Activity

A silica-supported monomeric alkylaluminum co-catalyst was prepared via Surface Organometallic Chemistry by contacting tris-(neopentyl)aluminum and partially dehydroxylated silica . A-366 inhibitor This system, fully characterized by solid-state 27 Al NMR augmented by computational studies, efficiently activates ( n Bu 3 P) 2 NiCl 2 towards dimerization of ethene demonstrating comparable activity to previously reported dimeric diethylaluminum chloride supported on silica. Three types of aluminum surface species have been identified monografted tetracoordinated Al species as well as two types of bis-grafted Al species – tetra- and pentacoordinated. Of them, only the monografted Al species is proposed to be able to activate the ( n Bu 3 P) 2 NiCl 2 complex and generate the active cationic species.Changes to the molecular properties of lignin over the course of biorefinery processing were investigated by using sweetgum as a feedstock. Hydrothermal pretreatment has been used because it is an economically attractive, green process. Three representative biorefinery lignin preparations were obtained, with about 70 % yield based on raw lignin. The three fractions included soluble lignin adsorbed on resin (XADL), solvent-extracted lignin (HTCELp), and an additional ball-milled residual lignin (HTRELp). By comparing the raw and biorefinery lignin preparations, it can be concluded that lignin undergoes both degradation and condensation throughout the various stages of the hydrothermal-based biorefinery process. The two fractions made soluble by biorefinery processing, XADL and HTCELp, were found to be low-molecular-weight degradation products enriched with free phenolic hydroxyl groups. In addition, about 15 % of noncondensed phenolic units were involved in condensation reactions. Quantitative NMR spectroscopy analysis revealed that at least about 28 % of β-O-4′ substructures were cleaved. Hibbert’s ketones were identified in XADL and HTRELp, which provided evidence of lignin undergoing acidolysis. The contents of β-5′ and β-β’ did not change significantly upon biorefinery processing. Finally, episyringaresinol was detected in XADL and HTCELp. It is hoped that these findings will help to further demonstrate the specific effects of biorefinery processing on lignin in hardwood and facilitate its utilization to improve biorefinery economics.The increasing pharmaceutical importance of trifluoromethylarenes has stimulated the development of more efficient trifluoromethylation reaction. Tremendous efforts have focused on copper- and palladium-mediated/catalyzed trifluoromethylation of aryl halides. In contrast, no general method exists for the conversion of widely available inert electrophiles, such as phenol derivatives, into the corresponding trifluoromethylated arenes. We report herein a practical nickel-mediated trifluoromethylation of phenol derivatives with readily available trimethyl(trifluoromethyl)silane (TMSCF3 ). The strategy relies on PMe3 -promoted oxidative addition and transmetalation, and CCl 3 CN-induced reductive elimination. The broad utility of this transformation has been demonstrated through the direct incorporation of trifluoromethyl to aromatic and heteroaromatic systems including bio-relevant compounds.In situ exsolution of metal nanoparticles in perovskite under reducing atmosphere is employed to generate a highly active metal-oxide interface for CO2 electrolysis in a solid oxide electrolysis cell. Atomic-scale insight is provided into the exsolution of CoFe alloy nanoparticles in La0.4 Sr0.6 Co0.2 Fe0.7 Mo0.1 O3-δ (LSCFM) by in situ scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy and DFT calculations. The doped Mo atoms occupy B sites of LSCFM, which increases the segregation energy of Co and Fe ions at B sites and improves the structural stability of LSCFM under a reducing atmosphere. In situ STEM measurements visualized sequential exsolution of Co and Fe ions, formation of CoFe alloy nanoparticles, and reversible exsolution and dissolution of CoFe alloy nanoparticles in LSCFM. The metal-oxide interface improves CO2 adsorption and activation, showing a higher CO2 electrolysis performance than the LSCFM counterparts.Aim The aim of this study was to determine the number of thromboembolism patients among Japanese users of female hormones. Methods A survey of confirmed thromboembolism patients among Japanese users of female hormones was conducted at randomly selected hospitals from across Japan. The survey examined six types of venous thromboembolism (VTE) and arterial thromboembolism (ATE) in all users of female hormones, including women and men pulmonary embolism (PE), deep vein thrombosis (DVT), other venous thrombosis (other VTE), cerebral infarction (stroke), myocardial infarction (MI) and other arterial thrombosis (other ATE). The survey covered 5 years from 2009 to 2013. This study was approved in an ethical review by the Hamamatsu University School of Medicine. Results The overall number of thromboembolism patients over the 5 years was estimated to be about 3211. They included 452 patients with PE, 795 with DVT, 157 with other VTE, 1228 with stroke, 478 with MI and 101 with other ATE. Among the abovementioned conditions, detailed information was available for 750 thromboembolism patients (645 women and 105 men), including 63 PE, 203 DVT, 159 PE + DVT, 65 other VTE, 189 stroke, 35 MI, 21 other ATE and 15 other cases. Thromboembolism increased year by year. The number of VTE was larger than that of ATE in younger people who used female hormones, while the number of ATE was larger than that of VTE in older people who used female hormones. Conclusion The number and characteristics of thromboembolism patients among Japanese female hormone users were revealed in this national survey.In the present study, a Fe3 O4 -TiO2 (FT) core-shell and a core-multishell structure of Fe3 O4 -SiO2 -TiO2 (FST) were synthesized, and their bactericidal capability was investigated on Escherichia coli (E.coli). SEM, UV-vis, XRD, BET, zeta potential and fluorimetry were carried out to characterize properties of synthesized nanoparticles (NPs). An efficiency of 98% adsorption and harsh bacterial damage was observed when E.coli was put in contact with FST. Weaker adsorption of bacteria in contact with FT demonstrated that heterojunction has destructive effects on nanostructure. Further investigation proved that more ·OH were produced on the surface of FST, which is a sign of its longer lifetime. Moreover, results revealed that the presence of SiO2 in the structure caused enhanced coverage, surface area and porosity in TiO2 outer layer, all of which have positive effects on adsorption. However, UV-vis showed smaller band gap for FT. It suggests that although photoactivity of FST is less influenced by light absorption, it possesses more e/h lifetime for generation of ROS.