Linking Chiral Clusters with Molybdate Building Blocks: From Homochiral Helical Supramolecular Arrays to Coordination Helices

The synthesis of four new oxo‐centered Fe clusters ( 1 a – c , 2 ) of the form [Fe^III₃(μ₃‐O)(CH₂=CHCOO)₆] with acrylate as the bridging ligand gives rise to potentially intrinsically chiral oxo‐centered {M₃} trimers that show a tendency to spontaneously resolve upon crystallization. For instance, 1 a , [Fe^III₃(μ₃‐O)(CH₂=CHCOO)₆‐(H₂O)₃]⁺, crystallizes in the chiral space group P3₁ as a chloride salt. Crystallization of 1 b , [Fe₃(μ₃‐O)(C₂H₃CO₂)₆(H₂O)₃]NO₃?4.5H₂O, from aqueous solution followed by recrystallization from acetonitrile also gives rise to spontaneous resolution to yield the homochiral salt [Fe₃(μ₃‐O)(C₂H₃CO₂)₆‐(H₂O)₃]NO₃?CH₃CN of 1 c (space group P2₁2₁2₁). Furthermore, the reaction of 1 a with hexamolybdate in acetonitrile gives the helical coordination polymer {[(Fe₃(μ₃‐O)L₆(H₂O))(MoO₄)‐(Fe₃(μ₃‐O)L₆(H₂O)₂)]?2CH₃CN?H₂O}_∞ 2 (L: H₂C?CHCOO), which crystallizes in the space group P2₁. The nature of the ligand geometry allows the formation of atropisomers in both the discrete ( 1 a – c ) and linked {Fe₃} clusters ( 2 ), which is described along with a magnetic analysis of 1 a and 2 .     

Analysis of Chlorogenic Acid in Herbal Medicines by Capillary Electrophoresis

Atpresent,thecommonlyusedmethodforanalyzingherbalmedicinesishighperformanceliquidchromatography(HPLC).However,theuseofHPLCisrestrictedformanyreasons.Themostseriousproblemisthatthechromatographiccolumniseasilycontaminated.ComparedwithHPLC,capillaryelectrophoresis(CE)ischaracterizedwithhighefficiency,rapidity,lowcostandmultiplemodestobechosen.Inaddition,thecapillarycanbeeasilyregenerated.SoCEisidealforanalyzing"dirty"samples,suchasChineseherbalmedicines.Infact,studiesintheareaarebecoming…     

Microstructure and Ion Exchange in Stearic Acid Langmuir-Blodgett Films Studied by Fourier Transform Infrared-Attenuated Total Reflection Spectroscopy

Fourier transform infrared-attenuated total reflection (FTIR-ATR) spectra have been recorded of 11-layer Langmuir-Blodgett (LB) films of stearic acid deposited at various surface pressures (0.1, 15, and 35 mN/m), and the molecular orientation angles were evaluated quantitatively, which supplied insight into the molecular order with the alkyl chains tightly packed like crystal in the LB films deposited at the zero and higher surface pressures. These experimental results indicate that, in the Langmuir film as the precursor of LB films, stearic acid molecules self-aggregate to form two-dimensional crystalline domains already even at the zero surface pressure, which results in the inhomogeneity of monolayer. The analysis of dependence of nu(C=O) intensity on the surface pressure, surface density, and subphase temperature leads to the conclusion that the defects in LB films originate from the Langmuir film and be conserved upon deposition. Annealing below 50 degrees C and cooling could improve the monolayer homogeneity, and thus a defect-free or low-defect LB films can be deposited. Furthermore, ion exchange conducted in the LB films, on the other hand, confirms the existence of structure defects in LB films of stearic acid. The polar plane microstructure, lateral transport along the polar planes and the coordination types of stearic acid/cation system may be the rate-limiting process. The results have implication on the possible uses of stearic acid LB films as ion-exchange materials or sensors. Copyright 2001 Academic Press.     

雷公藤的药效及毒性与微量元素的研究

雷公藤是一种药效大、毒性也大的中药。研究了雷公藤的28种无机元素，发现其有益元素铁、锰、锌、硒含量较高．其有害元素铅、砷、镉含量也较高，与其药效和毒性一一相对应。雷公藤对风湿性关节炎、肾病、肝脏病、皮肤病的疗效．与铁、锰、锌、硒在人体中生物学机理一致。雷公藤对消比道、心血管、肝脏、泌尿系统、造血系统的毒害作用，与铅、砷、镉在人体中的生物学效应一致。所以在使用雷公藤时，应考虑到微量元素作用．可提高雷公藤的疗效，降低其毒性。     

正丁基锂四氢呋喃引发α-甲基苯乙烯阴离子平衡聚合动力学及反应机理研究

本文研究了以正丁基锂为引发剂,四氢呋喃为添加剂,环己烷为溶剂中的α-甲基苯乙烯阴离子平衡聚合动力学。讨论了体系中的反应活性种;提出了聚合机理;得到了聚合温度为20℃时的平衡单体浓度与活性种速率常数及添加剂浓度之间的关系式。     

白血病骨髓移植病人全血微量元素铜的变化及其意义

为了研究白血病骨髓移植病人全血微量元素铜的变化及其意义 ,用原子吸收光谱法检测了正常对照组与白血病骨髓移植患者预处理前及移植后骨髓空虚期全血微量元素铜的含量。结果表明 ,正常对照组全血铜浓度与白血病骨髓移植患者预处理前全血铜浓度差异无显著性 (P >0 0 5 ) ,而与骨髓空虚期全血铜浓度有显著性差异 (P <0 0 5 ) ,说明白血病缓解后血铜接近正常对照组水平 ,而白血病骨髓移植患者预处理后骨髓空虚期全血铜含量高于正常对照组 ,说明预处理影响微量元素铜的代谢 ,本文就其影响机理进行了研究     

源内裂解液相色谱-质谱鉴别人参皂甙Rf和拟人参皂甙F11

研究了利用源内碰撞诱导解离(in-source collision-induced d issoc iation)的高效液相色谱-大气压化学电离质谱(HPLC-APC I/MS)获取人参和西洋参的化学标志物———人参皂甙R f和拟人参皂甙F11的特征结构信息及鉴别人参和西洋参的方法。在乙腈-水梯度洗脱反相液相色谱及源内碰撞诱导解离条件下,能获得人参皂甙R f和拟人参皂甙F11的母核离子及去糖基离子的源内碰撞诱导解离谱,从其差别能清楚区分这对同分异构体。本方法对人参皂甙R f和拟人参皂甙F11的检出限能达到10-7g柱上样量,简单、快速,单次质谱实验就能鉴别人参和西洋参。     

The first total synthesis of (-)-tamandarin A

[formula: see text] Tamandarin A (1), a newly isolated natural product similar in structure to didemnin B (2), was shown to be somewhat more active in vitro than 2 against pancreatic carcinoma with an ED50 value 1.5 to 2 ng/mL. We report here the first total synthesis of 1. The key steps include a practical stereoselective synthesis of the Hiv-isostatine unit, high-yielding linear precursor formation, a successful macrocyclization, and coupling of the macrocycle with the side chain to afford tamandarin A (1).     

The Study of Anti-tumor Activity of Trichosanthin by Cyclic Voltammogram

IthasbeenreportedthatTrichosanthi11(TCS),isolatedfromrkiI-ilolt)ii,hasanti-tumorI-4andanti-vira1activities5-'.Someanti-tun1orremedies,whicharedesignedfromTCS,arebeingtestedanddeveloped'-.'.StudyingthebioIogicalphenomenonbyelectrochemicalmethodsisanewhotresearchspotemerginginrecentyears".Manyresultsshowedthatnotonlytheenzymesystemsuchassuccinatedehydrogenasedisplayedthediode-likebehaviorduringtheelectrontransferprocess",butalsothehigh1yorganizedorganeIle,forexample,mitochondria,andevenintac…     

Mo－Cu－S原子簇化合物［Mo_2Cu_6S_6（SCMe_3）_2（O）_

基于标题簇合物的快原子质谱研究，提出该二簇合物在质谱过程中的可能断裂途径及其簇骼转换的相关性。