衍生化HPLC法测定α-苯乙胺的光学纯度

用4-甲氧基苯甲酸将手性对映体α-苯乙胺衍生化,产生相应的非对映体衍生物.以正己烷、异丙醇或乙醇为流动相,在DNB-pg手性固定相上对α-苯乙胺的对映体衍生物进行了拆分,考察了流动相组成和柱温对该对映体衍生物分离的影响,获得较好的分析条件,分离因子可达1.3以上.该结果进一步与旋光仪方法的测定比较,结果相当一致,相对偏差不超过1.2%.     

β-氨基酸对映体在键合型配体交换色谱固定相上的分离

制备了以L-α-氨基酸为手性配体和球型多孔硅胶为基质的键合型手性配体交换色谱固定相,用于β-氨基酸对映体的拆分。考察了硅胶基质、配体、流动相pH值、中心金属离子浓度和流动相阴离子等因素对5种β-苯丙氨酸对映体分离的影响,由此确立最佳色谱分离条件为以BaseLine硅胶为基质键合L-羟脯氨酸的手性固定相,5.0mmol/L和pH4.6的CuSO4溶液为流动相,紫外检测波长为254nm。在此条件下5种β-氨基酸对映体均可在35min内得到分离,分离因子在1.49~1.77之间。结果表明该方法操作简便,成本低廉,可用于β-氨基酸对映体的分离和分析。     

手性固定相HPLC法直接拆分奈他地尔对映体

以纤维素衍生物为手性固定相,建立药物奈他地尔的HPLC手性分析方法。以正己烷与乙醇或异丙醇为流动相,在Chiralpak AD-H手性固定相上对奈他地尔对映体进行了拆分,并考察了流动相组成、柱温和流速对该对映体分离的影响,获得较优分析条件,分析时间在15 min内,分离度大于1.7。结果表明,奈他地尔对映体在正己烷-异丙醇-二乙胺(80:20:0.1,V:V:V)为流动相、流速为1.0 m L/min、柱温为30℃时,分离效果最佳。本方法操作简单、重现性好,可用于奈他地尔对映体的质量控制。     

手性固定相HPLC法直接拆分奈他地尔对映体EI北大核心CSCD

以纤维素衍生物为手性固定相,建立药物奈他地尔的HPLC手性分析方法。以正己烷与乙醇或异丙醇为流动相,在Chiralpak AD-H手性固定相上对奈他地尔对映体进行了拆分,并考察了流动相组成、柱温和流速对该对映体分离的影响,获得较优分析条件,分析时间在15 min内,分离度大于1.7。结果表明,奈他地尔对映体在正己烷-异丙醇-二乙胺(80:20:0.1,V:V:V)为流动相、流速为1.0 m L/min、柱温为30℃时,分离效果最佳。本方法操作简单、重现性好,可用于奈他地尔对映体的质量控制。     

纤维素键合手性固定相拆分6种萘满酮衍生物对映体

使用Chiralpak IC（纤维素-三（3,5-二氯苯基氨基甲酸酯）共价键合硅胶）手性柱,建立了采用手性固定相高效液相色谱拆分6种 α -芳基萘满酮类衍生物对映体的方法。考察了流动相中有机改性剂的种类和比例、柱温和流速对对映体分离的影响。结果显示6种化合物在异丙醇为改性剂的条件下均可获得较高的对映体分离度。热力学研究表明6种化合物对映体的手性拆分过程均受焓驱动影响,且低温有利于对映体分离。最终推荐分离化合物Ⅰ对映体的流动相是正己烷-异丙醇（90：10,v/v）;分离化合物Ⅱ、Ⅲ、Ⅳ对映体的流动相是正己烷-异丙醇（99：1,v/v）;分离化合物Ⅴ对映体的流动相是正己烷-异丙醇（85：15,v/v）;分离化合物Ⅵ对映体的流动相是正己烷-异丙醇（80：20,v/v）。柱温为25℃,流速为1.0 mL/min。6种化合物对映体均可在Chiralpak IC手性固定相上得到完全分离,证明该色谱柱对6种化合物具有较高的对映体选择性。     

高效液相手性固定相法拆分1-苯乙烯基-3-己基丙炔醇

以纤维素衍生物为手性固定相,建立药物中间体1-苯乙烯基-3-己基丙炔醇对映体的HPLC手性分析方法。以正己烷与乙醇或异丙醇为流动相,在Chiralcel OD-H手性固定相上对1-苯乙烯基-3-己基丙炔醇进行了拆分,并考察了流动相组成、流速和柱温对该对映体分离的影响,获得较优分析条件,分析时间在15 min内,分离度大于1.5。结果表明,1-苯乙烯基-3-己基丙炔醇对映体在正己烷-异丙醇(体积比90:10)为流动相、流速为1.0 m L/min、柱温为25℃时,分离效果最佳。本方法可用于1-苯乙烯基-3-己基丙炔醇对映体的质量控制。     

高效液相色谱手性固定相法拆分克伦特罗对映体

以正己烷、异丙醇为流动相,用Whelk-O1手性固定相成功拆分了药物克伦特罗对映体。出峰时间在5min左右,峰形对称性好,完全达到基线分离,分离因子大于1．4,可用于该对映体药物的分析与制备分离。讨论了二元流动相中异丙醇含量及温度的变化对分离的影响,并对拆分机理进行了探讨。     

β-环糊精流动相添加剂在手性分离中的应用综述

介绍了β-环糊精的基本性质,综述了β-环糊精及其衍生物作为流动相添加剂在高效液相色谱和高效毛细管电泳手性分离中的应用,并探讨了其作为手性流动相添加剂的特点.指出β-环糊精是良好的手性识别体,不仅可作为色谱手性固定相,还可作为流动相添加剂,用于手性对映体的拆分.     

柱前衍生化-HPLC测定仲丁胺对映体的纯度

用3, 5-二硝基苯甲酸对仲丁胺进行柱前衍生, 将其衍生物在CHIRALCEL OD-H手性固定相上拆分, 并通过二极管阵列紫外检测器对其衍生物进行检测, 建立了一种拆分仲丁胺消旋体、测定仲丁胺光学纯度的新方法. 以正己烷和乙醇或异丙醇为流动相, 在CHIRALCEL OD-H手性固定相上对仲丁胺衍生物进行了拆分, 并考察了流动相组成和柱温对该对映体衍生物分离的影响, 获得较好的分析条件, 分离因子大于1.2. 非手性试剂柱前衍生化法测定仲丁胺光学纯度与旋光度方法比较, 结果一致. 方法可用于仲丁胺对映体的质量控制.     

高效液相色谱手性流动相法拆分酮基布洛芬对映体

以Lichrospher C18为分析柱, 将β-环糊精、2,6-二甲基-β-环糊精、2,3,6-三甲基-β-环糊精分别作为手性流动相添加剂, 系统地研究了R,S-酮基布络芬对映体在HPLC系统中的拆分. 建立了以2,3,6-三甲基-β-环糊精为手性流动相添加剂分离R,S-酮基布络芬对映体方法.     

Enantiomer separation by strong anion-exchange capillary electrochromatography with dynamically modified sulfated beta-cyclodextrin

A novel mode of capillary electrochromatography (CEC) based on a dynamically modified stationary phase was presented for chiral separation. The capillary column was packed with strong anion-exchange (SAX) stationary phase packing; the sulfated beta-cyclodextrin (S-CD), which was added to the mobile phase, was dynamically adsorbed to the packing surface. Separation of enantiomers was achieved by their different abilities to form an inclusion complex with the adsorbed S-CD. The enantiomers of tryptophan, praziquantel, atropine, metoprolol, and verapamil were successfully separated in this system with a column efficiency of 36000-412000 plates/m. The resolution value obtained for atropine was as high as 11.23. The superiority of CEC with a dynamically modified stationary phase over that with a physically adsorbed stationary phase was demonstrated. The influence of ionic strength, S-CD concentration, and methanol content on separation was also studied.     

Enantiomer separations by capillary electrochromatography using chiral stationary phases

The applicability of capillary electrochromatography (CEC) using packed capillary column to enantiomer separations was investigated. As chiral stationary phases, OD type packing materials of 5 and 3 microm particle diameters, originally designed for conventional high-performance liquid chromatography (HPLC) were employed. The chiral packing materials were packed by a pressurized method into a 100 microm I.D. fused-silica capillary. Several racemic enantiomers, such as acidic, neutral and basic drug components, were successfully resolved, typically by using acidic or basic solutions containing acetonitrile as mobile phases. The separation efficiencies for some enantiomers in the chiral CEC system using the 5 microm OD type packing were superior to those obtained in HPLC using chiral packings. The plate heights obtained for several enantiomers were 8-13 microm or the reduced plate height of 1.6-2.6, which indicates the high efficiency of this chiral CEC system.     

Vancomycin degradation products as potential chiral selectors in enantiomeric separation of racemic compounds

This review discusses the use of vancomycin-related substances as potential chiral stationary phase that can be used as a packing material for the enantioselective separation of various racemic compounds in various modalities including HPLC, CE and also as chiral mobile phase additives. The chiral recognition mechanisms involved including the role of dimerization are presented.     

吸附固定相电色谱和动态改性电色谱的手性分离

对动态改性电色谱手性分离进行了研究。电色谱柱填充强阴离子交换固定相（SAX0,添加在流动相中的磺化β－环糊精（S－CD）动态地吸陵于SAX填料表面,形成一层准手性固定相。色氨酸、阿托品和异博定对映体在本体系获得了很好的分离,它们的分离分别为2．06,10．1和1．96,对映体峰的柱效价于85,000塔板数／米和412,000塔板数／米之间。连续运行17次,死时间和色氨酸对映体的电色谱保留因子的相对标准偏差分别为0．53％,0．62％和0．69％。此外,以吸附于SAX填料的牛血清白蛋白和S－CD为手性固定相进行了电色谱手性分离的研究。在这两种体系下分离色氨酸对映体的分离度分别为3．86和2．97。吸附S－CD柱电色谱和动态改性电谱的重现性进行子比较,发现动态改性电色谱有更好的重现性。     

高效液相色谱法测定手性四面体金属簇合物对映体过量值

在自制的直链淀粉-三(苯基氨基甲酸酯)(ATPC)高效液相色谱手性固定相(HPLC—CSP)上，优化了手性四面体金属簇合物的手性分离条件，测定了不同合成条件下得到的手性四面体金属族合物CoMo(C0)5C5H4C(O)CH3(μη^2-HC≡CCH2OH)的对映体过量值(e.e)。结果表明：高效液相色谱手性固定相法是拆分这类化合物的一种理想方法。     

Recent progress in enantiomer separation by capillary electrochromatography

Enantiomer separation by electrochromatography (CEC) can be performed in three modes: (i) open-tubular capillary electrochromatography (o-CEC), in which the chiral selector is physically adsorbed coated, and thermally immobilized or covalently attached to the internal capillary wall; (ii) packed capillary electrochromatography (p-CEC), in which the capillary is either filled with chiral modified silica particles or with an achiral packing material, and a chiral selector is added to the mobile phase; and (iii) monolithic (rod)-capillary electrochromatography (rod-CEC) in which the chiral stationary phase (CSP) consists of a single piece of porous solid. We present an overview on methods and new trends in the field of electrochromatographic enantiomer separation such as CEC with either nonaqueous mobile phases or stationary phases with incorporated permanent charges, or with packing beds consisting of nonporous silica particles or particles with very small internal diameters.     

Chiral separation of beta-adrenergic antagonists, profen non-steroidal anti-inflammatory drugs and chlorophenoxypropionic acid herbicides using teicoplanin as the chiral selector in capillary liquid chromatography

Three groups of structurally diverse chiral compounds were used to study the interaction mechanism responsible for stereoselective recognition with teicoplanin as chiral selector in capillary liquid chromatography. Teicoplanin-based chiral stationary phase (CSP) was used. The effect of the variation of mobile phase composition on retention and enantioselective separation was studied. The mobile phase composition suitable for enantioresolution of the various chiral compounds differed according to the interaction forces needed for chiral recognition. Mobile phases with high buffer portion (70-90 vol.%) were preferred for separation of enantiomers of profen non-steroidal anti-inflammatory drugs and chlorophenoxypropionic acid herbicides that require hydrophobic interactions, inclusion and pi-pi interactions for stereoselective recognition with teicoplanin. Higher concentration triethylamine in the buffer (0.5-1.0%) increased resolution of these acids. On the other hand, H-bonding and electrostatic interactions are important in stereoselective interaction mechanism of beta-adrenergic antagonists with teicoplanin. These interaction types predominate in the reversed phase separation mode with high organic modifier content (95% methanol) and in polar organic mobile phases. For this reason beta-adrenergic antagonists were best enantioresolved in the polar organic mode. The mobile phase composed of methanol/acetic acid/triethylamine, 100/0.01/0.01 (v/v/v), provided enantioresolution values of all the studied beta-adrenergic antagonists in the range 1.1-1.9. Addition of teicoplanin to the mobile phase, which was suitable for enantioseparation of certain compounds on the CSP, was also investigated. This system was used to dispose of nonstereoselective interactions of analytes with silica gel support that often participate in the interaction with CSPs. Very low concentration of teicoplanin in the mobile phase (0.1 mM) resulted in enantioselective separation of 2,2- and 2,4-chlorophenoxypropionic acids.     

酸性外消旋联苯类药物在纤维素-三(3,5-二甲基苯基氨基甲酸酯)固定相上的直接拆分

 合成了纤维素 三 ( 3,5 二甲基苯基氨基甲酸酯 ) (CDMPC)衍生物 ,并将其涂敷于自制的球形硅胶上 ,制备出用于高效液相色谱手性拆分的固定相。在正相条件下 ,用该固定相对 5种酸性外消旋联苯类药物进行了直接拆分 ,并考察了流动相组成和样品结构对保留和拆分的影响 ,讨论了固定相对样品的作用模式。结果表明 ,在正己烷 /异丙醇流动相体系中加入少量三氟乙酸 ,可对外消旋羧酸类化合物进行有效的手性拆分。     

酸性外消旋联苯类药物在纤维素-三(3,5-二甲基苯基氨基甲酸酯)固定相上的直接拆分

合成了纤维素 三 ( 3,5 二甲基苯基氨基甲酸酯 ) (CDMPC)衍生物 ,并将其涂敷于自制的球形硅胶上 ,制备出用于高效液相色谱手性拆分的固定相。在正相条件下 ,用该固定相对 5种酸性外消旋联苯类药物进行了直接拆分 ,并考察了流动相组成和样品结构对保留和拆分的影响 ,讨论了固定相对样品的作用模式。结果表明 ,在正己烷 /异丙醇流动相体系中加入少量三氟乙酸 ,可对外消旋羧酸类化合物进行有效的手性拆分。     

麦草伏甲酯对对映体的高效液相色谱分离

手性分离;麦草伏甲酯对对映体的高效液相色谱分离