钐(Ⅱ)类卡宾CH_3SmCH_2X(X=Cl、Br和Ⅰ)促进乙烯环丙烷化反应途径的理论研究(英文)

用密度泛函B3LYP方法研究了过渡金属钐类卡宾与乙烯的环丙烷化反应的机理。对三种不同的钐的SS试剂CH_3SmCH_2X(其中X=Cl、Br和Ⅰ)分别和CH_2CH_2反应的各反应物、中间体、过渡态和产物构型的全部结构几何参数进行了优化,用内禀反应坐标(IRC)计算和频率分析方法,对过渡态进行了验证。结果表明：CH_3SmCH_2X(其中X=Cl、Br和Ⅰ)与CH_2CH_2环丙烷化反应按亚甲基转移通道(通道A)和卡宾金属化通道(通道B)都可以进行,与锂类卡宾的反应机理相同,只是按亚甲基转移通道(通道A)进行反应较容易一些,而且此反应在较低的温度下就可以发生。     

12-Ring Network Coordination Polymer——{[Cu(C_4N_2H_(10))_4]_2·H_4V_4O_(14)}_n Formed by Linking cyclo-[H_4V_4O_(14)]~(4-) with Cu(C_4N_2H_(10))~(2+)_4 Cation Clusters

IntroductionThe interest in polyoxometalates that are widelyused in medical chemistry, catalyst reactions, and ma-terial sciences stems from their complicated aggregatesformed by means of corner-, edge- and face-sha-ring[1—4]. The exploitation of new str…     

DISSIPATIVE SCHEMES WITH PROPERTY OF INHERITING HOMOCLINIC ORBITS FOR 2N-DIMENSIONAL HAMILTONIAN SYSTEMS

1　ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｉｓｐａｐｅｒｉｓｄｅｖｏｔｅｄｔｏｓｔｕｄｙｗｈａｔｋｉｎｄｏｆｄｉｓｃｒｅｔｅｓｃｈｅｍｅｓｏｆｔｈｅｆｏｌｌｏｗｉｎｇ 2ｎ ｄｉｍｅｎ ｓｉｏｎａｌＨａｍｉｌｔｏｎｉａｎｓｙｓｔｅｍｓｗｉｔｈｐａｒａｍｅｔｅｒｉｎｎｏｒｍａｌｆｏｒｍ ｕ=Ｊ2ｎ Ｈ ｕＴ,　　Ｈ =Ｈ(ｕ ,λ) ,(1 )ｗｈｅｒｅｕ∈Ｒ2ｎ,λ∈Ｒ ,Ｈ∈Ｃｋ+1(Ｒ2ｎ×Ｒ ,Ｒ) ,ｋ≥ 6,ａｎｄＪ2ｎ =0Ｉｎ-Ｉｎ 0 ,Ｉｎ:ｕｎｉｔｍａｔｒｉｘｏｆｏｒｄｅｒｎｈａｓｔｈｅｐｒｏｐｅｒｔｙｏｆｉｎｈｅｒｉｔｉｎｇｈｏｍ…     

Monitoring the Aggregation of Dansyl Chloride in Acetone through Fluorescence Measurements

The aggregation of dansyl chloride (DNS-Cl) in acetone has been studied in detail by steady-state fluorescence techniques.It has been demonstrated that DNS-Cl is stable in acetone during purification and aggregation study processes.The aggregates are not solvolyzed in acetone,and do not take part n any chemical reactions either.It has been found that DNS-Cl tends to aggregate even when its concentration is much lower than its solubility in acetone.The aggregation is reversible,and both the aggregation and the deaggregation are very slow processes.Introduction of SDS has a positive effect upon the formation and stabilization of the aggregates.     

A CLASS OF r-POINT (r+1)ST-ORDER A-STABLE ONE-BLOCK METHODS WITH DAMPING AT THE INFINITE POINT

1　ＩｎｔｒｏｄｕｃｔｉｏｎＦｏｒｓｏｌｖｉｎｇｓｔｉｆｆｉｎｉｔｉａｌｖａｌｕｅｐｒｏｂｌｅｍｓｆｏｒｓｙｓｔｅｍｓｏｆＯＤＥｓｙ′=ｆ(ｙ) ,ｙ(ｔ0 ) =ｙ0 ,ｔ0 <ｔ≤Ｔ ,ｙ0 ,ｙ∈Ｒｍ,ｆ :Ω Ｒｍ →Ｒｍ (1 .1 )ｍａｎｙｐａｒｔｉｃｕｌａｒｏｎｅ ｂｌｏｃｋｍｅｔｈｏｄｓｏｆｔｈｅｆｏｒｍＹｎ+1= ＡＹｎ+ｈ( Ｂ0 Ｆ(Ｙｎ) + Ｂ1Ｆ(Ｙｎ+1) ) , Ａ =Ａ Ｉｍ, Ｂｉ=Ｂｉ Ｉｍ,Ａ ,Ｂｉ∈Ｒｒ×ｒ,Ｙｎ =(ＹＴｎｒ,… ,ｙＴ(ｎ+1)ｒ- 1) Ｔ,Ｆ(Ｙｎ) =(ｆＴ(ｙｎｒ) ,… ,ｆＴ(ｙ(ｎ+1)ｒ- 1) ) Ｔ,ｙｊ≈ ｙ(ｔｊ) ,…     

THE INVERSE EIGENPROBLEM WITH RANK-ONE UPDATING AND ITS STABLITY

Let ∑, Г be two n-by-n diagonal matrices with σi,γi as their diagonals. For the inverse eigenvalue problem: look for y∈Rn such that Г + yyT is similar to ∑, we prove thatu also the sufficient condition for the solvability of this inverse problem. Its solution (set) is given explicitly. In some case, the problem is unstable. But we prove that the sums of the square of some contigious components keep stable, i.e., small sum keeps small, large sum has a small relative perturbation, see Theorem 3.     

腺嘌呤及其β-环糊精包结物的光谱研究

通过紫外光谱的摩尔比法确定了腺嘌呤与β-环糊精（β－CD）包结物的包结比为1：1，通过紫外光谱和荧光光谱研究了腺嘌呤在酸性，中性，及碱性条件下的光谱变化及与β－CD包结物的光谱变化，分别求得了它们与β－CD包结的平衡常数。     

基于变芯径光纤的光学系统在光造型中的应用

光学系统采用变芯径光纤，可大幅度提高光的传输效率，增加光学子系统柔性。描述了光造型工作原理及其理论依据，在介绍所研制的光的成型系统光学子系统的基础上，阐述了紫外光源的选择与设计，及变芯径光纤的设计、传输、耦合与聚焦等技术。该套基于变芯径光纤的光学子系统成本低、体积小、效率高，巳成功应用于所研制的台式低成本快速成型系统中，为该系统的进一步推广奠定了技术基础。     

20GHz注入锁模光纤激光器实验

稳定、波长可调谐的窄脉冲光源是未来光时分复用/波分复用光纤通信系统的重要组成部分。报道了一个20GHz的注入锁模光纤激光器的实验。利用一个10GHz的导体体激光器作为光源，最终得到了波长可调谐的重复频率为20GHz、脉冲宽度为12.4ps的光脉冲，波长的调谐范围为16nm。     

HIGH ACCURACY FINITE VOLUME ELEMENT METHOD FOR TWO-POINT BOUNDARY VALUE PROBLEM OF SECOND ORDER ORDINARY DIFFERENTIAL EQUATIONS

1　ＩｎｔｒｏｄｕｃｔｉｏｎＦｉｎｉｔｅｖｏｌｕｍｅｅｌｅｍｅｎｔｍｅｔｈｏｄｏｒＦＶＥＭｕｓｅｓａｖｏｌｕｍｅｉｎｔｅｇｒａｌｆｏｒｍｕｌａｔｉｏｎｏｆｔｈｅｄｉｆ ｆｅｒｅｎｔｉａｌｅｑｕａｔｉｏｎｗｉｔｈａｆｉｎｉｔｅｐａｒｔｉｔｉｏｎｉｎｇｓｅｔｏｆｖｏｌｕｍｅｔｏｄｉｓｃｒｅｔｉｚｅｔｈｅｅｑｕａｔｉｏｎ ,ｔｈｅｎｒｅ ｓｔｒｉｃｔｓｔｈｅａｄｍｉｓｓｉｂｌｅｆｕｎｃｔｉｏｎｓｔｏａｌｉｎｅａｒｆｉｎｉｔｅｅｌｅｍｅｎｔｓｐａｃｅｔｏｄｉｓｃｒｅｔｉｚｅｔｈｅｓｏｌｕｔｉｏｎ ([1 -4 ] ) .…