聚苯并咪唑金属复合物的X-射线光电子能谱(XPS)研究

本文报道以聚苯并咪唑(PBI)与某些过渡金属卤化物所形成的金属复合物的XPS研究,由反映在金属复合物N_(1s)和C_(1s)振起(Shake-up)伴峰的消失,反映在PBI中N_(1s)双峰变为复合物中的具有高结合能的单峰以及与其复合金属离子结合能的降低,这就从施受两个侧面确证金属复合物的形成。XPS结果也说明在金属复合物的制备中,不同溶剂条件所制得的复合物在硅氢加成中活性丧失归结於溶剂导致的金属离子的还原。     

Asymmetric Baeyer—Villiger oxidation: control of stereoelectronic demand

The recent development of asymmetric Baeyer—Villiger oxidation of prochiral and racemic ketones is briefly summarized, focusing on the regio- and stereocontrol of the oxidation attained by regulating the stereoelectronic demand in the step of rearrangement of the Criegee intermediate.Based on the report presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1784–1794, September, 2004.     

异核双金属有机化合物的合成方法与反应性能研究

本文对近年来异核双金属有机化学的发展作了简要的介绍和回顾, 文中对含金属-金属键和不含金属-金属键的d/d和d/f异核双金属有机化合物的合成方法及反应性能作了归纳。     

糖蛋白/胆红素钙水溶性复合物的形成及光谱研究

采用傅立叶变换红外光谱(FT-IR)，结合减法、二阶导、退卷积和曲线拟合等先进光谱技术，紫外可见光谱，ICP-AES分析方法，对不同质量比的α-酸性糖蛋白(AGP)和胆红素钙(CaBR)反应后的滤液进行了研究。结果表明，AGP和CaBR之间存在着较强的相互作用，导致AGP二级结构的有序性增加，CaBR的水溶性增大，两者形成了可溶性的AGP/CaBR复合物。     

Dicopper(I) oxalate complexes as molecular precursors for the deposition of copper compounds

The synthesis, characterization, and thermal decomposition behavior of dicopper(I) oxalato complexes L₄Cu₂(C₂O₄) (L = CNtBu (2a), CNCMe₂CH₂tBu (2b), CNC₆H₃Me₂-2,6 (2c)) is reported. 2c can be prepared in a straightforward manner by the reaction of stoichiometric amounts of Cu₂O and oxalic acid with four equivalents of CNC₆H₃Me₂-2,6, while those complexes with aliphatic isocyanides are better prepared from a copper(I) oxalato complex with alkine capping ligands (Me₃SiCCSiMe₃)₂Cu₂(C₂O₄) (1) via ligand exchange. Crystallographic and spectroscopic evidence for 2a-c confirms the anticipated dinuclear structure with the oxalate in a μ-1,2,3,4 bridging mode and an essentially σ-character of the terminal isocyanides. In solid form the complexes are stable at room temperature and can be handled in air for some time. Their decomposition was studied by thermal gravimetric analysis coupled with mass spectrometry, and the degradation pathway was shown to depend on the type of isocyanide capping ligand. Decomposition of 2a,b takes place between 150 and 200 °C to give CuCN in a clean process that involves isobutene elimination from the terminal ligands, with elimination of (CN)₂ and conversion to elemental copper at higher temperatures. Heating of 2c leads to CuO (and then to Cu₂O) via release of the intact isocyanide, CO₂, and CO in a well-behaved thermal process around 200-280 °C.     

复合蛋白锌在儿科疾患方面的应用

儿童缺锌是较普遍的社会现象，济南泉城微量元素生命研究所研制的复合蛋白锌系采用生物技术转化而得到的一种蛋白复合物，属生物合成的有机微量元素，经急性和长期毒性试验均未发现毒副作用，经检测不含兴奋剂，用于临床后，对纠正偏食厌食，反复呼吸道感染和智力低下等近千例儿童疾患，显示了可喜的临床效果，证明是优质有机补锌剂。     

First example of the formation of bipolar spiro σ-complexes from 6-bromo-5,7-dinitrobenzo[e]-1,2,3,4-tetrazine 1,3-di-N-oxide

The reactions of 3,5,7-trimethyltropolone and 2-(N-benzylamino)tropone with 6-bromo-5,7-dinitrobenzo[e]-1,2,3,4-tetrazine 1,3-di-N-oxide afforded novel bipolar spiro -complexes. The kinetic and activation parameters of the R,S-enantiotopomerization of a chiral spiro -complex of 2-(N-benzylamino)tropone were determined using dynamic ¹H NMR spectroscopy.     

纳米碳酸锌的制备和热分解动力学参数的测定

Nanosized zinc carbonate was prepared in the droplet of nano-reactor based on microemusion. The influences of the concentration of the surfactant and reactant on the diameter of nanoparticles were studied and the kinetic pa-rameters of thermal decomposition reaction were determined. It can be shown from experimental results， the di-ameter of the droplet in the microemulsion which have dissolved reactant zinc nitrate and sal volatile is between 4.9nm and 7.7nm， 6.2nm and 12.4nm， respectively. Nanosized zinc carbonate prepared by the method of mi-croemusion has shown good dispersion， narrow distribution and light agglomeration. The particle size of nanosized zinc carbonate is between 5nm and 40nm， and its kinetic parameters of thermal decomposition reaction-activation energy E and reaction order n are 110kJ·mol^-1 and 0.9， respectively.     

乙烯系单体自由基聚合的阻聚效应——Ⅸ.受阻胺-醌类电荷转移络合物对甲基丙烯酸甲酯自由基聚合的阻聚及历程

用膨胀计法研究了西氯苯醌(CA)、苯醌(BQ)与受阻胺二异丙胺(DIPA)、2,2,6,6-四甲基-4-羟基哌啶(TMP)形成的电荷转移络合物(CTC)对偶氮二异丁腈(AIBN)引发的甲基丙烯酸甲酯(MMA)自由基聚合阻聚效应。结果表明,CA-DIPA、CA-TMP、BQ-DIPA和BQ-TMP对MMA的自由基聚合均产生较单独的醌或胺更显著的阻聚能力。其中以CA-DIPA阻聚效果更佳。比较了MMA在苯或乙腈中的溶液聚合,得类似结果。初步讨论了受阻胺-醌电荷转移络合物对MMA自由基聚合的阻聚反应机理。     

The preparation of nano‐scope chitosan‐oligomer copper complexes and their interaction with DNA

Water‐soluble low molecular weight chitosan of nanometer level and its copper complexes were prepared, and characterized by IR spectra, elemental analysis and gel permeation chromatography (GPC). The modes and mechanism of these copper complexes interaction with DNA were studied by a fluorescent probe method and electrophoresis analysis. It is suggested that there are electrostatic and intercalation modes of copper complexes interacting with DNA. At first, the cationic complex electrostaticly binds to the negatively charged phosphate backbone of DNA, and then a portion of the complex intercalates between the base pairs on the DNA duplex strand. Copyright © 2005 John Wiley & Sons, Ltd.