自由基-分子反应:F+Propene(CH2CHCH3)的从头算研究

采用从头算CCSD(T)/6-311 G(2d,2p)//B3LYP/6-311G(d,p)方法,研究了自由基-分子反应F CH2CHCH3的各种不同的反应通道．该反应主要是通过复合物形成机制进行,即F分别加到碳碳双键的两端形成自由基复合物1和2．这两种亚稳态自由基会解离成三种产物:H C3H5F、CH3 C2H3F和HF C3H5．理论计算结果表明,生成CH3 C2H3F是反应的主要通道,而生成H C3H5F和HF C3H5对产物也有一定的贡献．这一结果和实验符合得很好．     

Mechanism of catalytic asymmetric hydrogenation of 2-formyl-1-methylene-1,2,3,4-tetrahydroisoquinoline using Ru(CH3COO)2[(S)-binap]

The mechanism of the asymmetric hydrogenation of 2-acyl-1-alkylidene-1,2,3,4-tetrahydroisoquinolines, the first reported reaction with the Noyori-Takaya Ru(CH₃COO)₂(binap) complex, has been investigated by means of deuterium labeling, kinetics, and NMR analysis. A series of experiments has revealed that (1) a monohydride-unsaturated mechanism operates involving the initial formation of RuH followed by reaction with the enamide substrate, (2) the hydride transfer from RuH to the olefinic double bond is endothermic and reversible, and (3) the rate is determined in the hydrogenolysis step. This view is consistent with that of proposed for the BINAP-Ru catalyzed Kagan reaction.     

4-Hydroxy-2-quinolones. 93. Synthesis and biological properties of 2-hydroxy-4-imino-1,4-dihydroquinoline-3-carboxylic acid N-R-amides

Various methods of synthesizing amides of 2-hydroxy-4-imino-1,4-dihydroquinoline-3-carboxylic acids have been studied. Results of investigations on the antitubercular and antiinflammatory activity of the obtained compounds are discussed. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 542–555, April, 2006.     

玻璃中CdSeS纳米晶体的生长及其性能

对掺有镉、硒、硫的玻璃在500—800℃退火2—24h,生长了不同尺寸的CdSxSe1x纳米晶体.用分光光度计和光致发光光谱(PL)分析了纳米晶体的性能.退火温度低于550℃,纳米晶体处于成核阶段,600—625℃处于正常扩散生长阶段,700—800℃处于竞争生长阶段;而650℃处于两种生长阶段之间.虽然650℃下生长的纳米晶体的尺寸分布比较窄,但纳米晶体的尺寸随退火时间的延长几乎不变,在该温度改变退火时间很难改变纳米晶体的平均尺寸.在所有样品中出现了深能级缺陷,在650℃退火时间小于4h或大于16h有利 关键词： 纳米晶体 生长机理 深能级缺陷     

基于内生信息的股票发售机制比较研究

本文在内生信息成本的基础上，通过引入投资银行的信息成本函数，考察了国际上主要股票发售机制的内在机理，并用一个统一的框架比较了各种发售机制的差异及演进趋势。本研究表明，在投资银行和投资者信息成本相同的情况下，由于固定价格发售机制须用额外的折价去解决投资者之间的信息问题，因而相对于累计投标询价制是一种处于劣势的机制选择。同时指出，具有信息成本优势的机构投资者的出现和发展，是固定价格发行向询价发行过渡的一个必要条件。     

Very high coercivities of top-layer diffusion Au/FePt thin films

The Au/FePt samples were prepared by depositing a gold cap layer at room temperature onto a fully ordered FePt layer, followed by an annealing at 800 °C for the purpose of interlayer diffusion. After the deposition of the gold layer and the high-temperature annealing, the gold atoms do not dissolve into the FePt Ll₀ lattice. Compared with the continuous FePt film, the TEM photos of the bilayer Au(60 nm)/FePt(60 nm) show a granular structure with FePt particles embedded in Au matrix. The coercivity of Au(60 nm)/FePt(60 nm) sample is 23.5 kOe, which is 85% larger than that of the FePt film without Au top layer. The enhancement in coercivity can be attributed to the formation of isolated structure of FePt ordered phase.     

Study on Phase-Formation Mechanism and Intergrowth for Bi(Pb)-Sr-Ca-Cu-O System

In this paper, the phase-formation mechanism of Bi-based superconductors was systematically investigated by using high-temperature X-ray diffraction, differential thermal analysis (DTA) and crystallization of amorphous state. The transformations among Bi-based 2201, 2212 and 2223 phases were observed, and the intergrown phenomenon of the 2201, 2212 and 2223 phases was explained. It was proposed that there exist a composition equilibrium between 2212 phase and Ca2CuO3 and a competition of thermody-namic stability among Ca2CuO3, 2212 and 2223 phases. This is why it is difficult to prepare the 2223 phase. After Pb was doped in Bi-Sr-Ca-Cu-O system, Ca2CuO3 phase in the Bi-Sr-Ca-Cu-O system was replaced by Ca2PbO4, so that the composition equilibrium and competition of thermodynamic stability mentioned above were avoided.     

Regiochemistry of the addition of mercury salts to bornylene

The dependence of the regiochemistry of the mercuration of bornylene on the nature of the mercurating reagent and on the solvent has been found. The structures of the intermediate and transition state in these reactions have been proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 501–505, March, 1994.     

The decisive role of calorimetric measurements in equilibrium phase diagram calculations

In this paper, examples are given of how calorimetric values can give greater certainty to phase equilibria calculated from thermodynamic data. Errors that may arise when phase diagram evaluations are carried out largely from the basis of Gibbs energy information only are illustrated by reference to recent evaluations of the Ti?Si system and the resulting calculated oxidation behaviour of titanium silicides. The importance of calorimetric values for calculation of metastable phase equilibria is demonstrated by results of work on the AlN?TiN hard-metal coating system. Finally, suggestions are made with regard to areas of work where calorimetric data are urgently needed.