手性膦氮配体的合成及其钯配合物催化的不对称烯丙基烷基化反应

以价廉的天然产物辛可宁和奎宁为原料,在温和的条件下方便地合成了两个手性膦氮配体.考察了它们与过渡金属钯配合物在不对称烯丙基烷基化反应中的催化活性和不对称诱导作用.在1,3-二苯基-2-烯丙基-1-醇的乙酸酯与丙二酸二甲酯的反应中,两个配体均表现出中等的手性诱导活性(最高为73.5%e.e.).     

高分子药物研究Ⅰ．5－氨基水杨酸与二元羧酸缩聚物的合成

通过５－氨基水杨酸与二元羧酸进行缩聚反应，合成了六种主链含有５－氨基水杨酸的高分子化合物，用红外光谱和元素分析确定了聚合物的结构。聚合物水解实验表明，它们在酸性、中性和碱性介质中均能水解，水解速率（ｒ）的大小依次为ｒｐＨ＝１３．０＞ｒｐＨ＝７．０＞ｒｐＨ＝２．０。     

芥子气纯度测定不确定度分析与评定

采用酸碱滴定法测定芥子气纯度,对测量结果的不确定度进行评定。分析了测定过程中不确定度来源,包括滴定剂的标定、消耗滴定剂体积、样品称量等引入的不确定度及其计算方法,最后合成得到标准不确定度。当芥子气纯度测定结果为94.78%时,扩展不确定度为0.34%(k=2)。实验结果表明,样品称量引入的不确定度对测量结果的影响最大。     

一氧化氮选择还原锡锆固溶体催化剂的结构特性

采用双股并流共沉淀方法制备了SnO2含量从10％至90％的锡锆体系DeNOx催化剂,用XRD、微区电子衍射、FT-Raman及FT-IR等技术深入研究了锡锆体系氧化物的结构及其随组成的变化规律.结果表明，由于Sn4＋与Zr4＋离子半径接近,SnO2与ZrO2易于形成固溶体,并随组成变化表现出不同的结构特征.纯ZrO2为单斜相,当少量Sn4＋（SnO2 ≤ 20％）进入ZrO2晶格时形成四方相富锆固溶体,Sn4＋起到稳定ZrO2四方相的作用;随着SnO2含量的增大,结构从无定形或微晶态的富锆固溶体(含SnO2 30～50％)经富锆固溶体与金红石结构的富锡固溶体在55％ SnO2含量的共存状态变化到具有金红石结构的富锡固溶体（SnO2 ≥ 60％）.FT-Raman和FT-IR光谱测试证明,Zr进入SnO2晶格使得Sn－O键的结合减弱,Sn离子上的有效正电荷减小,降低了SnO2对丙烯的燃烧能力,从而提高了对NO的还原活性.     

Tris（2,2＇-bipyridyl） Ruthenium（Ⅱ） Doped Silica Film Modified Indium Tin Oxide Electrode and Its Electrochemiluminescent Properties

An approach was reported to synthesize silica hybridized ruthenium bipyridyl complex through amidation reaction by covalent attachment of bis（bipyridyl）-4,4＇-dicarboxy-2,2＇-bipyridyl-ruthenium to （3-aminopropyl）-triethoxysilane. The hybrid complex then was gelatinized through acid catalytic hydrolysis method and a sol-gel modified indium tin oxide electrode was prepared via spin coating technique. As prepared indium tin oxide electrode possesses good stability therein with excellent electrochemiluminescence behavior.     

Asymmetric reduction of representative ketones with a bis-chiral oxazaborolidine system

In recent years, many optically active β-amino alcohols, mostly derived from naturally occurring α-amino acids, have been incorporated into the asymmetric synthesis as chiral auxiliaries or ligands.1 An effective asymmetric catalysts, the oxazaborolidine-borane reagents, which were originally pioneered by Itsuno and Corey,2 were generally prepared from chiral β-amino alcohols by the reaction with boric acid or formed in situ in the presence of borane. These reagents provide excellent enanti…     

Electroosmotic flow controllable coating on a capillary surface by a sol-gel process for capillary electrophoresis

A simple coating procedure employing a sol-gel process to modify the inner surface of a bare fused-silica capillary with a positively charged quaternary ammonium group is established. Scanning electron microscopic studies reveal that a smooth coating with 1 to approximately 2 microm thickness can be obtained at optimized coating conditions. With 40 mM citrate as a running electrolyte, the plot of electroosmotic flow (EOF) versus pH shows a unique three-stage EOF pattern from negative to zero and then to positive over a pH range of 2.5 to 7.0. At pH above 5.5, the direction of the EOF is from the anode to the cathode, as is the case in a bare fused-silica capillary, and the electroosmotic mobility increases as the pH increases. However, the direction of the EOF is reversed at pH below 4.0. Over the pH range of 4.0 to 5.5, zero electroosmotic mobility is obtained. Such a three-stage EOF pattern has been used to separate six aromatic acids under suppressed EOF and to separate nitrate and nitrite with the anions migrating in the same direction as the EOF. The positively charged quaternary ammonium group on the coating was also utilized to minimize the adsorption problem during the separation of five basic drugs under suppressed EOF and during the separation of four basic proteins with the cations migrate in the opposite direction as the EOF. Also, the stability and reproducibility of this column are good.     

[C6N2H18]2[Mo5O15(HPO4)2]·H2O的水热合成与结构表征

通过水热法合成了一个新化合物[C6N2H18]2[Mo5O15(HPO4)2]·H2O,并通过IR光谱、ICP、元素分析、差热与热重分析和X射线单晶衍射分析等手段进行了表征.结果表明,晶体属三方晶系,P3(2)21空间群,a=1.1231(1)nm,c=2.2802(5)nm,V=2.4911(7)nm3,Dx=2.835Mg/m3,Z=6,最后的一致性因子R=0.0227,wR=0.0675.阴离子中Mo5O15构成一环状结构,2个HPO4一个连在环的下方,一个连在环的上方,形成类似于“飞碟”状的结构,阳离子为2个质子化的四甲基乙二胺.     

Me4Bzo2[14]六烯(2-)N4金属配合物的结构和反应性研究——Ⅱ. ML和MLXx型配合物的电子吸收光谱研究

本文研究了ML及MLX_x型配合物电子吸收光谱的电荷转移谱带,求得了所用N₄大环配体的光学电负性值,证实金属的形式D_q值与成键有关.对阐明有关化合物的结构提供了新的证据.     

Antiplasmodial cembradiene diterpenoids from a Southwestern Caribbean gorgonian octocoral of the genus Eunicea

Five new representatives of the cembrane class of marine natural products have been isolated as minor metabolites from an undescribed species of Eunicea, a sea whip collected near the Colombian Southwestern Caribbean Sea. The structure of the crystalline metabolite 1 was solved by single-crystal X-ray diffraction analysis. Structures could then be proposed for cembradienes 2-5 by comprehensive spectral analyses involving 2D NMR, IR, UV, and high-resolution mass spectrometry, as well as chemical interconversion studies. Compound 1 exhibited weak cytotoxicity in the NCI 3-cell line panel human cancer screening program, whereas compounds 1, 2 and 4 displayed significant antiplasmodial activity against Plasmodium falciparum.