Spacial Structure of Cationic Phosphorus Ligand–Ru (II) Halide Complexes—by DFT Study

The increasing demand to produce enantio-pure pharmaceuticals, flavors, and other fine chemicals has advanced the field of asymmetry catalytic technologies. Among all asymmetry catalytic methods, catalytic enantioselective hydrogenation of unsaturated bonds such as olefins, ketones, and imines, which employs dihydrogen and small amounts of transition-metal complexes modified intrinsically by chiral ligands, is now recognized as being the most promising strategy for the synthesis of large amount…     

Solid-state synthesis of a conducting polythiophene via an unprecedented heterocyclic coupling reaction

Prolonged storage ( approximately 2 years) or gentle heating (50-80 degrees C) of crystalline 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) affords a highly conducting, bromine-doped poly(3,4-ethylenedioxythiophene) (PEDOT), as confirmed by solid-state NMR, FTIR, CV, and vis-NIR spectroscopies. The novel solid-state polymerization (SSP) does not occur for 2,5-dichloro-3,4-ethylenedioxythiophene (DCEDOT), and requires a much higher temperature (>130 degrees C) for 2,5-diiodo-3,4-ethylenedioxythiophene (DIEDOT). X-ray structural analysis of the above dihalothiophenes reveals short Hal.Hal distances between adjacent molecules in DBEDOT and DIEDOT, but not in DCEDOT. The polymerization may also occur in the melt but is significantly slower and leads to poorly conductive material. Detailed studies of the reaction were performed using ESR, DSC, microscopy, and gravimetric analyses. SSP starts on crystal defect sites; it is exothermic by 14 kcal/mol and requires activation energy of approximately 26 kcal/mol (for DBEDOT). The temperature dependence of the conductivity of SSP-PEDOT (sigma(rt) = 20-80 S/cm) reveals a slight thermal activation. It can be further increased by a factor of 2 by doping with iodine. Using this approach, thin films of PEDOT with conductivity as high as 20 S/cm were fabricated on insulating flexible plastic surfaces.     

Synthesis, Crystal Structure and Properties of [Co(1,3- bdoaH)_2·4H_2O]·4H_2O with Benzene-1,3-dioxyacetate Ligand

1INTRODUCTIONTheorganicaromaticcarboxylatemetalcom-plexeshavearousedmuchattentionandbeenwidelyinvestigated.However,thestrategyofdesignandsynthesisofthesecomplexesismostlyfocusedonrigidligands,suchasterephthalicacidandbenzenetricarboxylicacid,etc.[1～5].Theassemblyofcom-plexesbyusingflexiblearomaticcarboxylateli-gandsisfarlessdeveloped[6,.Phenylenedioxydia-7]ceticacids(bdoaH2)withbiologicalactivitiesandwideapplicationsinagriculture[8]areafamilyofmultidentateflexibleligandswithversatilebind…     

Quantum chemical study on the mechanism of the consecutive addition of HCN to aminoacetonitrile

MINDO/3 method has been used to study the mechanism of the consecutive addition ofHCN to aminoacetonitrile.The results obtained for the first three steps show that the reaction isexothermic,and step I is the rate determining step.     

微量稀土对超导稳定化基体铜材的性能和组织的影响

研究了微量稀土元素对铜的机械性能、导电性和组织的影响，在铜中加入微量钇、钕、镝、铒和富铈混合稀土后，使铜的抗拉强度有所提高，并保持良好的塑性和导电性。     

醇脱氢酶结构和作用机理研究进展

介绍了醇脱氢酶的种类, 酵母醇脱氢酶和肝醇脱氢酶等两类常用的醇脱氢酶的物理化学性质和活性位点结构. 归纳了对肝醇脱氢酶和酵母醇脱氢酶作用机理的研究, 重点评述了醇脱氢酶催化反应中的两个关键步骤质子转移和氢化物转移过程机理的研究进展.     

电化学合成铜配合物的研究

采用金属铜为"牺牲"阳极,首次在无隔膜电解槽中,电化学溶解金属铜一步制备了纳米CuO前体Cu(OEt)2, Cu(OBu)2, Cu(acac)2, Cu(OEt)(acac), Cu(OBu)(acac) (acac为乙酰丙酮基).产物通过红外光谱(FT-IR)、拉曼光谱(Raman spectrum)进行表征.同时讨论了影响电合成铜醇盐及其配合物的关键因素.实验表明,防止阳极钝化,温度控制在30～50 ℃,采用有机胺溴化物为导电盐, 电极电位控制在0.8～1.2 V之间,可以提高电合成效率.实验同时表明Cu(acac)2, Cu(OEt)(acac), Cu(OBu)(acac)可作为制备含铜纳米材料前驱体.     

New Photoluminescence Phenomena of Ge／SiO2 Glass Synthesized by Sol-gel Method

New Ge/SiO2 glasses have been synthesized by heating the GeO2/SiO2 dry gels under H2 gas at 700℃. The resulting fluorescence spectra show that this kind of Ge/SiO2 glasses emit strong photoluminescence at 392 nm (3.12 eV), medium strong photoluminescence at 600 nm (2.05 eV) and weak photoluminescence at 770 nm (1.60 eV) respectively. Possible photoluminescence mechanisms are also discussed based on the results of X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS).     

钴(Ⅱ)与5-(5-硝基-2-吡啶偶氮)-2,4-二氨基甲苯络合物吸附波及其应用

钴 (Ⅱ )在NH3·H2O -NH2OH·HCl-5_(5_硝基_2_吡啶偶氮)_2,4_二氨基甲苯体系中有一灵敏的极谱波 ,其峰电位Vp 为 -1.20V(vsSCE) ,钴质量浓度在0.25～25μg/L范围内与峰电流Ip′有良好的线性关系 ,检出限为0.12μg/L;经多种电化学方法证明该波为络合物吸附波 ,其电极过程为不可逆过程 ,电子转移数为2 ,此外还试验了多种离子对峰电流Ip′的影响;所拟方法已用于维生素B12 和模拟样中痕量钴的测定