónico frontoparietal izquierdo con desplazamiento de línea media e imagen compatible con quiste aracnoideo gigante de fosa temporal y cisura silviana izquierda. El paciente fue valorado por el Servicio de Neurocirugía, donde ingresó para completar estudio. Dada la estabilidad que mostraba, sin focalidad neurológica y adecuado control clínico con analgesia, se realizó, de forma programada, resonancia magnética cerebral (RM) (Figura 2) y tratamiento quirúrgico mediante drenaje parcial del quiste y la colección  subdural, con óptimos resultados.

Autolesión por arma blanca

Varón de 36 años, traído a Urgencias por 061, tras lesiones con arma blanca  por motivos autolíticos. Presenta herida incisiva profunda cervical anterior, y objeto  punzante introducido en zona temporal derecha, correctamente fijado, paciente consciente, GCS 15, con respiración espontánea, y estabilidad hemodinámica, siendo valorado por ORL y UCI se decide intervención quirúrgica urgente, realizando reconstrucción faringo-laríngea y traqueotomía

Half-sandwich complexes of iridium and ruthenium containing cysteine-derived ligands

The dimers [{(η-ring)MCl}(μ-Cl)] ((η-ring)M = (η-CMe)Ir, (η-p-MeCHiPr)Ru) react with the modified cysteines S-benzyl-l-cysteine (HL1) or S-benzyl-α-methyl-l-cysteine (HL2) affording cationic complexes of the formula [(η-ring)MCl(κN,S-HL)]Cl (1, 2) in good yield. Addition of NaHCO to complexes 1 and 2 gave equilibrium mixtures of neutral [(η-ring)MCl(κN,O-L)] (3, 4) and cationic [(η-ring)M(κN,O,S-L)]Cl (6Cl, 7Cl) complexes. Similar mixtures were obtained in one-pot reaction by successive addition of the modified cysteine and NaHCO to the above formulated dimers. Addition of the N-Boc substituted cysteine derivative S-benzyl-N-Boc-l-cysteine (HL3) and NaHCO to the dimers [{(η-ring)MCl}(μ-Cl)] affords the neutral compounds [(η-ring)MCl(κO,S-L3)] ((η-ring)M = (η-CMe)Ir (5a), (η-p-MeCHiPr)Ru (5b)). Complexes of the formula [(η-ring)MCl(κN,O,S-L)][SbF] (6Sb-8Sb), in which the cysteine derivative acts as a tridentate chelate ligand, can be prepared by adding one equivalent of AgSbF to the solutions of compounds 5 or to the mixtures of complexes 3/6Cl and 4/7Cl. The amide proton of compounds 8aSb and 8bSb can be removed by addition of NaHCO affording the neutral complexes [(η-ring)M(κN,O,S-L3)] ((η-ring)M = (η-CMe)Ir (9a), (η-p-MeCHiPr)Ru (9b)). Complexes 9a and 9b can also be prepared by reacting the dimers [{(η-ring)MCl}(μ-Cl)] with HL3 and two equivalents of NaHCO. The absolute configuration of the complexes has been established by spectroscopic and diffractometric means including the crystal structure determination of (R,R,R)-[(η-CMe)Ir(κN,O,S-L1)][SbF] (6aSb). The thermodynamic parameters associated with the epimerization at sulphur that the iridium compound [(η-CMe)Ir(κN,O,S-L3)] (9a) undergoes have been determined through variable temperature H NMR studies.We thank the Ministerio de Economía y Competitividad of Spain (CTQ2012-32095, CTQ2013-40855-R and CTQ2015-67366-P) Gobierno de Aragón and the European Social Fund (Grupos Consolidados: Catalizadores Organometálicos Enantioselectivos, Aminoácidos y Péptidos and Inorganic Molecular Architecture) for financial support. M. C. acknowledges Diputación General de Aragón, CSIC and the European Social Fund for a grant. R. R. and P. G. O. acknowledge CSIC, the European Social Fund and the Ministerio de Economía y Competitividad of Spain for the JAE and Ramón y Cajal (RYC-2013-13800) grants and for a PTA contract, respectively.Peer Reviewe

Half-sandwich complexes of rhodium containing cysteine-derived ligands

The modified cysteine ligand, S-benzyl-α-methyl-l-cysteine (HL2), was prepared from l-cysteine hydrochloride methyl ester. The reaction of commercial S-benzyl-l-cysteine (HL1) or HL2 with the dimer, [{(η-CMe)RhCl}(μ-Cl)], gives rise to the cationic complexes, [(η-CMe)RhCl(HL)]Cl (HL = HL1 (1), HL2 (2)), in which the cysteine ligand exhibits a κN,S coordination mode. In a basic medium, HL1 or HL2 reacts with [{(η-CMe)RhCl}(μ-Cl)] to afford mixtures of two epimers at the metal centre of the neutral complexes, [(η-CMe)RhCl(κN,O-L)] (HL = HL1 (3), HL2 (4)), in which amino carboxylate adopts a κN,O mode of coordination along with variable amounts of the cationic compounds, [(η-CMe)Rh(κN,O,S-L)]Cl (HL = HL1 (6Cl), HL2 (7Cl)), which contain κN,O,S coordinated cysteine-derived ligands. However, in a basic medium, the N-Boc substituted cysteine S-benzyl-N-Boc-l-cysteine (HL3) only yields the κO,S coordinated derivative, [(η-CMe)RhCl(κO,S-L3)] (5), as a mixture of two diastereomers depending on the configuration of the metal centre. The bidentate chelate complexes 3-5 react with AgSbF to give the hexafluoroantimonates [(η-CMe)Rh(κN,O,S-L)][SbF] (HL = HL1 (6Sb), HL2 (7Sb), HL3 (8Sb)) with tridentate coordination. Compound 8Sb reacts with NaHCO to give the neutral complex [(η-CMe)Rh(κN,O,S-L3)] (9), which can also be prepared by reacting the dimer [{(η-CMe)RhCl}(μ-Cl)] with HL3 in the presence of two equivalents of NaHCO. The new compounds contain up to four stereogenic centres, namely, Rh, S, N, and C. The absolute configuration of the complexes has been established by spectroscopic and diffractometric investigations, including the crystal structure determination of [(η-CMe)RhCl(κO,S-L3)] (5), [(η-CMe)Rh(κN,O,S-L1)][SbF] (6Sb), [(η-CMe)Rh(κN,O,S-L2)][SbF] (7Sb) and [(η-CMe)Rh(κN,O,S-L3)] (9). Variable temperature H NMR studies reveal the existence of epimerization processes and theoretical calculations were used to discriminate their nature.We thank the Ministerio de Economía y Competitividad of Spain (CTQ2012-32095, CTQ2014-53033-P, CTQ2015-67366-P and CTQ2013-408555R) and Gobierno de Aragón and European Social Fund (Grupos Consolidados: Catalizadores Organometálicos Enantioselectivos, Aminoácidos y Péptidos and Inorganic Molecular Architecture) for financial support. This work was supported by the CONSOLIDER INGENIO 2010 program under the project “Factoría de Cristalización” (CSD2006-0015). M. C. acknowledges Diputación General de Aragón, CSIC and European Social Fund for a grant. R. R. and P. G. O. acknowledge CSIC, European Social Fund and Ministerio de Economía y Competitividad of Spain for a JAE and a Ramón y Cajal (RYC-2013-13800) grants and for a PTA contract, respectively.Peer Reviewe

Intoxicación con dosis inusualmente altas de Paracetamol

La intoxicación por paracetamol es la principal causa de fracaso hepático agudo (FHA) en países desarrollados, sin embargo, en España es infrecuente (2,2% de los casos). El diagnóstico de FHA se basa en la exploración fisica (alteración del estado mental) y los hallazgos de  laboratorio (INR>1,5). Además de la elevación de las transaminasas, las alteraciones del INR, la hiperbilirrubinemia, la hipoglucemia y la acidosis metabólica son las que definen mejor el grado de insuficiencia hepática. Es frecuente la insuficiencia renal progresiva (25% de la hepatopa a grave) y la encefalopa a que es secundaria a edema cerebral en el FHA de inicio rápido. Presenta una mortalidad del 20-40%. Presentamos un caso de intoxicación por PCT que debuta con fracaso hepático agudo por ingesta de dosis inusualmente altas y letales (100 grm), y realizamos una revisión del tema