生物体系中电子转移机理的研究Ⅱ: 分子间电子转移及 电子供、受体间不同基 团的影响

利用自编程序MOPAC-ET中AM1方法,及KT(Koopman'sTheorem)法,研究了二苯负离子体系的分子间电子转移现象,计算了其电子供、受体在不同距离下的V~A~B及它们之间的相关性,另外,还对两苯环间不同介入基团对电子转移的影响做了初步研究,发现不同的介入基团存在着较大的差异。     

Ab initio through‐space/bond interaction analysis of the long C–C bonds in Bi(anthracene‐9,10‐dimethylene) photoisomers

The bi(anthracene‐9,10‐dimethylene) photoisomer has remarkably long C–C single bonds. To examine the lengthening of the C–C bond, we propose a novel procedure for quantitatively analyzing orbital interactions in a molecule at the level of the ab initio molecular orbital method. In this procedure, we can cut off the specific through‐space/bond interactions in a molecule by artificially increasing the absolute magnitude of the exponents in a Gaussian function. Then, the spatial orbital interactions were perfectly cut off, and, each term that makes up the total energy, that is, the nuclear–electron attractions, the electron–electron repulsions, and the nuclear–nuclear repulsions cancel each other. Several model molecules of the photoisomer were analyzed by this procedure. It was found that the orbital interaction between the p orbital on the benzene ring and the σ* orbital on the C–C bond in question, σ→σ* electron transfer through π orbital, weakens the C–C bond efficiently when these orbitals were located in the “periplanar” conformation. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Flow-through microdispenser for interfacing micro-HPLC to Raman and mid-IR spectroscopic detection

A flow-through microdispenser has been coupled to a micro HPLC separation system and used as a solvent elimination interface for Fourier transform infrared (FTIR) and Raman spectroscopic detection of the separated compounds. Using the microdispenser picoliter sized droplets can be generated and deposited on an appropriate target placed on a computerized x, y-stage. Evaporation of volatile solvent and buffer is rapid and allows analysis of the obtained dry deposits by various techniques. Due to the destruction free character of Raman and FTIR spectroscopy they can be applied sequentially to interrogate the same deposit. In the reported application five phenolic acids typically present in wine have been separated on a C-18 column technique using a mixture of water, methanol and acetic acid as mobile phase. For spectrum acquisition infrared and Raman microscopes have been used. The spectra recorded from the dried deposits of the separated compounds agreed well with the reference spectra of corresponding components.     

Modification of HPTLC-plates by in situ chemical bonding with non-polar and polar organosilanes

A method has been developed for the preparation of modified silica plates for high performance thin-layer chromatography (HPTLC). Some typical organosilanes were thus allowed to react in situ with the silica of Merck HPTLC-plates. This method was found to be highly reproducible, simple and cheap. Non-polar plates were prepared and compared with commercial plates from Merck, Whatman and Macherey-Nagel. Modification with cyanodecyltrichlorosilane resulted in plates that showed good coverage, efficiency and low residual silica activity. Silica modified with a multifunctional silane has different properties in different organic solvents. It will appear to be non-polar in a polar solvent and vice versa. New advantageous separation systems are thus made feasible by the presence of cyano groups on the plate. The utility of modified thin-layer plates is demonstrated by the separation of some homologues of p-hydroxybenzoic acid esters and of some polycyclic aromatic hydrocarbons.     

Understanding the conformational dependence of spin-spin coupling constants: through-bond and through-space J(31P,31P) coupling in tetraphosphane-1,4-diides [M(L)x]2[P4R4

The characteristic dependence of J(31P,31P) spin-spin coupling constants of alkali metal tetraphosphane-1,4-diides on structure and composition has been analyzed by density functional methods. The computations confirm that the structure of the contact ion pairs is conserved in solution. Calculations on model systems M2P4H4, on naked P4H4(2-) anions, and on models including point charges, show that the role of the cations is mainly structural and to a smaller extent electrostatic. Three of the four J(P,P) coupling constants depend characteristically on the conformation of the anion, which in turn is determined by the substituents R and by cation-anion interactions. Several couplings exhibit a large through-space component and are thus strongly dependent on the relative orientation of nonbonding electron pairs on the phosphorus atoms involved. This is shown by visualization of coupling pathways using the recently introduced coupling energy density (CED), in combination with the electron localization function (ELF).     

X波段低副瓣波导缝隙阵列天线特性

:根据Stevenson等效电路法设计了两个X波段低副瓣波导缝隙阵列天线。通过建立多个缝隙时的谐振长度提取模型,计算了存在缝隙间互耦时的谐振长度。两个阵列天线测试结果和仿真结果吻合良好,线阵中心频率实测增益为17.83 dB,其仿真结果为18.2 dB,实测副瓣为-28.12 dB,其仿真结果为-29.97 dB;平面阵列中心频率实测增益为27 dB,其仿真结果为27.9 dB, 实测H面副瓣为-27.2 dB,其仿真结果为-29.9 dB,实测E面副瓣为-22 dB,其仿真结果为-22 dB。     

涡轮叶栅前缘槽缝气膜冷却的数值模拟

应用FINE/TURBO软件包,求解三维雷诺平均N-S方程,对叶片前缘有两列冷却槽缝的气膜冷却流场进行了数值模拟,获得了不同吹风比下叶片表面静压分布与极限流线.在计算结果与实验数据良好符合的基础上,详细分析了槽缝冷却三维定常流场结构与槽缝附近的流动细节.研究结果表明,槽缝冷却对前缘压力分布影响较大,且在压力面引起较大的分离流动,不利于冷却.     

沟槽对建筑物减震作用的动光弹研究

本文用动光弹方法实验研究了沟槽对爆炸地震波的衰减作用和对建筑物的保护作用分析表明:在模型实验条件下,当槽深大于20mm时,地震波的大部分能量被槽挡住,地震波对槽后的建筑物影响甚小,当槽深小于15mm时,槽与建筑物之间应力场较强,临界深度在15～20mm左右,这一深度大约是爆生瑞利波波峰深度的3～4倍。槽宽度对地震波衰减作用不大。     

光子晶体全反射贯穿偏振滤波器的理论研究

为了研究1维光子晶体中光的全反射贯穿效应及其偏振滤波特性,利用传输矩阵法计算了TE波和TM波在大于全反射角入射1维光子晶体的透射率,发现在透射波中出现了全反射贯穿效应。研究了TE波和TM波的全反射贯穿效应随介质光学厚度和周期数的变化特征,表明：全反射贯穿峰的频率随介质光学厚度的增加而减少,全反射贯穿峰数与周期数相等。且全反射贯穿效应具有优良的偏振滤波特性,利用这些特性可以设计出结构简单、控制方便的1维光子晶体的偏振滤波器。