Progressive studies on the novel samarium-catalyzed diastereoselective tandem semipinacol rearrangement/Tishchenko reduction of secondary alpha-hydroxy epoxides

A novel and highly diastereoselective samarium-catalyzed tandem rearrangement/reduction of secondary alpha-hydroxy epoxides, which involves a C1 to C3 carbon migration rearrangement and a very interesting hetero-Tishchenko reduction of the intermediate aldehyde and the reductant aldehyde, has been reported. This reaction could be developed to provide a facile and stereoselective construction of 2-quarternary 1,3-diol units with an hydroxymethyl moiety attached to the diastereogenic quaternary carbon center. Detailed investigations have been carried out concerning the screening of the aldehydes as a reductant, the optimization of reaction conditions, and the substrate scope of this tandem reaction. A catalytic cycle for this reaction, the electronic and steric effects of the reductant aldehydes, and the mechanism for the acyl migration of 1,3-diol monoesters are proposed.     

A new two‐dimensional CdII coordination polymer constructed by pyrazine‐2,3‐dicarboxyl­ate

In the title compound, poly[μ₅‐pyrazine‐2,3‐dicarboxyl­ato‐cadmium(II)], [Cd(C₆H₂N₂O₄)]_n or [Cd(pdc)]_n, where pdc is the pyrazine‐2,3‐dicarboxyl­ate anion, the Cd^II atom is six‐coordinated by five carboxyl­ate O atoms and one N atom from five different pdc ligands in a distorted octa­hedral CdO₅N coordination geometry. Two Cd^II atoms are bridged by carboxyl­ate groups of the pdc ligands to create a dimeric unit. The dimeric units are further connected by the pdc ligands to generate an inter­esting two‐dimensional structure.     

大庆渣油族组分非等温热反应的研究

采用动态热重分析法在升温速率为６．２Ｋ·ｍｉｎ￣（－１）及惰性气流量１００ｃｍ￣３·ｍｉｎ￣（－１）的条件下，对大庆渣油族组分的热转化行为进行了考察，获得了族组分的热转化速率峰值、速率峰值处的反应温度、转化率和剧裂分解温度区间等动力学基本数据以及各族组分的生焦性能。数据分析表明，族组分的热反应活性顺序为：饱和分＞胶质＞芳香分＞沥青质。在大庆渣油族组分热转化的两个温区内，采用分段一级动力学模型较好地拟合了实验数据，确定了各族组分在两个温区内的热反应动力学参数。     

Effects of injector geometry and sample matrix on injection and sample loading in integrated capillary electrophoresis devices

The double-T injector design employed in many microchip capillary electrophoresis devices allows for the formation of very small (50-500 pL) sample plugs for subsequent analysis on-chip. In this study, we show that sample plugs formed at the channel junction can be geometrically defined. The channel width and injector symmetry prove to be of great importance to good performance. A unique pushback of solvent into the side channels can be induced when the side channels have a very low resistance to flow, and this helps to better define the injected sample plug. Samples and running buffers of differing ionic strength (e.g., 10 mM KCl buffer and 20 mM KCl sample) can yield widely variable results in terms of plug shape and amount injected (variations of 1.5 to 10x). Applying bias voltages to all the intersecting channels aids in controlling the plug shape. However, when the ionic strengths of buffer and sample are not matched, the actual amount injected (up to 10x variations) can be inconsistent with the appearance of the plug formed in the injector (up to only 30 % variations). Operating at constant pH and ionic strength produced the most consistent results. This report examines the effects of altering the injector geometry and solution ionic strengths, and presents the results of using bias voltages to control plug formation. The observed results should provide a benchmark for modeling of the fluid dynamics in channel intersections.     

随机环境中带移民分枝过程的Cramér大偏差展式北大核心CSCD

本文考虑独立同分布的随机环境中带移民的分枝过程(Z_(n)).基于(Z_(n))的结构,利用测度变换技巧,并借助随机游动的相关结果,我们得到关于logZ_(n)的Cramer型大偏差展式.     

The structure characteristics of photoproducts of indolinospirooxazines

Photochromic reactions of four indolinospirooxazine derivatives have been studied using nanosecond laser flash photolysis techniques. Photolysis of the four compounds in acetonitrile and in cyclohexane all leads to the formation of the short-lived CT intermediates as the predominant photoproducts. In certain circumstances few photomerocyanines (PMC) can be observed. From the absorption bands and the lifetimes of CT intermediates, it has been speculated that the substituents at the nitrogen atom of the indole ring influence the structural characteristics of CT intermediates mainly through steric hindrance effects, whereas the substituents at the 5 position of the indoline ring influence mainly through electron effects. A potential energy surface model is established to explain the results.     

Upper bounds of Schubert polynomials

Science China Mathematics - Let w be a permutation of {1, 2, …, n}, and let D(w) be the Rothe diagram of w. The Schubert polynomial ${\mathfrak{S}_w}\left(x \right)$ can be realized as the...