C_(70)与臭氧反应机理的理论研究

用半经验AM1方法研究了C_(70)与臭氧环加成反应的反应机理。采用Berny梯度 法优化得到反应的过滤度，并进行了振动分析确诊。计算结果表明：臭氧在C_(70) 6－6单、双键上的环加成反应均为复杂反应，由三步组成：第一步是O_3分子与C_ (70)的6-6单、双键发生1,3-偶极环加成反应，生成分子臭氧化物（即中间体I）， 6－6双键加成为放热反应，6－6单键加成为吸热反应，活化势垒分别为84.7和181. 2 kJ·mol~(-1)；第二步是中间体I的加成，C－C键断裂，生成两性离子中间体II 的放热反应，其势垒分别为61.3和13.3 kJ·mol~(-1)；第三步是中间体II脱去一 个Q_2分子生成具有环氧结构的C_(70)O，均为放热反应，活化势垒分别为169.3和 101.2 kJ·mol~(-1)；第三步是中间体I脱去一个O_2分子生成具有环氧结构的C_ (70)O，均为放热反应，活化势垒分别为169.3和101.2 kJ·mol~(-1)，从反应机理 和动力学角度解释了6－6双键加成优于6-6双键加成优于6-6双键加成优于6-6单键 加成的原因。O_3分子与C_(70)6-6双键的加成反应是协同且同步进行的，与6－6单 键的加成反应是协同但不同步的过程。     

Amidation of unfunctionalized hydrocarbons catalyzed by ruthenium cyclic amine or bipyridine complexes

Selective amidation of simple hydrocarbons with pre-isolated and in-situ formed iminoiodanes catalyzed by ruthenium complexes [Ru(III)(Me(3)tacn)(CF(3)CO(2))(3).H(2)O] (2b, Me(3)tacn = N,N', N"-trimethyl-1,4,7-triazacyclononane) and cis-[Ru(II)(6, 6'-Cl(2)bpy)(2)Cl(2)] (3, 6,6'-Cl(2)bpy = 6,6'-dichloro-2, 2'-bipyridine) was investigated. With PhI=NTs as nitrogen source, both catalysts efficiently promote the amidation of adamantane, cyclohexene, ethylbenzene, cumene, indan, tetralin, and diphenylmethane to afford N-substituted sulfonamides in 80-93% yields with high selectivity. Competitive amidations of para-substituted ethylbenzenes and kinetic isotope effect for the amidation of cyclohexene/cyclohexene-d(10) suggest that the amidation processes probably proceed via the hydrogen abstraction by a reactive Ru=NTs species to form a carboradical intermediate. The amidation with PhI(OAc)(2)/TsNH(2) gave results comparable to those obtained with PhI=NTs. Extension of the "PhI(OAc)(2)/TsNH(2) + catalyst 2b or 3" protocol to MeSO(2)NH(2) and PhCONH(2) with ethylbenzene as substrate produced the corresponding N-substituted amides in up to 89% yield.     

On the arc component of a locally compact Abelian group

For a topological group G, we denote by G _a the arc component of the neutral element and by the character group of G, i.e. the group of all continuous homomorphisms from G into T. We prove the following theorem: Let G be a connected locally compact abelian group and let be the embedding. Then is a topological isomorphism. In particular, the character group of the arc component of a compact abelian group is discrete. Some conclusions will be drawn.     

Numerical methods for backward Markov chain driven Black-Scholes option pricing

The drift, the risk-free interest rate, and the volatility change over time horizon in realistic financial world. These frustrations break the necessary assumptions in the Black-Scholes model (BSM) in which all parameters are assumed to be constant. To better model the real markets, a modified BSM is proposed for numerically evaluating options price-changeable parameters are allowed through the backward Markov regime switching. The method of fundamental solutions (MFS) is applied to solve the modified model and price a given option. A series of numerical simulations are provided to illustrate the effect of the changing market on option pricing.     

On the determination of natural frequencies and mode shapes of cable-stayed bridges

An accurate analysis of the natural frequencies and mode shapes of a cable-stayed bridge is fundamental to the solution of its dynamic responses due to seismic, wind and traffic loads. In most previous studies, the stay cables have been modelled as single truss elements in conventional finite element analysis. This method is simple but it is inadequate for the accurate dynamic analysis of a cable-stayed bridge because it essentially precludes the transverse cable vibrations. This paper presents a comprehensive study of various modelling schemes for the dynamic analysis of cable-stayed bridges. The modelling schemes studied include the finite element method and the dynamic stiffness method. Both the mesh options of modelling each stay cable as a single truss element with an equivalent modulus and modelling each stay cable by a number of cable elements with the original modulus are studied. Their capability to account for transverse cable vibrations in the overall dynamic analysis as well as their accuracy and efficiency are investigated.     

Passively mode-locked Nd:YVO4 laser with up to 13 GHz repetition rate

We demonstrate passive mode locking of a Nd:vanadate (Nd:YVO₄) laser to repetition rates of up to 13 GHz. With Ti:sapphire pumping, we achieved mode locking at 13 GHz with 310 mW of average output power and pulse widths of 9.5 ps. With diode pumping, we achieved mode locking at a repetition rate of 12.6 GHz with 198 mW of average output power and a pulse duration of 8.3 ps. Received: 6 July 1999 / Published online: 30 July 1999     

介孔SiO2负载的纳米金及其催化应用

金（Au）的催化作用已成为催化领域的前沿研究课题。本文综述了近年来采用不同方法制备介孔二氧化硅(MCM-41, MCM-48, SBA-15)负载的纳米Au催化剂以及在CO低温氧化、环己烯加氢和环己烷氧化等反应中的催化作用。讨论了影响纳米Au催化剂活性的相关因素, 包括载体的种类、表面性质、Au纳米颗粒的尺寸、分散度以及稳定性等。最后对各种制备纳米Au的方法进行了总结。     

CO2加氢合成甲醇催化反应中CO的作用

研究了铜基催化剂上CO₂加氢合成甲醇反应中掺人CO的作用,结果表明,在原料中添加少量CO,甲醇的选择性提高38%,收率提高25%;TPD-MS和TPSR-MS结果表明,CO能抑制催化剂表面起逆水汽变换作用的活性位对CO₂的吸附,从而提高了CO₂加氢合成甲醇的选抒性.