显微共焦拉曼光谱研究电化学合成聚苯胺膜

显微共焦拉曼技术被用来研究电化学合成的聚苯胺（PANI）膜. 研究结果表明：在不同的激发光聚焦深度，聚苯胺膜的拉曼光谱有明显变化.从而反映出聚苯胺膜的掺杂程度在膜生长过程中随膜厚度的增长而增加. 并由X射线电子能谱（XPS）和紫外吸收光谱（UV）分析证实.     

Novel Cyanine Dyes: Synthesis,Characterization and Photosensitization‐Structure Correlation

Novel furo, thieno and pyrrolo[2,3‐b]pyrazole cyanine dyes were synthesized. The structure‐photosensitization properties correlation of the dyes were examined in 95% ethanol solution by absorption spectroscopy. The chemical structure of the starting biheterocyclic compounds and their derived cyanine dyes were confirmed by elemental analysis, IR and ¹H NMR spectroscopy.     

桥联双（甲巯咪唑）化合物的合成和配位性能

研究了桥联双(甲巯咪唑)化合物(Ⅰ_a—Ⅳ_a、Ⅰ_b)的合成和配位性能。UV谱显示Ⅰ_a—Ⅳ_a与UO_2~(2+)离子(硬酸)配位,溶液中形成3:1的配合物。Ⅰ_b与Hg~(2+)、Au~(3+)离子(软酸)配位形成2:1的配合物,用CNDO/2方法计算了各配体分子中原子净电荷密度和HOMO、LUMO能量。     

红外光谱中溶剂效应机理研究(IV) 溶剂受电子位阻效应常数的确定

In the previous paper(Ⅲ), the following equation of solvent effect in organic chemistry was suggested:
Ei=a﹒Ai(1-Va﹒VAi)+d﹒Di(1-Vd﹒VDi)+E0
Where Ei is a physical or chemical property of the substrate in the solvent i and E0 is that in n-hexane. Ai and Di are constants of electron acception and donation effect of the solvent i respectively. VAi and VDi are constants of electron acception and donation space effect of the solvent i respectively, a and d are the sensitivities of E of the substrate vs the change of Ai and Di. Va and Vd are the constants of electron acception and donation space effect of the substrate respectively. In IR spectra E could be substituted by the wavenumber(ν). Ai and VAi have been established for 18 organic solvents (n-C6H14, n-C7H16, cyclohexane, CCl4, Ph-Me, ClCH:CCl2, Et2O, CHCl3, C6H6, CH2Cl2, ClCH2CH2Cl, Ph-NO2, THF, 1,4-dioxane, Et-NO2. MeCO2Et, Me-NO2, Me-CN).
In this paper Di and VDi have been established for these solvents. The equation also has been tested by the νC-X(X=Cl, Br) of five alkylhalides (t-BuCl, n-C5H11Cl, t-BuBr, Et-Br, EtC(H)BrMe) and νC=O of three carboxyl compounds (t-BuCOMe, Me2CO, MHB) and seven organotin compounds [(Ph2MeSiCH2)3SnO2C-C6H4-X-p(X=H-, CH3-, CH3O-, NO2-, F-. Cl-, I-)].
The relationship (ν=ρ﹒σ+ν0) between νC=O of organotin compounds and Hammett constants(σ) of the substituted groups in different solvents was studied and a relationship betweenρ and Ai, VAi, Di, VDi of the solvents was found.     

二价铜、镍EDTA络合物晶体的电子吸收光谱

络合物晶体的电子吸收光谱作为研究晶体的电子结构的基础内容,很早以前就得到人们注意,虽然对Cu~(2+)、Ni~(2+)等络合物电子光谱的能级的经验指认已是一项较为成熟的工作,但对吸收光谱的系统的理论计算和定量解释在以前的文献中尚不多见.近年来,我们对多种晶体的电子吸收光谱进行了定量的解释,结果表明理论计算值总是能很好地符合于实验测定值。一般说来,吸收峰位的波数误差在8%以内. 早在本世纪四十年代就奠定了乙二胺四乙酸(EDTA)在分析化学中的应用基础。     

Darstellung und Charakterisierung der Trisilylphosphane (Ph 3Si) n P(SiMe 3)3−n,n=1,2,3

A simple preparation of the title compounds is achieved by reacting Na₃P/K₃P with stoichiometric mixtures of chlorotriphenylsilane and chlorotrimethylsilane.³¹P- and²⁹Si-NMR-Data as well as Ir and Raman spectra of the compounds are reported.

     

New diphthalocyanine complexes of rare-earth metals based on 4,5-isopropylidenedioxyphthalonitrile

A series of the earlier unknown diphthalocyanine complexes of rare-earth metals based on 4,5-isopropylidenedioxyphthalonitrile were prepared. Their compositions and yields depend on the radius of the complexing ion. The synthesized compounds were studied by spectroscopy and electrochemical methods. The redox potentials of the complexes studied change nonlinearly with a decrease in the lanthanide ion radius. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 274—279, February, 2006.     

赖氨酸-Ag反应机理的研究

The interaction of silver(Ⅰ) ion with lysine has been investigated by UV-Vis, fluorescent spectra and electrophoresis method. The effect of pH medium and multicomponent concentration on interaction of lysine-silver has also been studied. Lysine-silver system showed maximum absorbance at 239 nm and 448 nm. Lysine showed fluorescence. The fluorescence excitation wavelength was about 356.6 nm (fluorescence emission wavelength was about 438.6 nm). When the reaction of silver(Ⅰ) ion with lysine happened, fluorescence was quenching. Lysine-silver system carried negative charge, and the electrokinetic potential of double electrode layer was -2.35×10^-4 V.     

配体形状对多吡啶铜(Ⅱ)配合物与DNA作用的影响

合成了一系列含有平面配体的Cu(Ⅱ)多吡啶配合物[Cu(IP)₂]²⁺、[Cu(PIP)₂]²⁺、[Cu(DPPZ)₂]²⁺和[Cu(HPIP)₂]²⁺，用吸收光谱、CD光谱和粘度等方法研究了这些配合物与小牛胸腺DNA的作用。结果表明配体上的取代基及配体的平面性对这些四面体配合物与DNA的结合强弱产生一定的影响。[Cu(DPPZ)₂]²⁺与DNA的结合较强，而[Cu(HPIP)₂]²⁺与DNA的结合较弱。CD光谱显示配合物[Cu(DPPZ)₂]²⁺、[Cu(PIP)₂]²⁺和[Cu(HPIP)₂]²⁺的加入会导致DNA的CD光谱减弱。而[Cu(IP)₂]²⁺的加入则会使DNA的CD光谱增强。同时，[Cu(IP)₂]²⁺与DNA结合后，还会引起一定程度的DNA构型转换，即DNA从B型转换成Z型。     

Synthesis, structure, and electrochemical properties of 12,42-dioxo-21,31-diphenyl-7,10,13-trioxa-1,4(3,1)-diquinoxalina-2(2,3),3(3,2)-diindolizinacyclopentadecaphane

The oxidative dehydrocyclization of the 3-(indolizin-2′-yl)-2-oxoquinoxaline monopodand performed either electrochemically or under the action of molecular iodine affords new redox-active heterocyclophane consisting of the redox-switchable biindolizine fragment combined with the polyether-bridged π-deficient quinoxaline systems. The single-crystal X-ray diffraction study showed that the trioxaundecane chain of heterocyclophane adopts an extended conformation, and one of the phenyl substituents of the molecule closes the pseudocavity formed by the spacer from one of the sides. The cyclic voltammetric study of heterocyclophane in MeCN and DMF showed the three-step oxidation of the indolizine fragments accompanied by the single-electron transfer in each step. The first and third steps are reversible, and the second step is irreversible. The oxidation at potentials of the first peak gives rise to stable radical cations detected by the ESR method (g = 2.0024, a _2N = 0.26 mT). Dedicated to Professor E. A. Berdnikov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1991–2003, October, 2007.