Enantioselection on Heterogeneous Noble Metal Catalyst: Proline-Induced Asymmetry in the Hydrogenation of Isophorone on Pd Catalyst.

In the (S)-proline-mediated asymmetric hydrogenation of isophorone (IP) on supported Pd catalyst, excellent enantioselectivity is achieved, with an enantiomeric excess of up to 99%. The role of the heterogeneous catalyst has been the subject of a controversial debate, and the current mechanistic understanding cannot explain the observed enantioselectivity of this catalytic system. The lack of in situ information about the role of the heterogeneous catalyst has prompted us to investigate the surface processes occurring at the methanol-Pd catalyst interface using attenuated total reflection infrared spectroscopy. Time-resolved monitoring of the homogeneous solution and of the catalytic solid-liquid interface coupled with catalytic data provides crucial information on the catalytically relevant enantiodifferentiating processes. While the condensation of IP and the corresponding chiral product 3,3,5-trimethylcyclohexanone with the chiral amine is connected to the enantiodifferentiation, it was found that the crucial enantioselectivity-controlling steps take place on the metal surface, and the reaction has to be classified as heterogeneous asymmetric hydrogenation. The presented spectroscopic and catalytic results provide strong evidence for the existence of two competing enantioselective processes leading to opposing enantioselection. Depending on surface coverage of the Pd catalyst, the reaction is controlled either by kinetic resolution ((S)-pathway) or by chiral catalysis ((R)-pathway). Steering the hydrogenation on the (R)-reaction pathway requires sufficient concentration of IP-(S)-proline condensate, as this chiral reactive intermediate becomes the most abundant surface species, inhibiting the competing kinetic resolution. The unraveled (R)-reaction pathway emphasizes an intriguing strategy for inducing chirality in heterogeneous asymmetric catalysis.

Early Pleistocene human humeri from the Gran Dolina-TD6 site (Sierra de Atapuerca, Spain).

In this report, we present a morphometric comparative study of two Early Pleistocene humeri recovered from the TD6 level of the Gran Dolina cave site in Sierra de Atapuerca, northern Spain. ATD6-121 belongs to a child between 4 and 6 years old, whereas ATD6-148 corresponds to an adult. ATD6-148 exhibits the typical pattern of the genus Homo, but it also shows a large olecranon fossa and very thin medial and lateral pillars (also present in ATD6-121), sharing these features with European Middle Pleistocene hominins, Neandertals, and the Bodo Middle Pleistocene humerus. The morphology of the distal epiphysis, together with a few dental traits, suggests a phylogenetic relationship between the TD6 hominins and the Neandertal lineage. Given the older geochronological age of these hominins (ca. 900 ka), which is far from the age estimated by palaeogenetic studies for the population divergence of modern humans and Neandertals (ca. 400 ka), we suggest that this suite of derived "Neandertal" features appeared early in the evolution of the genus Homo. Thus, these features are not "Neandertal" apomorphies but traits which appeared in an ancestral and polymorphic population during the Early Pleistocene.

Revealing Catalytically Relevant Surface Species by Kinetic Isotope Effect Spectroscopy: H-Bonding to Ester Carbonyl of trans-Ethyl Pyruvate Controls Enantioselectivity on a Cinchona-Modified Pt Catalyst.

Monitoring active surface species on an operating technical catalyst is a challenging task due to the presence of multiple different adsorption sites and the abundance of bulk species. In this work, kinetic isotope effect (KIE) spectroscopy is introduced to capture the signals of catalytically relevant hydrogenation species from the IR spectroscopic detection in attenuated total reflection mode. The catalytic interface formed between a cinchona-modified Pt/Al2O3 catalyst and the solvent toluene is sensitively probed directly at the rate limiting step(s) during the asymmetric hydrogenation of ethyl pyruvate by measuring the effects of substituting H2 by D2 kinetically and spectroscopically in the same operando experiment. The application of KIE spectroscopy provides unprecedented molecular level insight into the structure of the diastereomeric intermediate surface complex and the phenomenon rate enhancement, which revolutionizes our understanding of chirally modified metal catalysts.

Evaluación de una intervención para mejora en la administración segura de medicación en el turno de noche / An Intervention to Improve Safe Administration of Medication in the Night Shift

Introducción: Uno de cada siete pacientes hospitalizados experimenta un evento adverso relacionado con la administración de medicación. Los errores de medicación son una de las causas más importantes de mortalidad y morbilidad prevenible. Objetivo: Evaluar la eficacia de una intervención formativa sobre la población de enfermeras de turno de noche de un hospital de agudos para mejorar el cumplimiento del protocolo de administración segura de medicación. Métodos: Ensayo experimental, pre-post intervención formativa, realizado en Hospital Clínic de Barcelona, durante 2015-2016. Población: 268 enfermeras en dos turnos de noche, muestra: 177 participantes (88 Grupo Control y 89 Grupo Experimental). La intervención consistió en sesiones informativas y acceso a Procedimiento escrito. El instrumento de medida fue el Procedimiento Normalizado de Trabajo de la institución mediante check-list de cumplimiento. Se realzó estudio uni-bivariable, mediante Chi2 y test de Fisher con significancia para p < 0,05. Resultados: Se realizaron 219 observaciones en Grupo Control y 207 en Grupo Experimental. De 17 variables analizadas, solo tres mostraron diferencias significativas: en Grupo Experimental mejoró el conocimiento del Procedimiento; se incrementó el uso del agua y jabón sobre la solución hidroalcohólica; y empeoró la identificación normalizada de fármacos pendientes de administrar. Ninguna de las 14 variables restantes mostró diferencias significativas. De 426 observaciones, solo se produjeron 3 errores de medicación en Grupo control, subsanados antes de su administración, y 0 en Grupo Experimental. Conclusiones: Las intervenciones formativas clásicas con receptores pasivos pueden no ser eficaces para mejorar la práctica enfermera en administración segura de medicación(AU)

Introduction: One in seven hospitalized patients experiences an adverse event related to administration of medication. Medication errors are one of the most important causes of preventable mortality and morbidity. Objective: To assess the efficacy of a training intervention with the population of night shift nurses in an acute care hospital, in order to improve compliance with the protocol for the safe administration of medication. Methods: Experimental trial, pre-post training intervention, carried out at Hospital Clínic of Barcelona, during 2015-2016. The population consisted of 268 nurses in two night shifts. The sample consisted of 177 participants (88 from the control group and 89 from the experimental group). The intervention consisted in information sessions and access to a written procedure. The measurement instrument was the Institution's Standard Work Procedure by means of a compliance check-list. Uni-bivariate study was performed, using chi-square and Fisher's test with a significance of P < 0.05. Results: 219 observations were carried out in the control group and 207, in the experimental group. Of seventeen variables analyzed, only three showed significant differences: in the experimental group, knowledge of the procedure improved, increase in the use of soap and water over hydroalcoholic solution, and worsening of standardized identification of drugs pending from being administered. None of the fourteen remaining variables showed significant differences. Of 426 observations, only three medication errors occurred in the control group, corrected before its administration, and zero occurred in the experimental group. Conclusions: Classic training interventions with passive receptors may not be effective to improve nursing practice in safe administration of medication(AU)

Metric and morphological study of the upper cervical spine from the Sima de los Huesos site (Sierra de Atapuerca, Burgos, Spain).

In this article, the upper cervical spine remains recovered from the Sima de los Huesos (SH) middle Pleistocene site in the Sierra de Atapuerca (Burgos, Spain) are described and analyzed. To date, this site has yielded more than 5000 human fossils belonging to a minimum of 28 individuals of the species Homo heidelbergensis. At least eleven individuals are represented by the upper cervical (C1 and C2) specimens: six adults and five subadults, one of which could represent an adolescent individual. The most complete adult vertebrae (three atlases and three axes) are described, measured, and compared with other fossil hominins and modern humans. These six specimens are associated with one another and represent three individuals. In addition, one of these sets of cervical vertebrae is associated with Cranium 5 (Individual XXI) from the site. The metric analysis demonstrates that the Sima de los Huesos atlases and axes are metrically more similar to Neandertals than to our modern human comparative sample. The SH atlases share with Neandertals a sagittally elongated canal. The most remarkable feature of the SH (and Neandertal) axes is that they are craniocaudally low and mediolaterally wide compared to our modern male sample. Morphologically, the SH sample shares with Neandertals a higher frequency of caudally projected anterior atlas arch, which could reflect greater development of the longus colli muscle. In other features, such as the frequency of weakly developed tubercles for the attachment of the transverse ligament of the atlas, the Sima de los Huesos fossils show intermediate frequencies between our modern comparative samples and the Neandertals, which could represent the primitive condition. Our results are consistent with the previous phylogenetic interpretation of H. heidelbergensis as an exclusively European species, ancestral only to H. neanderthalensis.

Confiabilidad del cuestionario Brief COPE inventory en versión en español para evaluar estrategias de afrontamiento en pacientes con cáncer de seno / Confiabilidade do questionário Brief COPE inventory em versão em espanhol para avaliar estratégias de afrontamento em pacientes com câncer de mama / Reliability of the questionnaire brief COPE inventory in Spanish version for Assessing Coping strategies in patients with breast cancer, Bogotá, Colombia, 2009

Introducción: El cáncer de seno no sólo se caracteriza por sus elevadas cifras estadísticas, sino por las cargas emocionales que conlleva y que desempeñan un papel importante en la enfermedad, pues estas se equilibran a través del proceso de afrontamiento mediante dos estrategias: una activa (relacionada con enfrentar la enfermedad de manera directa) y una pasiva (que trata de evitar y negar el conflicto que vive la mujer). Objetivo: Establecer la confiabilidad del cuestionario Brief COPE Inventory (BCI) en versión en español para evaluar estrategias de afrontamiento en mujeres con cáncer de seno. Metodología: Estudio psicométrico con 140 aplicaciones del cuestionario a pacientes en una unidad oncológica de Bogotá. Para el análisis se utilizó el programa estadístico SPSS 16.0, que determinó la confiabilidad a través del modelo alfa de Cronbach. Resultados: El estudio determinó para el BCI un alfa de Cronbach total de 0,698. Para la dimensión afrontamientoactivo, el valor del alfa fue de 0,663, y para la dimensión afrontamiento pasivo, de 0,523. El cuestionario quedó conformado por 28 ítems que evalúan dos dimensiones:afrontamiento activo y afrontamiento pasivo, cada una con siete estrategias. Conclusión: El BCI en versión en español aplicado a mujeres con cáncer de seno no sufrió cambios significativos en su constructo teórico, lo que muestra que puede utilizarse en esta población, así como en las que ya fue validado; sin embargo, se recomienda continuar con el análisis psicométrico, aplicándolo a población colombiana para evaluar estrategias de afrontamiento con el fin de obtener indicadores de validez externa...

Introduction: Breast cancer is not only characterized by their high statistical figures but also by emotional burdens that play an important role in the disease which are balanced through the process of coping, which is carried out using various strategies, with two forms: An active form (associated with the disease face a direct), and a passive form (seeks to avoid conflict and deny the patient lives). Objective: To establish the reliability of the questionnaire Brief COPE Inventory (BCI) in Spanish to assess coping strategies in women with breast cancer. Methodology: A psychometric questionnaire applications with 140 patients in an oncology unit in Bogota was used to analyze the statistical program SPSS 16.0, determining the reliability by Cronbach’s alpha model. Results: Showed the BCI in a Spanish Cronbach alpha of 0.698. For the active coping dimension value was 0.663, and for passive coping dimension 0.523. The questionnaire was composed of 28 items that assess two dimensions: coping and stand, each with seven coping strategies. Conclusion: The BCI in Spanish applied to women with breast cancer did not suffer significant changes in his theoretical construct, which shows that can be used in this population as well as the already approved and recommended to continue with the analysis applied to psychometric Colombian population to assess coping strategies in order to obtain indicators of external validity...

Introdução: O câncer de mama não só está caracterizado por seu alto número de casos, senão também pela carga emocional, que desempenha um papel importante na doença, aspecto que é equilibrado através do processo de afrontamento realizado por os doentes, mediante duas estratégias que incluem: uma forma ativa (relacionada com o afrontamento da doença) e uma forma passiva (que tenta evitar e negar o conflito). Objetivo: Determinar a confiabilidade do questionário Brief COPE Inventory (BCI) em versão ao espanhol para avaliar as estratégias de afrontamento em mulheres com câncer de mama. Metodologia: Foi feito um estudo psicometrico com 140 aplicações do questionário em doentes de uma unidade de cuidado de oncologia de Bogotá. Para o analise dos dados foi utilizado o programa estatístico SPSS 16.0, e se estabeleceu a confiabilidade com o modelo de alfa de Cronbach. Resultados: O estudo encontrou para o BCI um alfa de Cronbach global de 0,698. A dimensão de afrontamento ativo teve um valor de alfa de 0,663, e para a dimensão de afrontamento passivo, de 0,523. O questionário finalmente esta composto por 28 itens que avaliam duas dimensões: ativa e passiva, cada uma com sete estratégias de afrontamento. Conclusão: A versão em espanhol do BCI aplicado a mulheres com câncer da mama não sofreu alterações significativas na sua construção teórica, o que mostra que pode ser usado nesta população e naqueles onde foi validado o questionário, mas recomenda-se a continuar o análise psicométrica, aplicando-o à população colombiana com características similares para determinar os indicadores de validade externa...