Theoretical study of the reaction of Sc with SCO in gas phase

In order to elucidate the mechanism of reaction M⁺ + SCO, both triplet and singlet potential energy surfaces (PESs) for the reaction of Sc⁺ + SCO have been theoretically investigated using the DFT (B3LYP/6-311+G*) level of theory. The geometries for reactants, intermediates, transition states and products were completely optimized. All the transition states were verified by the vibrational analysis and the intrinsic reaction coordinate calculations. The involving potential energy curve-crossing dramatically affects reaction mechanism, reaction rate has been discussed, and the crossing points (CPs) have been localized by the approach suggested by Yoshizawa et al. The present results show that the reaction mechanism are insertion–elimination mechanism both along the C–S and C–O bond activation branches, but the C–S bond activation is much more favorable in energy than the C–O bond activation. All theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction.     

Evanescent fluorobiosensor for the detection of polyaromatic hydrocarbon based on DNA intercalation

A flow-injection analysis (FIA) system coupled with an evanescent wave (EW) Biosensor employing total internal reflection of fluorescence radiation (TIRF) for the detection of polyaromatic hydrocarbon that intercalates into DNA is reported. A highly fluorescent intercalator, “ethidium bromide,” has been used as the reference compound for detection. The EW Biosensor was developed according to the procedure described earlier (1,2). Data on the analysis of Naphthalene, 3-methy cholanthrene, 7,12-dimethylbenz(a)anthracene, 1,2-benzanthracene, and some standard reference materials supplied by the National Institute of Standards and Technology are reported. The relative ability of the polyaromatic hydrocarbon to displace ethidium bromide, based on the relative binding ratio, is found to be on the order of 7,12-dimethylbenz[a]anthracene > 3-methylcholanthrene > 1,2-benzanthracene > napthalene.     

Synthesis,complexation, and photochemistry of benzobisthiazole-based bis(crown ether)

Benzobisthiazole-based bis(crown ether) was synthesized and its complexation with alkali and alkaline earth cations was studied. Photochemical transformations of the free ligand and its complexes with alkaline earth cations involve E,Z-photoisomerization and [2+2] photocycloaddition. Dedicated to Academician N. S. Zefirov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2056–2065, September, 2005.     

从头计算方法比较TiSi_2的C54相和C49相

采用平面波超软赝势描述多电子体系,利用密度泛函理论和广义梯度近似,计算出C54相和C49相TiSi2的晶格常数、体弹性模量、形成能、电子态密度(DOS)和Mulliken电荷布居等性质.通过比较这两种物质的性质,发现尽管两者形成能很相近,但C49相结构对称性差、体弹性模量小、熔点低,Ti原子d轨道的反键强、离子性弱.这些性质上的差异和C49相TiSi2在固相反应中优先形成有关.     

少量人发中硫的测定

建立了测定一根长2～3cm人发中硫的间接分光光度法,表观吸光系数为5.1×10~4,络合物组成Ba:CPA-mA为1:2,比耳定律范围为0～20μg硫。硫的检测限为0.025μg/mL,变动系数为2.7%,回收率为91.2～97.2%,且不用掩蔽即可直接进行测定,测定211例人发的结果表明,含硫量范围为(28.5±3.2)×10~3μg/g。     

Preparation,properties and X-ray cystal structures of complexes of 4,4-diethylmorpholinium with 2,5-dibromo- and 2,5-dichloro-7,7,8,8-tetracyano-p-quinodimethane : DEM(TCNQBr2)2 and DEM-TCNQCl2

4,4-Diethylmorpholinium forms a 1:2 complex with 2,5-dibromo-TCNQ and a 1:1 complex with 2,5-dichloro-TCNQ; both are insulators at room temperature, and their single crystal $\text{X}$-ray structures have been determined at 293 K.     

异构丁醇在四氯化碳、正庚烷、苯和1,2-二氯乙烷中的红外光谱研究

利用FT-IR,测定了四种异构丁醇十四氯化碳、 正庚烷, 苯和1,2-二氯乙烷稀溶液在3800—3000cm~(-1)内的红外吸收光谱。缔合峰与自由羟基峰的面积之比与溶质、溶剂的性质有关,且在极稀溶液区与溶质的质量百分比浓度之间有良好的直线关系。本文又运用1-n(环状)模型对有关体系进行了对比研究。结果表明,丁醇分子支链度的增加以及丁醇分子与苯和1,2-二氯乙烷之间的特殊相互作用,降低了醇分子的缔合能力。稀溶液中,丁醇分子在苯和1,2-二氯乙烷中主要以单体和环状二聚体形式存在,在四氯化碳中以单体和环状三聚体形式存在,而正丁醇分子在正庚烷中主要为单体和环状四聚体,异、仲、特丁醇主要为环状三聚体和单体。     

Crystallographic parameters in α-UF5 and U2F9 by multiphase refinement of high-resolution neutron powder data

The crystal structures of α-UF₅ and U₂F₉ were refined with high-resolution neutron powder diffraction data from an $\text{α-}\text{UF}{}_5\text{U}{}_2\text{F}{}_9$ mixture. Refinement was achieved by a multiphase Rietveld profile refinement technique. The results are compared with previous X-ray and neutron powder studies.