新显色剂7-(苯并噻唑-2-偶氮)-8-羟基喹啉-5-磺酸的分析性能及其与锌显色反应的研究

报道了新显色剂７－（苯并噻唑－２－偶氮）－８－羟基喹啉－５－磺酸（简称ＢＴＨＱＳＡ）的离解常数的测定，同时研究了该显色剂对锌离子光度分析的条件，摩尔吸光系数ε＝５．１×１０４Ｌ·ｍｏｌ－１·ｃｍ－１，锌离子浓度在０～６．５μｇ／２５ｍＬ符合比尔定律，并对人发中的微量锌进行测定。     

2-氨基-4-溴-5-氯苯甲酸的合成

以硝基苯为原料，经溴化、还原、缩合、环合、氯化和氧化等６步反应合成了２－氨基－４－溴－５－氯苯甲酸，总收率为１１．７％。     

2,5-二甲氧基-4-氯-N-乙酰基乙酰苯胺及其颜料的合成研究

研究了以２，５－二甲氧基－４－氯苯胺为原料，在酸性情况下用双乙烯酮为酰化剂制备２，５－二甲氧基－４－氯－Ｎ－乙酰基乙酰苯胺，收率为９２．０％，并用之与３，３′－二氯邻苯二胺的重氮盐进行偶合反应合成了永固黄ＨＲ（Ｃ．Ｉ．ＰＹ８３），收率为９５％。     

2-乙酰基-7-甲胺基酮与TMB等取代芳香醛的反应

本文探讨了２－乙酰基－７－甲胺基卓酮与３，４，５－三甲氧基苯甲醛（ＴＭＢ）等取代芳香醛的羟醛缩合反应。２－乙酰基－７－甲胺基卓酮与ＴＭＢ、丁香醛、二溴醛等取代芳香醛进行反应分别生成了２－（３，４，５－三甲氧基）肉桂酰基－７－甲胺基卓酮；２－（４－羟基－３，５－二甲氧基）肉桂酰基－７－甲胺基卓酮；２－（４－羟基－３，５－二溴）肉桂酰基－７－甲胺基卓酮等三种尚未见文献报道的新化合物。它们的结构经红外光谱、核磁共振谱及元素分析得以证实。     

联立方程法测定2-重氮-1-萘醌-5-磺酰氯含量的研究

报告了测定２－重氮－１－萘醌－５－磺酰氯含量的光度分析的联立方程法。无水乙醇溶液中,分别在３７２５、４０７ｎｍ波长处测定吸光度,建立联立方程式,通过解联立方程计算出２１５－磺酰氯含量。平均回收率为１００１６％,相对标准偏差为０６９％。     

3-(2-氯苯基)-5-甲基-4-异唑甲酸的合成研究

以邻氯苯甲醛、羟胺和乙酰乙酸乙酯为主要原料，经过肟化、氯代、环合和水解反应，合成了氯唑青霉素中间体———３－（２－氯苯基）－５－甲基－４－甲基异唑甲酸。总收率达５０％以上。     

新试剂糠醛缩7-氨基-8-羟基喹啉-5-磺酸的合成及催化荧光测定超痕量钒(Ⅴ)

合成了新试剂糠醛缩７－氨基－８－羟基喹啉－５－磺酸（简称Ｆ７Ｎ８Ｑ５Ｓ）。试剂在酸性介质中被ＫＢｒＯ３氧化分解，生成强荧光物质，Ｖ（Ⅴ）对该反应具有强烈的催化作用，由此建立了测定痕量钒的催化荧光法。反应在酸性介质中进行，０．０５％Ｆ７Ｎ８Ｑ５Ｓ３．０ｍＬ，５％ＫＢｒＯ３０．６ｍＬ，沸水浴中加热２０ｍｉｎ，λｅｘ／λｅｍ＝３２６ｎｍ／３８６ｎｍ。钒的量在０．０～４．８μｇ／Ｌ范围内呈线性，检测限为０．４μｇ／Ｌ。该方法用于实际样品中痕量钒的测定，结果满意。此外还详细研究了反应机理。     

(4R,5R)-2-乙基-2-(6-甲氧基-2-萘基)-1,3-二氧戊环-4,5-二羧酸二甲酯的合成

以对甲苯碘酸为催化剂合成（４Ｒ,５Ｒ）－２－乙基－２－（６－甲氯基－２－萘基）－１,３－二氧戊环－４,５－二羧酸二甲酯     

5-(苯并-15-冠-5)-10,15,20-碘化三(对三甲铵苯基)卟啉铑、钌、钯配合物的合成

合成了一种水溶性的５－（苯并－１５－冠－５）－１０，１５，２０－碘化三（对三甲铵苯基）卟啉及其与铑、钌、钯的３种新配合物。进行了元素分析、电子光谱、ＩＲ、１ＨＮＭＲ表征和光助还原水放Ｈ２的实验。     

导数-双波长分光光度法测定镍

报告了应用一阶导数－双波长分光光度法测定钴、镍共存试样中的镍含量。在表面活性剂ＯＰ存在下形成Ｎｉ－５－Ｂｒ－ＰＡＤＡＰ三元配合物，对配合物吸光度的一阶导数曲线取波长组合５７２．５ｎｍ和５５３．５ｎｍ处的ｄＡ／ｄλ值进行测定，其Δ（ｄＡ／ｄλ）值对镍浓度的线性关系良好。对模拟样品和工厂排放水样进行了测定，结果说明该法灵敏度高，相对标准偏差为０．８％～２．２％，加标回收率为１００．２％～１０２．５％。     

Synthesis of polymers from chiral monomers in chiral liquid crystals

Polymer prepared from a monomer ((S)‐configuration at stereogenic center) in a cholesteric liquid crystal (CLC) medium consisting of chiral molecules in (R)‐configuration, a three‐dimensional (3D) chiral continuum, exhibits intense Cotton effect compared to polymer prepared in the CLC with (S)‐configuration. This result can be explained by intermolecular interaction between the monomer and the CLC medium in the polymerization process. The intramolecular twisted structure along the polymer chain (secondary structure) and the helical aggregation between the polymer chains (intermolecular structure and tertiary structure) induced by the liquid crystal medium as 3D chiral continuum are discussed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

方兴未艾的手性化学

简要介绍了手性化学中的手性合成、手性拆分的重要性。重点介绍了:1新型手性化合物的合成拆分及应用;2聚集诱导荧光在手性化学中的应用;3手性化学在反应机理研究中的应用。并对手性化学的发展进行了展望。     

方兴未艾的手性化学

简要介绍了手性化学中的手性合成、手性拆分的重要性。重点介绍了:1新型手性化合物的合成拆分及应用;2聚集诱导荧光在手性化学中的应用;3手性化学在反应机理研究中的应用。并对手性化学的发展进行了展望。     

高效液相色谱法纤维素类手性固定相分离手性化合物

在手性柱OJ-H上直接分离了三种手性化合物,并初步探讨了手性化合物在不同流动相的组分———醇的种类及结构对手性拆分的影响,结果发现,溶质与固定相分子之间的氢键作用、π-π作用对溶质的手性分离有一定的影响。另外,不同直链醇作为流动相也影响着手性化合物的保留与分离。     

高效液相色谱手性固定相法拆分金属簇合物

在正相条件下,ChiralcelR○OD手性色谱柱上,首次直接拆分了3种外消旋过渡金属簇合物,考察了手性化合物结构以及流动相中的醇在手性识别过程中对手性拆分的影响。     

Polymeric chiral crown ethers

Summary Copolymerizations of (S)-3,3-dimethyl-2,2-bis[2-(2-vinyloxyethoxy)ethoxy]-1, 1-binaphthyl (S-MVN) or 1,3:4,6-di-O-benzylidene-2,5-bis-O-[2-(2-vinyloxyethoxy)ethyl]-d-mannitol (D-BVM) with isobutyl vinyl ether (IBVE) were carried out with BF₃·OEt₂ in CH₂Cl₂ at 0 °C. The copolymers obtained were soluble in CHCl₃ and THF, and consited of (S)-binaphtho-21-crown-6 or d-manno-21-crown-6 units and IBVE, i.e., poly(S-DVN-co-IBVE) and poly(D-BVM-co-IBVE). These host copolymers dominantly formed complexes with l-phenylglycine methyl ester, whose properties were similar to those for homopolymers of S-MVN and D-BVM.Part 8: H. Hashimoto, T. Kakuchi, O. Haba, K. Yokota: Macromolecules 25 1828 (1992)     

Electrochemical polymerization of chiral pyrrole derivatives in electrolytes containing chiral camphor sulfonic acid

N‐Substituted pyrrole derivatives with chiral side groups have been synthesized and electrochemically polymerized in acetonitrile containing tetrabutylammonium perchlorate (TBAClO₄) and (S)‐(+)‐camphor‐10‐sulfonic acid ((S)‐(+)‐CSA) or (R)‐(?)‐camphor‐10‐sulfonic acid ((R)‐(?)‐CSA). The resulting N‐substituted polypyrrole films were characterized by cyclic voltammetry, infrared, Raman and X‐ray photoelectron (XPS) spectroscopies. XPS results demonstrated that the as‐grown polymer films are preferably doped by CSA anions when the monomer and the CSA anion have the same optical rotation dispersion (ORD). Furthermore, the conductivities of the polymers synthesized in the media containing CSA with the same ORD of the corresponding monomers were measured to be about 2–10 times higher than those of polymers obtained from electrolytes without CSA. Copyright © 2004 Society of Chemical Industry     

Lipase-catalyzed synthesis of chiral triglycerides

Under certain reaction conditions, the acidolysis of tripalmitin with oleic acid using immobilized lipase from Rhizomucor miehei resulted in a higher level of monosubstituted oleoyldipalmitoyl (OPP) triglycerides than had been predicted according to kinetic modeling. The reaction products were subjected to chiral analysis by high-performance liquid chromatography (HPLC), which indicated that the enzyme was more active at the sn-1 position of the triglyceride than at the sn-3 position, resulting in synthesis of the chiral triglyceride 1-oleoyl-2,3-dipalmitoyl-sn-glycerol. A kinetic model was developed and was correlated with the HPLC method to provide a simple means to predict the stereoselectivity of lipase-catalyzed reactions. By using the model, the stereoselectivity of immobilized Rhizomucor miehei lipase was found to depend strongly on the initial water activity (a _w) of the reaction mixture, with greater selectivity occurring at lower a _w. The sn-1 selectivity was essentially maintained using various solvents, or without solvent, when a _w was kept constantly low. Variation in the fatty acid composition of the triglyceride indicated that shorter-chain fatty acids result in greater stereoselectivity, while variation of the chainlength of the free fatty acid indicated an enhancement by the longest chainlength. The stereoselectivity of this lipase was confirmed using a new ¹³C nuclear magnetic resonance method. By using immobilized R. miehei lipase at low a _w approximately 80% of the chiral triglyceride found in the reaction mixture was the sn-1 enantiomer, at high reaction conversion.     

手性HMPA类似物的合成

以磷酰氯为原料通过与手性肿胺的亲核取代反应高产率地合成了手性ＨＭＰＡ类似物。