Helicate tris(aryl)carbinolates bearing pendant NR2 donors – a new family of supporting ligands for the synthesis of Sc3+ alkyl complexes

The reactions of aryllithium reagents o-LiC₆H₄CH₂NR₂ with (MeO)₂CO afford two new tris(aryl)carbinols bearing pendant-NR₂ donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C₆H₄CH₂NMe₂)₃CO]Sc(CH₂SiMe₃)₂ featuring rigid binding of the alkoxy anion through a κ¹-O, κ²-N chelating coordination mode     

Ratiometric Detection of microRNA Using Hybridization Chain Reaction and Fluorogenic Silver Nanoclusters

miRNA (miR)-155 is a potential biomarker for breast cancers. We aimed at developing a nanosensor for miR-155 detection by integrating hybridization chain reaction (HCR) and silver nanoclusters (AgNCs). HCR serves as an enzyme-free and isothermal amplification method, whereas AgNCs provide a built-in fluorogenic detection probe that could simplify the downstream analysis. The two components were integrated by adding a nucleation sequence of AgNCs to the hairpin of HCR. The working principle was based on the influence of microenvironment towards the hosted AgNCs, whereby unfolding of hairpin upon HCR has manipulated the distance between the hosted AgNCs and cytosine-rich toehold region of hairpin. As such, the dominant emission of AgNCs changed from red to yellow in the absence and presence of miR-155, enabling a ratiometric measurement of miR with high sensitivity. The limit of detection (LOD) of our HCR-AgNCs nanosensor is 1.13 fM in buffered solution. We have also tested the assay in diluted serum samples, with comparable LOD of 1.58 fM obtained. This shows the great promise of our HCR-AgNCs nanosensor for clinical application.     

Synthesis of partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions

Partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions (ps‐PES‐FPES), with ionic exchange capacity (IEC) ranging between 0.9 and 1.5 meq H⁺/g, are synthesized by regioselective bromination of partially fluorinated poly(arylene ether sulfone) multiblock copolymers (PES‐FPES), followed by Ullman coupling reaction with lithium 1,1,2,2‐tetrafluoro‐2‐(1,1,2,2‐tetrafluoro‐2‐iodoethoxy)ethanesulfonate. The PES‐FPES are prepared by aromatic nucleophilic substitution reaction by an original approach, that is, “one pot two reactions synthesis.” The chemical structures of polymers are analyzed by ¹H and ¹⁹F NMR spectroscopy. The resulted ionomers present two distinct glass transitions and α relaxations revealing phase separation between the hydrophilic and the hydrophobic domains. The phase separation is observed at much lower block lengths of ps‐PES‐FPES as compared with the literature. AFM and SANS observations supported the phase separation, the hydrophilic domains are well dispersed but the connectivity to each other depends on the ps‐PES block lengths. The thermomechanical behavior, the water up‐take, and the conductivity of the ps‐PES‐FPES membranes are compared with those of Nafion 117^® and randomly functionalized polysulfone (ps‐PES). Conductivities close or higher to those of Nafion 117^® are obtained. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1941–1956     

基于串联两阶段网络DEA模型的供应链规模收益分析

数据包络分析(DEA)是评价供应链系统(Supply chain system)间相对有效性的一种重要的工具,但是传统的DEA不考虑供应链的内部结构,对系统效率评价偏高;而本文所研究两阶段串联供应链系统,考虑把部分中间产品作为最终产品输出,增加额外中间投入的情形.基于所提出的供应链系统结构,本文建立相应的串联结构下的网络DEA模型,并针对所建立模型进行相关理论的研究,给出了串联结构下的生产可能集和规模收益情况判定方法.最后,进行数值实验,以验证我们提出的结论.     

Semilinear wave models with friction and viscoelastic damping

In this paper, we study the global (in time) existence of small data solutions to the Cauchy problem for the semilinear wave equation with friction, viscoelastic damping, and a power nonlinearity. We are interested in the connection between regularity assumptions for the data and the admissible range of exponents p in the power nonlinearity.     

DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex

DFT computations have been performed to investigate the mechanism of H₂‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H₂ can react with the deactivated [Zr]?pMS?PP_n facilely, which displace functionalized pMS?PP_n chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585     

Extended Open-Chain Polyenides as Versatile Delocalized Anion Ligands for Metal Chain Clusters

Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd₄]⁴⁺ chain.     

杂多酸催化合成乙酸乙酯

回流吸附法制备的负载型12-钨磷酸(HPW/C)是合成乙酸乙酯的高效催化剂。最佳反应条件下乙醇转化率达96％,酯化选择性100％。催化剂的高活性是由于HPW在活性炭上高度分散,使活性位增多,有效酸量增大。HPW/C还具有热稳定性高和不易流失等优点。     

A profit-maximizing supply chain network design model with demand choice flexibility

We present a profit-maximizing supply chain design model in which a company has flexibility in determining which customers to serve. The company may lose a customer to competition if the price it charges is too high. We show the problem formulation and solution algorithm, and discuss computational results.     

一类小缺陷码的链条件

利用射影几何方法在小缺陷码中,NMDS码是链条件码;给出k维NμMDS(0μk-2)码满足链条件的一个充要条件与一些易判断的充分条件.