Cobalt Based Nanoparticles Embedded Reduced Graphene Oxide Aerogel for Hydrogen Evolution Electrocatalyst

Efficient water electrolysis catalyst is highly demanded for the production of hydrogen as a sustainable energy fuel. It is reported that cobalt derived nanoparticle (CoS₂, CoP, CoS|P) decorated reduced graphene oxide (rGO) composite aerogel catalysts for highly active and reliable hydrogen evolution reaction electrocatalysts. 7 nm level cobalt derived nanoparticles are synthesized over graphene aerogel surfaces with excellent surface coverage and maximal expose of active sites. CoS|P/rGO hybrid aerogel composites show an excellent catalytic activity with overpotential of ≈169 mV at a current density of ≈10 mA cm^?2. Accordingly, efficient charge transfer is attained with Tafel slope of ≈52 mV dec^?1 and a charge transfer resistance (R_ct) of ≈12 Ω. This work suggests a viable route toward ultrasmall, uniform nanoparticles decorated graphene surfaces with well‐controlled chemical compositions, which can be generally useful for various applications commonly requiring large exposure of active surface area as well as robust interparticle charger transfer.     

Bis-tridentate IrIII Phosphors Bearing Two Fused Five-Six-Membered Metallacycles: A Strategy to Improved Photostability of Blue Emitters

Iridium complexes bearing chelating cyclometalates are popular choices as dopant emitters in the fabrication of organic light-emitting diodes (OLEDs). In this contribution, we report a series of blue-emitting, bis-tridentate Ir^III complexes bearing chelates with two fused five-six-membered metallacycles, which are in sharp contrast to the traditional designs of tridentate chelates that form the alternative, fused five-five metallacycles. Five Ir^III complexes, Px-21 – 23 , Cz-4 , and Cz-5 , have been synthesized that contain a coordinated dicarbene pincer chelate incorporating a methylene spacer and a dianionic chromophoric chelate possessing either a phenoxy or carbazolyl appendage to tune the coordination arrangement. All these tridentate chelates afford peripheral ligand–metal–ligand bite angles of 166–170°, which are larger than the typical bite angle of 153–155° observed for their five-five-coordinated tridentate counterparts, thereby leading to reduced geometrical distortion in the octahedral frameworks. Photophysical measurements and TD-DFT studies verified the inherent transition characteristics that give rise to high emission efficiency, and photodegradation experiments confirmed the improved stability in comparison with the benchmark fac-[Ir(ppy)₃] in degassed toluene at room temperature. Phosphorescent OLED devices were also fabricated, among which the carbazolyl-functionalized emitter Cz-5 exhibited the best performance among all the studied bis-tridentate phosphors, showing a maximum external quantum efficiency (EQE_max) of 18.7 % and CIE_x,y coordinates of (0.145, 0.218), with a slightly reduced EQE of 13.7 % at 100 cd m⁻² due to efficiency roll-off.     

Rational Development of Remote C−H Functionalization of Biphenyl: Experimental and Computational Studies

A simple and efficient nitrile-directed meta-C−H olefination, acetoxylation, and iodination of biaryl compounds is reported. Compared to the previous approach of installing a complex U-shaped template to achieve a molecular U-turn and assemble the large-sized cyclophane transition state for the remote C−H activation, a synthetically useful phenyl nitrile functional group could also direct remote meta-C−H activation. This reaction provides a useful method for the modification of biaryl compounds because the nitrile group can be readily converted to amines, acids, amides, or other heterocycles. Notably, the remote meta-selectivity of biphenylnitriles could not be expected from previous results with a macrocyclophane nitrile template. DFT computational studies show that a ligand-containing Pd–Ag heterodimeric transition state (TS) favors the desired remote meta-selectivity. Control experiments demonstrate the directing effect of the nitrile group and exclude the possibility of non-directed meta-C−H activation. Substituted 2-pyridone ligands were found to be key in assisting the cleavage of the meta-C−H bond in the concerted metalation–deprotonation (CMD) process.     

Dimeric Manganese-Catalyzed Hydroarylation and Hydroalkenylation of Unsaturated Amides

An unprecedented Mn(I)-catalyzed selective hydroarylation and hydroalkenylation of unsaturated amides with commercially available organic boronic acids is reported. Alkenyl boronic acids have been successfully employed for the first time in Mn(I)-catalyzed carbon–carbon bond formation. A wide array of β-alkenylated amide products can be obtained in moderate to good yields, which offers practical access to five- and six-membered lactams. This protocol has predictable regio- and chemoselectivity, excellent functional group compatibility and ease of operation in air, representing a significant step-forward towards manganese-catalyzed C−C coupling.     

Studies on metabolism of total glucosides of paeony from Paeoniae Radix Alba in rats by UPLC‐Q‐TOF‐MS/MS

Total glucosides of paeony are the active constituents of Paeoniae Radix Alba. In this study, a novel strategy was proposed to find more metabolites and the differences between paeoniflorin, albiflorin and total glucosides of paeony (TGP). This strategy was characterized as follows: firstly, the animals were divided into three groups (paeoniflorin, albiflorin and TGP) to identify the source of TGP metabolites from paeoniflorin or albiflorin; secondly, a generic information‐dependent acquisition scan for the low‐level metabolites was triggered by the multiple mass defect filter and dynamic background subtraction; thirdly, the metabolites were identified with a combination of data‐processing methods including mass defect filtering, neutral loss filtering and product ion filtering; finally, a comparative study was used in the metabolism of paeoniflorin, albiflorin and TGP. Based on the strategy, 18 metabolites of TGP, 10 metabolites of paeoniflorin and 13 metabolites of albiflorin were identified respectively. The results indicated that the hydrolysis, conjugation reaction and oxidization were the major metabolic pathways, and the metabolic sites were the glycosidic linkage, the ester bond and the benzene ring. This study is first to explore the metabolism of TGP, and these findings enhance our understanding of the metabolism and the interactions of paeoniflrin and albiflorin in TGP. Copyright © 2015 John Wiley & Sons, Ltd.     

A posteriori error estimation with finite element methods of lines for one-dimensional parabolic systems

Summary Consider the solution of one-dimensional linear initial-boundary value problems by a finite element method of lines using a piecewiseP ^th -degree polynomial basis. A posteriori estimates of the discretization error are obtained as the solutions of either local parabolic or local elliptic finite element problems using piecewise polynomial corrections of degreep+1 that vanish at element ends. Error estimates computed in this manner are shown to converge in energy under mesh refinement to the exact finite element discretization error. Computational results indicate that the error estimates are robust over a wide range of mesh spacings and polynomial degrees and are, furthermore, applicable in situations that are not supported by the analysis.This research was partially supported by the U.S. Air Force Office of Scientific Research, Air Force Systems Command, USAF, under Grant Number AFOSR 90-0194; by the U.S. Army Research Office under Contract Number DAAL03-91-G-0215; and by the National Science Foundation under Institutional Infrastructure Grant Number CDA-8805910     

聚硅烷研究进展 (1)聚硅烷的合成及应用

聚硅烷的合成及应用因可溶性聚硅烷的发现而成为聚合物研究的又一热点。本文综述了聚硅烷合成与应用的近期发展。     

Au/SiO2纳米复合薄膜的微结构及光吸收特性研究

用多靶磁控溅射技术制备了Au/SiO2纳米多层薄膜.利用透射电子显微镜以及吸收光谱对Au/SiO2复合薄膜的微观结构、表面形貌及光学性能进行了表征和测试.研究结果表明:单层Au/SiO2薄膜中Au沉积时间小于10s时,分散在SiO2中的Au颗粒随Au的沉积时间的延长而增大;当沉积时间超过10s后,Au颗粒的尺寸几乎不随沉积时间变化,但Au颗粒的形状由网络状结构变为薄膜状结构.[Au(t1)SiO2(600)]×5多层薄膜在540-560nm波长附近有明显的表面等离子共振吸收峰,且吸收峰的强度随Au的沉积时间增加而增强.基于修正后的Maxwell-Garnett (M-G)有效媒质理论,讨论了金属颗粒的形状对等离子共振吸收峰的峰位和强度的影响.模拟的吸收光谱与实验吸收光谱形状、趋势及吸收峰位相符合.     

置换模,ρ置换模与Conlon比析

本文对特征P的基域F引入适当的Galois群T,讨论p置换模的Green环的Conlon比析在Galois群T作用下的动态,证明了在T作用下p置换模的Green环的不动点集重合于置换模的Green环。     

Au/SiO2纳米多层薄膜的制备及其性质表征

利用多靶磁控溅射技术制备了Au/SiO2纳米颗粒分散氧化物多层复合薄膜.研究了在保持Au单层颗粒膜沉积时间一定时薄膜厚度一定、变化SiO2的沉积时间及SiO2的沉积时间一定而改变薄膜厚度时,多层薄膜在薄膜厚度方向的微观结构对吸收光谱的影响.研究结果表明:具有纳米层状结构的Au/SiO2多层薄膜在560nm波长附近有明显的表面等离子共振吸收峰,吸收峰的强度随Au颗粒的浓度增加而增强,在Au颗粒浓度相同的情况下,复合薄膜光学吸收强度随薄膜厚度的增加而增强.但当金属颗粒的浓度增加到一定程度时,金属颗粒相互接触,没有观察到纳米层状结构,薄膜不显示共振吸收峰特征.用修正后的M-G(Maxwell-Garnett)理论对吸收光谱进行了模拟,得到了与实验一致的结果.