三唑酮对映体的手性拆分研究

合成了纤维素—三(3，5-二甲基苯基氨基甲酸酯)(CDMPC)，涂敷于氨基丙烷化硅胶上制备成涂敷量15％的手性固定相。以正己烷-异丙醇为流动相，在高效液相色谱上实现了对三唑酮光学异构体的直接拆分，研究了流动相中异丙醇的比例对分离效果的影响，优化了色谱拆分条件。     

CDMPC手性柱的制备及色谱条件优化

研究了自制CDMPC手性柱制备过程中合成的纤维素—三(3,5-二甲基苯基氨基甲酸酯)(CDMPC)酯化情况,对自制CDMPC手性柱柱温及流动相比例对马拉硫磷分离效果的影响进行了分析,最后利用液相质谱仪对手性柱流出物质进行了确认,说明自制CDMPC手性柱具有马拉硫磷手性分离能力。     

乙氧呋草黄对映体的手性拆分研究

进行了除草剂乙氧呋草黄对映体在自制的纤维素-三(3,5-二甲基苯基氨基甲酸酯)(CDMPC)高效液相色谱手性柱上的拆分研究。使用了两种流动相体系:正己烷-异丙醇;石油醚-异丙醇,并分别考察了流动相中加入的极性改性剂对手性拆分的影响。试验结果显示,乙氧呋草黄在两种流动相体系中都能得到最好的拆分,但正己烷体系优于石油醚体系,流动相中的极性改性剂的含量减少有利于手性拆分。在正己烷流动相条件下考察了柱长、温度对手性拆分的影响。对对映体的拆分机理进行了讨论。     

6种手性化合物在键合型直链淀粉苯基氨基甲酸酯类手性固定相上的拆分比较

自制了3种键合型直链淀粉苯基氨基甲酸酯类(苯基氨基甲酸酯IAT、3-氯苯基氨基甲酸酯IAC、3,5-二甲基苯基氨基甲酸酯IAD)手性固定相,比较了3种固定相对6种手性化合物的手性识别能力,同时也将商品柱Chiralcel OD-H、Chiralcel AD-H对6种手性化合物的拆分结果进行了比较。实验结果表明:所合成的键合型手性固定相对样品托儿格碱、2-羟基-3-(2-萘氧基)丙基-2',3'-二甲基苯基硒醚和戊唑醇表现出更好的手性识别能力,并且直链淀粉衍生物苯环上引入吸电子基团或给电子基团对固定相手性识别能力均有明显的影响。     

聚S-3-(9-乙基-9-芴基)-1,2-环氧丙烷螺旋聚醚手性固定相的制备及其对外消旋体分离能力的研究

用偶联剂3-(环氧丙氧基)丙基三甲氧基硅烷(GPTMS)将手性螺旋聚3-(9-烷基芴-9-基)-1,2-环氧丙烷键合到硅胶表面上,制备成高效液相色谱手性固定相。将该类手性固定相应用于拆分外消旋体。研究发现,在该类手性固定相中,以聚3-(9-乙基-9-芴基)-1,2-环氧丙烷键合硅胶手性固定相拆分效果为最佳。而且,这类手性固定相应用于高效液相色谱,解决了以往单手性螺旋的聚甲基丙烯酸酯类作为手性固定相一直存在的溶剂问题。     

β-环糊精衍生物作为流动相添加剂在纤维素三苯基氨基甲酸酯手性柱上的应用

以微晶纤维素和苯基异氰酸酯为原料合成了纤维素三苯基氨基甲酸酯,涂敷于氨丙基硅烷化硅胶上制成手性固定相。并以β-环糊精衍生物为手性流动相添加剂在手性柱上进行对映体的拆分。结果表明,当使用手性固定相和含有手性添加剂的流动相分离手性化合物时存在手性两相协同作用,其中以2,3,6-三甲基-β-环糊精(TM-β-CD)为流动相添加剂时的效果最好。     

键合纤维素手性固定相的合成及手性拆分

合成了键合型纤维素-（二苯基甲基二氨基甲酸酯,苯基氨基甲酸酯）手性固定相,并用此键合柱在流动相正自己烷／异丙醇下对几种手性化合物进行了拆分,实验结果表明,此手性固定相具有一定的拆分能力。     

纤维素-三(3,5-二甲基苯基氨基甲酸酯)对烯唑醇对映体的直接拆分

制备了纤维素-三(3，5-二甲基苯基氨基甲酸酯)手性固定相(CDMPC)，以正己烷为流动相，添加异丙醇为改性剂，在高效液相色谱上实现了对烯唑醇光学异构体的直接拆分，探讨了改性剂的含量及色谱柱长对拆分效果的影响，从而优化了拆分条件。试验结果显示，流动相中异丙醇含量的减少有利于对映体的拆分，但保留增强；长色谱柱也有利于对映体的分离。使用两色谱柱串连，当流动相中正己烷与异丙醇的比例为95：5时可达到最佳分离效果，分离因子为1．17。     

外消旋体喹禾灵在纤维素类手性柱上的直接拆分

通过在自制的球形氨丙基硅胶上涂敷纤维素-三（4-甲基苯基氨基甲酸酯）（CMPC）制备了手性固定相，并采用此手性固定相成功地对外消旋体喹禾灵进行了高效液相色谱拆分。     

13种手性醚类化合物在多糖衍生物手性柱上的拆分比较

采用高效液相色谱法,在纤维素-三(3,5-二甲基苯基氨基甲酸酯)(OD)、直链淀粉-三(3,5-二甲基苯基氨基甲酸酯)(AD)和纤维素-三(4-甲基苯基甲酸酯)(OJ)3种手性柱上对13种手性醚类化合物进行了拆分,考察了流动相中醇对手性拆分的影响。实验结果发现,大多数样品在3根手性柱上的保留因子都比较小,这或许与样品只能接受质子与OD或AD形成氢键,而与OJ无氢键作用有关。所拆分的手性醚类化合物在这3种手性固定相上获得了不同程度的拆分,OD对所分析样品具有更好的手性识别能力,13种手性醚类化合物分别获得了基线或部分拆分。     

Enantioselective Gas Chromatography with Derivatized Cyclodextrins in the Flavour and Fragrance Field

This article deals with enantioselective gas chromatography (Es-GC) utilizing cyclodextrin derivatives as chiral stationary phases (CSPs) for chiral recognition in the flavour and fragrance field. It consists of two main parts. The first one concerns cyclodextrins and their use in Es-GC, and it deals with their introduction and evolution as CSPs in GC, together with some theoretical aspects involved with enantiomeric separation and their consequent influence on routine chiral recognition. The second part reports on the strategy of chiral recognition in routine analysis with cyclodextrin derivatives as CSP, illustrated with examples from the authors’ everyday experiences. This part describes how to identify enantiomers or to measure their excess or ratio determination in complex mixtures; in particular, it discusses the opportunities offered by multidimensional and fast GC techniques, the role of mass spectrometry, and the application of total analysis systems to chiral recognition.     

Synthesis of Cellulose-2,3-bis(3,5-dimethylphenylcarbamate) in an Ionic Liquid and Its Chiral Separation Efficiency as Stationary Phase

A chiral selector of cellulose-2,3-bis(3,5-dimethylphenylcarbamate) (CBDMPC) was synthesized by reacting 3,5-dimethylphenyl isocyanate with microcrystalline cellulose dissolved in an ionic liquid of 1-allyl-3-methyl-imidazolium chloride (AMIMCl). The obtained chiral selector was effectively characterized by infrared spectroscopy, elemental analysis and ¹H NMR. The selector was reacted with 3-aminopropylsilanized silica gel and the CBDMPC bonded chiral stationary phase (CSP) was obtained. Chromatographic evaluation of the prepared CSPs was conducted by high performance liquid chromatographic (HPLC) and baseline separation of three typical fungicides including hexaconazole, metalaxyl and myclobutanil was achieved using n-hexane/isopropanol as the mobile phase with a flow rate 1.0 mL/min. Experimental results also showed that AMIMCl could be recycled easily and reused in the preparation of CSPs as an effective reaction media.     

西酞普兰对映体的手性色谱拆分及吸附平衡

以添加醇类和二乙胺的正己烷为流动相,考察了多糖类、酒石酸类和环糊精类手性固定相对西酞普兰外消旋体的拆分效果,优选合适的手性固定相、流动相和温度等色谱条件,在此基础上利用前沿色谱法测定了西酞普兰对映体的吸附等温线。优化的色谱操作条件为：Chiralpak AD-H柱为固定相,正己烷∶异丙醇∶二乙胺（95∶5∶0.1,体积比）为流动相,柱温35℃。西酞普兰对映体的吸附等温线为优惠型,采用Langmuir方程拟合,效果较好。本研究为模拟移动床（SMB）制备西酞普兰对映体提供重要的基础数据。     

聚硅氧烷手性固定相的发展及应用

对聚硅氧烷手性固定相的发展及应用进行了评述。从最初Frank等发明的酰胺型聚硅氧烷手性固定相,到当前应用较多的改性环糊精(CD)、冠醚类接枝聚硅氧烷,聚硅氧烷手性固定相在色谱分离中的优异性能越来越引起人们的重视。聚硅氧烷手性固定相的制备方法主要有两种,而应用最多的是催化硅氢加成技术。     

纤维素及其衍生物作为高效液相色谱手性固定相的研究进展

对纤维及其衍生物作为高效液相色谱手性固定相的研究进展进行了综合综述。     

Synthesis of chiral stationary phase via surface‐initiated atom transfer radical polymerization of vinylated cellulose 3,5‐dimethylphenylcarbamate

A polysaccharide‐immobilized chiral stationary phase (CSP) was prepared by the surface‐initiated atom transfer radical polymerization (SI‐ATRP), in pyridine, of cellulose 2,3‐bis(3,5‐dimethylphenylcarbamate), having a polymerizable vinyl group, on the surface of SiO₂ support. The successful preparation of the CSP was confirmed via Fourier transform infrared spectroscopy, field‐emission scanning electron microscopy, X‐ray photoelectron spectroscopy, elemental analysis and thermal analysis. The chiral recognition ability of the prepared CSP was evaluated with high‐performance liquid chromatography using 10 racemates with various mobile phases of hexane/alcohol, hexane/tetrahydrofuran and hexane/chloroform. As a result, this CSP prepared using SI‐ATRP can be used in tetrahydrofuran and chloroform solutions as eluents. Copyright © 2011 Society of Chemical Industry     

基于β-环糊精/SiO_2手性固定相的薄层色谱法拆分DL-萘普生的研究

用β-环糊精(-βCD)键合硅胶合成了一种新型的β-环糊精/S iO2手性固定相,用红外对其进行了结构鉴定。将该手性固定相用于薄层色谱分离萘普生外消旋体,考察多种溶剂对萘普生外消旋体的展开效果,结果表明,乙酸乙酯∶氯仿(体积比)=1∶4为展开剂时,合成的手性固定相对DL-萘普生的分离度为1.45,具有很好的拆分DL-萘普生的能力。     

Synthesis of a novel polymethacrylamide bearing cyclic perfluoroalkyl groups

A novel chiral methacrylamide bearing perfluoropyrrolidino groups was synthesized. Perfluoro(2‐pyrrolidinopropionyl fluoride), the starting material, was prepared by electrochemical fluorination and resolved into enantiomeric derivatives by preparative high performance liquid chromatography (HPLC) performed with optically active 1‐phenethylamine as the diastereomeric counterpart. The polymethacrylamide was obtained by radical polymerization. A clear, colorless, tough film of the polymer was formed by the solution‐casting technique, which showed excellent water repulsion with a contact angle of water greater than 100°. Column packings prepared by the coating of silica gels with the optically active polymer showed potential as the chiral stationary phase for HPLC resolving racemic 1,1′‐bi‐2‐naphthol (separation factor = 1.56) with a hexane–isopropanol mixture as the eluent. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1443–1448, 2002     

非高聚物HPLC手性固定相研究进展

HPLC手性拆分对映体化合物是高效液相色谱的重要研究领域。概述了近年来HPLC中非聚合物手性固定相的研究现状。对此类手性固定相在HPLC中拆分对映体的应用发展作了简要的概述。