过碳酸钠-醋酸酐作用下的Baeyer-Villiger反应

在醋酸酐介质中, 过碳酸钠可以与酮进行Baeyer-Villiger反应, 将它们氧化成相应的酯。其中脂环酮的反应结果较好, 环内酯的产率约为80%。芳香酮除芳环被活化的以外, 效果欠佳。当反应施加超声辐射后可显著加快反应速度, 并对过碳酸钠的作用机理进行了讨论。     

A new anode material LiMoS2 for use in rechargeable Lithium Ion Batteries

The novel applications of molybdenum disulfide in recent research were reviewed, such as in lubricant, catalyst and photoelectrochemical solar cells. Recently, we found that LiMoS2 is a good candidate for new anode materials for lithium ion batteries with high lithium storage capacity.Here, the anode material LiMoS2 was synthesized by a hydrothermal method at 150℃ and the electrochemical characterization as an anode material for lithium ion batteries was examined.put in Teflon-lined stainless steel autoclaves of capacity 40 mL. Distilled water was used to fill the autoclaves to 70 % of the total volume. The autoclaves were maintained at 150℃ for 24 h and then cooled naturally. The resulting dark-gray powders were filled and washed with distilled water,diluted hydrochloric acid and ethanol, successively. The final products were dried at 80℃ for 24 h.The powder X-ray diffraction pattern showed the prepared LiMoS2 was amorphous structure. A test cell using LiMoS2 as the active material was discharged and charged between 3 and 0.01 V with respect to Li metal at a constant current density of C/5 (that is, one lithium per formula unit in 5 hours). During the first discharge, the potential rapidly drops to reach a large plateau at 2.2 V, then slowly drops to the other plateau at 0.8 V, and then continuously decreases down to 0.01V. There is only a plateau at 1.35 V in the subsequent discharge curves. The plateaus of charge potential appear at about 1.9 V.The irreversible loss was 41% in the first cycle. The ratio of discharge and charge is more than 99%in the subsequent cycles. Moreover, the ratio of discharge and charge almost reaches 100% after thedemonstrated that LiMoS2 has a very high capacity and a good cycle-ability as an anode material forlithium ion batteries.     

环戊二烯基氟尿嘧啶基钛（Ⅳ）、锆（Ⅳ）配合物的合成及其抗肿瘤活性的研究

用（ＲＣｐ）２ＭＣｌ２和（ＲＣｐ）ＴｉＣｌ３（Ｒ＝Ｈ，Ｍｅ；Ｍ＝Ｔｉ，Ｚｒ）分别与具有生物活性的２－甲氧基－５－氟尿嘧啶、２－甲硫基－５－氟尿嘧啶在甲苯溶剂中１１０℃下反应，合成了２０个未见报道的（ＲＣｐ）·Ｍ（Ｏｐｍ）２Ｃｌ、（ＲＣｐ）２Ｍ（ＯＰｍ）Ｃｌ和（ＲＣｐ）Ｍ（ＯＰｍ）Ｃｌ２（ＯＰｍ＝２－甲氧基－５－氟尿嘧啶基，２－甲硫基－５－氟尿嘧啶基）型钛锆配合物，这些配合物均经元素分析、１ＨＮＭＲ、ＩＲ光谱鉴定．初步动物试验表明，配合物１、４、１１、１４对小白鼠移植性艾氏腹水场的抑制作用居首，而配合物２、３、５、６、１２、１３、１５、１６次之，其它锆配合物几乎没有抑制作用。     

微波辅助-光催化降解氯酚的QSPR研究

本文运用PM3算法计算得到氯酚(CPs)的分子结构参数,并结合光解速率进行PLS分析,建立了速率与量子化参数之间的关系模型,模型的Q2cum分别为0.8776和0.9545(>0.5),具有良好的预测能力。研究结果表明,参数Ehomo、Elumo Ehomo、Elumo、N、Mw、Elumo-Ehomo、(Elumo-Ehomo)2是决定CPs光解速率的主要因素;CPs的光解速率随Ehomo、Elumo Ehomo、Elumo、Elumo-Ehomo、(Elumo-Ehomo)2的增大而增大,随N、Mw的增大而减小。     

利用“网包法”制备高效液相色谱大环抗生素类手性固定相

万古霉素和替考拉宁都属于糖肽类的大环抗生素，具有立体的环状结构和多个手性中心，是两种常见的手性识别材料，广泛应用于对映体的色谱手性分离分析。该文以万古霉素和替考拉宁为手性选择剂，哌嗪为单体，4，4'-二苯基甲烷二异氰酸酯（MDI）、1，6-己二异氰酸酯（HDI）和2，4-甲苯二异氰酸酯（TDI）为交联剂，通过界面聚合反应形成网状层包裹硅胶载体的方法制得6种高效液相色谱手性固定相，用于分离外消旋化合物，并与MDI直接交联万古霉素和替考拉宁在硅胶表面所得固定相进行了比较。结果表明，利用"网包法"和直接交联法制备的手性柱与商品万古霉素和替考拉宁柱之间具有互补性，均对不同的外消旋体有不同程度的拆分。     

Heterocyclization of functionalized heterocumulenes with C,N-, C,O-, and C,S-binucleophiles: VIII. Synthesis of pyrano(chromeno)[3,4-e][1,3]oxazines by condensation of 1-chloroalkyl isocyanates with 4-hydroxy-6-methylpyran-2-one and 4-hydroxycoumarin

1-Chlorobenzyl isocyanates react with 4-hydroxy-6-methylpyran-2-one and 4-hydroxycoumarin forming 4-aryl-3,4-dihydro-2H,5H-pyrano(chromeno)[3,4-e][1,3]oxazine-2,5-diones. The reaction of 1-aryl-2,2,2-trifluoro-1-chloroethyl isocyanates with the above substrates gives rise to structurally isomeric 2-aryl-2-trifluoromethyl-2,3-dihydro-2H,5H-pyrano(chromeno)[3,4-e][1,3]-oxazine-4,5-diones.     

Polyfunctional pyrazoles. 4. Synthesis of 3-[3-aryl-1-(2-ethoxycarbonyl)-4-pyrazolyl]acrylic and-propionic acids

3-(3-Aryl-4-formyl-1-pyrazolyl)propionic acids are converted by Knoevenagel condensation under conditions of microwave activation into 3-[3-aryl-1-(2-ethoxycarbonyl)-4-pyrazolyl]acrylic acids. Reduction of the latter with hydrazine hydrate in the presence of Raney nickel gives 3-[3-aryl-1-(2-ethoxycarbonyl)-4-pyrazolyl]propionic acids. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 686–690, May, 2006.     

酵母核糖核酸在碳纳米管修饰电极上的电化学行为及其分析测定

研究了酵母核糖核酸（yRNA）在碳纳米管（MWNT）修饰电极上的电化学行为，优化了测定参数，在此基础上建立了一种直接测定yRNA的电分析测试方法。yRNA在碳纳米管修饰电极上于磷酸盐缓冲溶液中在0．758V处产生不可逆的氧化电流峰，峰电流与yRNA的质量浓度在1～10mg／mL之间有良好的线性关系，线性回归方程为：Iρ=0．0813ρ＋0．1807，相关系数r为0．9980，检出限为0．6mg／mL。     

Functionally Substituted 3-Heterylpyrazoles: XI. 3-[3-Aryl(heteryl)pyrazol-4-yl]propenoic and Propanoic acids

3-Aryl(heteryl)-4-formylpyrazoles by condensation with malonic acid furnish 3-[3-aryl(heteryl)- pyrazol-4-yl]propenoic acids that in the presence of Raney nickel are reduced by hydrazine hydrate to 3-[3-aryl(heteryl)pyrazol-4-yl]propanoic acids. The successive conversion of both type acids into the corresponding acyl chlorides, esters, and amides was performed.     

两种气相色谱固定相的研究

使用硫杂冠醚、穴醚[2.2.2]作气相色谱固定相制备毛细管柱,考察两种固定相的使用比例、极性、热稳定性,并对甲苯-苯、乙苯-甲苯、甲基苯酚（o/p）、二氯苯（o/p,m）、硝基氯化苯（m,o）、苯-环己烷、庚醇-辛醇、苯胺-N,N二甲基苯胺等混合样品进行色谱分离.实验结果表明：两种固定相在OV-1701中的比例均为15%时有较好的分离效果,都属于中等极性的固定相.硫杂冠醚、穴醚[2.2.2]的平均极性分别为815、832,其中硫杂冠醚固定相的热稳定性较好,有较高的使用温度（185℃）,而穴醚[2.2.2]的最高使用温度为120℃,因此穴醚[2.2.2]的使用温度受到一定的限制.从它们较好的分离性能看,固定相硫杂冠醚、穴醚[2.2.2]均具有较好的应用前景.