Synthesis, x-ray structure and anion binding properties of a cryptand-like hybrid calixpyrrole

The novel cryptand in/out-3, containing two tripyrrolemethane units briged by three 1,3- diisopropylidenbenzene arms was readily synthesized by a convergent three-step synthesis. It binds fluoride by inclusion with excellent selectivity with respect to a number of other tested anions. The structure of the free receptor and that of its fluoride complex were investigated in solution by NMR spectroscopy. The solid state X-ray structure of the free cryptand 3 was also determined

A synchrotron study of Ba5Ta2Cl2O9

The structure of pentabarium ditantalum dichloride nonaoxide, Ba5Ta2Cl2O9, is isotypic with Ba5Ru1.6W0.4Cl2O9 and with one polymorph of Ba5Ru2Cl2O9. It is related to the perovskite structure and shows a ten-layer stacking of BaO3 and BaCl blocks along the c axis. The Ta cations occupy octahedral interstices, forming Ta2O9 dimers of distorted face-shared TaO6 octahedra. Except for one O atom, all atoms are situated on special positions: Ba1 (Wyckoff position (6) over bar m2), Ba2 and Ba3 (3m.), Ta (3m.), Cl (3m.) and O1 (mm2)

Coral distribution and bleaching vulnerability areas in Southwestern Atlantic under ocean warming

Global climate change is a major threat to reefs by increasing the frequency and severity of coral bleaching events over time, reducing coral cover and diversity. Ocean warming may cause shifts in coral communities by increasing temperatures above coral’s upper thermal limits in tropical regions, and by making extratropical regions (marginal reefs) more suitable and potential refugia. We used Bayesian models to project coral occurrence, cover and bleaching probabilities in Southwestern Atlantic and predicted how these probabilities will change under a high-emission scenario (RCP8.5). By overlapping these projections, we categorized areas that combine high probabilities of coral occurrence, cover and bleaching as vulnerability-hotspots. Current coral occurrence and cover probabilities were higher in the tropics (1°S–20°S) but both will decrease and shift to new suitable extratropical reefs (20°S–27°S; tropicalization) with ocean warming. Over 90% of the area present low and mild vulnerability, while the vulnerability-hotspots represent ~ 3% under current and future scenarios, but include the most biodiverse reef complex in South Atlantic (13°S–18°S; Abrolhos Bank). As bleaching probabilities increase with warming, the least vulnerable areas that could act as potential refugia are predicted to reduce by 50%. Predicting potential refugia and highly vulnerable areas can inform conservation actions to face climate change.Postprint2,92

Synthesis and antibacterial effects of cobalt–cellulose magnetic nanocomposites

© The Royal Society of Chemistry. Green synthesis is employed to prepare cobalt/cellulose nanocomposites with cubic (α-cobalt) cobalt as a main component with antibacterial and magnetic properties. An in situ reduction of aqueous solutions of cobalt ions on a model cellulose substrate surface using hydrogen gas affords spherical, cellulose-stabilised cobalt nanoclusters with magnetic properties and an average diameter of 7 nm that are distributed evenly over the surface of the cellulose fibres. These cobalt/cellulose nanocomposites exhibit good antibacterial action against opportunistic pathogens both Gram-positive (S. aureus) and Gram-negative (E. coli, A. baumannii and P. aeruginosa), with zones of inhibition up to 15 mm, thereby encouraging the deployment of these advanced materials for the treatment of wastewater or within medical dressings. This method of preparation is compared with the analogous in situ reduction of cobalt ions on a cellulose surface using sodium borohydride as reducing agent

Identification of single-site gold catalysis in acetylene hydrochlorination

There remains considerable debate over the active form of gold under operating conditions of a recently validated gold catalyst for acetylene hydrochlorination. We have performed an in situ x-ray absorption fine structure study of gold/carbon (Au/C) catalysts under acetylene hydrochlorination reaction conditions and show that highly active catalysts comprise single-site cationic Au entities whose activity correlates with the ratio of Au(I):Au(III) present. We demonstrate that these Au/C catalysts are supported analogs of single-site homogeneous Au catalysts and propose a mechanism, supported by computational modeling, based on a redox couple of Au(I)-Au(III) species. View Full Tex

Análise de endemismo de táxons neotropicais de Pentatomidae (Hemiptera: Heteroptera)

The definition of areas of endemism is central to studies of historical biogeography, and their interrelationships are fundamental questions. Consistent hypotheses for the evolution of Pentatomidae in the Neotropical region depend on the accuracy of the units employed in the analyses, which in the case of studies of historical biogeography, may be areas of endemism. In this study, the distribution patterns of 222 species, belonging to 14 Pentatomidae (Hemiptera) genera, predominantly neotropical, were studied with the Analysis of Endemicity (NDM) to identify possible areas of endemism and to correlate them to previously delimited areas. The search by areas of endemism was carried out using grid-cell units of 2.5° and 5° latitude-longitude. The analysis based on groupings of grid-cells of 2.5° of latitude-longitude allowed the identification of 51 areas of endemism, the consensus of these areas resulted in four clusters of grid-cells. The second analysis, with grid-cells units of 5° latitude-longitude, resulted in 109 areas of endemism. The flexible consensus employed resulted in 17 areas of endemism. The analyses were sensitive to the identification of areas of endemism in different scales in the Atlantic Forest. The Amazonian region was identified as a single area in the area of consensus, and its southeastern portion shares elements with the Chacoan and Paraná subregions. The distribution data of the taxa studied, with different units of analysis, did not allow the identification of individual areas of endemism for the Cerrado and Caatinga. The areas of endemism identified here should be seen as primary biogeographic hypotheses.A definição de áreas de endemismo é central aos estudos de Biogeografia Histórica e suas inter-relações são questões fundamentais. Hipóteses consistentes sobre a evolução de Pentatomidae (Hemiptera) na Região Neotropical dependem da acuidade das unidades empregadas nas análises, que no caso de estudos de biogeografia histórica, podem ser áreas endêmicas. Neste trabalho foram estudados os padrões de distribuição de 222 espécies, pertencentes a 14 gêneros de Pentatomidae, com ocorrência predominantemente neotropical, com base em uma Análise de Endemicidade (NDM) a fim de inferir possíveis áreas endêmicas e relacioná-las a áreas previamente delimitadas. A busca por áreas endêmicas foi realizada com quadrículas de 2,5° e 5° latitude-longitude. A análise com base em agrupamentos de 2,5° latitude-longitude permitiu identificar 51 áreas de endemismo, sendo que o consenso destas áreas resultou em quatro agrupamentos de quadrículas. A segunda análise, com quadrículas de 5° latitude-longitude, resultou em 109 áreas de endemismo. O consenso flexível empregado resultou em 17 áreas de endemismo. As análises foram sensíveis à identificação de áreas de endemismo na Mata Atlântica em diferentes escalas. A região Amazônica foi identificada como uma área única no consenso, sendo que a porção sudeste compartilha elementos com as sub-regiões do Chaco e Paraná. Os dados de distribuição dos táxons estudados, com diferentes unidades de análises, não permitiram a identificação de áreas endêmicas para o Cerrado e a Caatinga. As áreas de endemismo aqui identificadas devem ser tratadas como hipóteses biogeográficas primárias.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Universidade Federal do Rio Grande do Sul Laboratório de Entomologia Sistemática Departamento de ZoologiaUniversidade Federal do Paraná Departamento de Zoologia Programa de Pós-Graduação em EntomologiaUniversidade Federal de São Paulo (UNIFESP) Departamento de Ciências BiológicasUNIFESP, Depto. de Ciências BiológicasSciEL

Direct amine-functionalisation of γ-Fe2O3nanoparticles

A novel and simple preparation of amine-modified γ-Fe2O3 nanoparticles is described. The presence of amine groups on the surface, instead of hydroxyl groups, will allow conjugation of biologically active molecules to the iron oxide nanoparticles without the need for a size increasing silica shell. Furthermore, the outer amine-layer increases the temperature of the γ-Fe2O3 to α-Fe2O3 structural transition in a similar way to previously reported cationic substitutions. This may suggest the formation of an oxide–nitride outer layer. Re-dispersion of the amine-modified γ-Fe2O3 nanoparticles led to the preparation of stable ferrofluids

All-optical switching at the two-photon limit with interference-localized states

We propose a single-photon-by-single-photon all-optical switch concept based on interference-localized states on lattices and their delocalization by interaction. In its 'open' operation, the switch stops single photons while allows photon pairs to pass the switch. Alternatively, in the 'closed' operation, the switch geometrically separates single-photon and two-photon states. We demonstrate the concept using a three-site Stub unit cell and the diamond chain. The systems are modeled by Bose-Hubbard Hamiltonians, and the dynamics is solved by exact diagonalization with Lindblad master equation. We discuss realization of the switch using photonic lattices with nonlinearities, superconductive qubit arrays, and ultracold atoms. We show that the switch allows arbitrary 'ON'/'OFF' contrast while achieving picosecond switching time at the single-photon switching energy with contemporary photonic materials