Oxidation chemistry of d^0 organometallic complexes

Electron-transfer processes can play an important role in organometallic chemistry. Herein, we demonstrate that even d^0 organometallic complexes exhibit a rich redox chemistry and present electrochemical, kinetics, and stereochemical studies that establish a general outer-sphere oxidation process for d^0 group 4 metallocene complexes. This oxidation chemistry closely parallels the reported LMCT photochemistry of these complexes

Oxidation chemistry of d^0 organometallic complexes

Electron-transfer processes can play an important role in organometallic chemistry. Herein, we demonstrate that even d^0 organometallic complexes exhibit a rich redox chemistry and present electrochemical, kinetics, and stereochemical studies that establish a general outer-sphere oxidation process for d^0 group 4 metallocene complexes. This oxidation chemistry closely parallels the reported LMCT photochemistry of these complexes

Chemical conversions in supercritical media: Environmentally sound approaches to processes and materials

This is the final report of a two-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The aim of this effort was to evaluate the potential of supercritical fluids (SCF) as reaction media in an effort to develop new, environmentally-friendly methods for chemical synthesis or processing. The use of novel media creates the possibility of opening up substantially different chemical pathways, increasing selectivity (eliminating waste by-products), and enhancing reaction rates (decreasing hold-up times and saving energy). In addition, the use of SCF as reaction media facilitates downstream separations and mitigate or eliminate the need for hazardous solvents on scales from bench top to production. This project employed a highly interdisciplinary approach to investigate the utility of SCFs as reaction media for polymer synthesis and synthetic organic chemistry

Heterogenization of Homogeneous Catalysts: the Effect of the Support

We have studied the influence of placing a soluble, homogeneous catalyst onto a solid support. We determined that such a 'heterogenized' homogeneous catalyst can have improved activity and selectivity for the asymmetric hydrogenation of enamides to amino acid derivatives. The route of heterogenization of RhDuPhos(COD){sup +} cations occurs via electrostatic interactions with anions that are capable of strong hydrogen bonding to silica surfaces. This is a novel approach to supported catalysis. Supported RhDuPhos(COD){sup +} is a recyclable, non-leaching catalyst in non-polar media. This is one of the few heterogenized catalysts that exhibits improved catalytic performance as compared to its homogeneous analog

Fostering effective and sustainable scientific collaboration and knowledge exchange: a workshop-based approach to establish a national ecological observatory network (NEON) domain-specific user group

The decision to establish a network of researchers centers on identifying shared research goals. Ecologically specific regions, such as the USA’s National Ecological Observatory Network’s (NEON’s) eco-climatic domains, are ideal locations by which to assemble researchers with a diverse range of expertise but focused on the same set of ecological challenges. The recently established Great Lakes User Group (GLUG) is NEON’s first domain specific ensemble of researchers, whose goal is to address scientific and technical issues specific to the Great Lakes Domain 5 (D05) by using NEON data to enable advancement of ecosystem science. Here, we report on GLUG’s kick off workshop, which comprised lightning talks, keynote presentations, breakout brainstorming sessions and field site visits. Together, these activities created an environment to foster and strengthen GLUG and NEON user engagement. The tangible outcomes of the workshop exceeded initial expectations and include plans for (i) two journal articles (in addition to this one), (ii) two potential funding proposals, (iii) an assignable assets request and (iv) development of classroom activities using NEON datasets. The success of this 2.5-day event was due to a combination of factors, including establishment of clear objectives, adopting engaging activities and providing opportunities for active participation and inclusive collaboration with diverse participants. Given the success of this approach we encourage others, wanting to organize similar groups of researchers, to adopt the workshop framework presented here which will strengthen existing collaborations and foster new ones, together with raising greater awareness and promotion of use of NEON datasets. Establishing domain specific user groups will help bridge the scale gap between site level data collection and addressing regional and larger ecological challenges

Novel phase diagram behavior and materials design in heterostructural semiconductor alloys

Structure and composition control the behavior of materials. Isostructural alloying is historically an extremely successful approach for tuning materials properties, but it is often limited by binodal and spinodal decomposition, which correspond to the thermodynamic solubility limit and the stability against composition fluctuations, respectively. We show that heterostructural alloys can exhibit a markedly increased range of metastable alloy compositions between the binodal and spinodal lines, thereby opening up a vast phase space for novel homogeneous single-phase alloys. We distinguish two types of heterostructural alloys, that is, those between commensurate and incommensurate phases. Because of the structural transition around the critical composition, the properties change in a highly nonlinear or even discontinuous fashion, providing a mechanism for materials design that does not exist in conventional isostructural alloys. The novel phase diagram behavior follows from standard alloy models using mixing enthalpies from first-principles calculations. Thin-film deposition demonstrates the viability of the synthesis of these metastable single-phase domains and validates the computationally predicted phase separation mechanism above the upper temperature bound of the nonequilibrium single-phase region

Toll-Like Receptor 8 Agonist and Bacteria Trigger Potent Activation of Innate Immune Cells in Human Liver

This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.The study was supported by a Grant core funding from the Agency for Science Technology and Research (A*STAR, Singapore) and a Singapore Translational Research Investigator Award (NRMC/StaR/013/2012) to AB as well as NIHR Biomedical Centre, Oxford, WT 091663MA, NIAID1U19AI082630-01, Oxford Martin School funding and an NIHR Senior Investigator award to PK

Adolescents opinions regarding Plato del Bien Comer Maya as nutrition health promotion tool

Conocer opiniones sobre el Plato del Bien Comer Maya de adolescentes de Cholul, Yucatán, para mejorar la herramienta comunicativa y utilizarla en actividades de promoción de la salud. Material y métodos. Estudio cualitativo, de investigación formativa. Se realizaron tres grupos focales, participaron 28 adolescentes de secundaria: 12-16 años. Criterios de inclusión: pertenecer a alguno de los tres grados de la escuela y tener familias originarias del poblado. El análisis de los datos se realizó manualmente. Resultados. En comparación con el Plato del Bien Comer nacional, el Plato Maya fue mejor identificado por tener elementos locales a los que pueden acceder fácilmente y con costos menores. Se identificó la palabra fruto como una variación lingüística que representa en ese contexto tanto a las frutas como a las verduras. Conclusiones. Para tener mejores resultados en intervenciones nutricionales es necesario diseñar estrategias educativo-comunicativas acordes con la cultura local.To know opinions of adolescents from Cholul, Yucatán, about Plato del Bien Comer Maya in order to improve it as health promotion tool. Qualitative study, formative research. Three focus groups were carried out, participating 28 adolescents: 12-16 years old. Criteria of inclusion: studying middle school; to have native family from the town. Analysis of the data made manually. Results. Comparatively with the national Plato del Bien Comer, the Plato Maya was better identified because have local food products easier to obtain and cheaper. The principal finding was to understand Fruto is a linguistic variation word which represents in Maya context both fruits and vegetables. This might be an important key to improve health promotion activities with that population. In order to have better results in nutritional interventions, it is necessary to design educational-communicative strategies in accordance with the local culture.Fil: Zulema Morayma Cabrera Araujo. Universidad Autónoma de Yucatán; MéxicoFil: Víctor Hernández Escalante. Universidad Autónoma de Yucatán; MéxicoFil: Alina Marín Cárdenas. Universidad Autónoma de Yucatán; MéxicoFil: Rocío Murguía Argüelles. Universidad de Oriente; MéxicoFil: Noel Magaña Be. Universidad de Oriente; MéxicoFil: Karla Ramón Escobar. Universidad de Oriente; MéxicoFil: Javier Hirose López. Universidad de Oriente; MéxicoFil: Lázaro Tuz Chi. Universidad de Oriente; MéxicoFil: Abril Salas Góngora. Universidad de Oriente; MéxicoFil: Joed Peña Alcocer. Universidad de Oriente; MéxicoFil: Tumas, Natalia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones y Estudios sobre Cultura y Sociedad. Universidad Nacional de Córdoba. Centro de Investigaciones y Estudios sobre Cultura y Sociedad; ArgentinaFil: Carlos Castro Sansores. Universidad Autónoma de Yucatán; MéxicoFil: Clara Juárez Ramírez. Instituto de Salud Pública de México; Méxic

Perovskite-Inspired Photovoltaic Materials: Toward Best Practices in Materials Characterization and Calculations

Recently, there has been an explosive growth in research based on hybrid lead–halide perovskites for photovoltaics owing to rapid improvements in efficiency. The advent of these materials for solar applications has led to widespread interest in understanding the key enabling properties of these materials. This has resulted in renewed interest in related compounds and a search for materials that may replicate the defect-tolerant properties and long lifetimes of the hybrid lead-halide perovskites. Given the rapid pace of development of the field, the rises in efficiencies of these systems have outpaced the more basic understanding of these materials. Measuring or calculating the basic properties, such as crystal/electronic structure and composition, can be challenging because some of these materials have anisotropic structures, and/or are composed of both heavy metal cations and volatile, mobile, light elements. Some consequences are beam damage during characterization, composition change under vacuum, or compound effects, such as the alteration of the electronic structure through the influence of the substrate. These effects make it challenging to understand the basic properties integral to optoelectronic operation. Compounding these difficulties is the rapid pace with which the field progresses. This has created an ongoing need to continually evaluate best practices with respect to characterization and calculations, as well as to identify inconsistencies in reported values to determine if those inconsistencies are rooted in characterization methodology or materials synthesis. This article describes the difficulties in characterizing hybrid lead–halide perovskites and new materials and how these challenges may be overcome. The topic was discussed at a seminar at the 2015 Materials Research Society Fall Meeting & Exhibit. This article highlights the lessons learned from the seminar and the insights of some of the attendees, with reference to both recent literature and controlled experiments to illustrate the challenges discussed. The focus in this article is on crystallography, composition measurements, photoemission spectroscopy, and calculations on perovskites and new, related absorbers. We suggest how the reporting of the important artifacts could be streamlined between groups to ensure reproducibility as the field progresses