红霉素作为手性选择剂对手性药物的毛细管电泳拆分

以大环内酯类抗生素红霉素作为手性选择剂，在普通熔融石英毛细管上对两种酸性联苯双酯类保肝的性药物进行了毛细管电泳手性拆分研究；当用30mmol/L的红霉素、50mmol/L的磷酸盐体系（pH=6.0，含50％（Φ）的甲醇）时两种手性化合物的分离度分别为3.11和8.28，证明红霉素可以作为一种新的手性选择剂应用于毛细和泳手性分离中；通过实验研究了缓冲液种类及浓度、红霉素浓度、分离电压及温度、样品载入量、有机添加剂种类及含量对手性分离的影响。     

手性药物山莨菪碱的毛细管电泳拆分研究

以新型环糊精衍生物单3-O-苯基胺甲酰基-β-CD为手性选择剂,用毛细管区带电泳法对手性药物山莨菪碱进行了拆分。考察了手性选择剂浓度、缓冲液pH值和浓度及有机溶剂对拆分的影响。结果表明,手性选择剂浓度和缓冲液pH值是影响药物对映体分离的重要因素,有机溶剂亦对分离有很大影响。单3-O-苯基胺甲酰基-β-CD对山莨菪碱的分离度为2．16。     

新型环糊精衍生物单6-O-苯基胺甲酰基-β-环糊精的合成及其在手性药物毛细管区带电泳拆分中的应用

合成了新型的环糊精衍生物单6-O-苯基胺甲酰基—β-环糊精，并对合成产物进行了表征。以新型环糊精衍生物为手性选择剂，考察了手性选择剂浓度、缓冲液PH值和浓度及有机溶质对8种手性药物对映体的毛细管电泳分离的影响。结果表明：手性选择剂浓度和缓冲液PH值是影响药物对映体分离的重要因素，有机溶质亦对分离有很大影响。单6-O-苯基胺甲酰基—β-环糊精能使所研究的8种手性药物中的5种达基线分离，3种达部分分离。而在同样条件下．β-环糊精仅能使上述药物中的菜心安达部分分离(及。＝0．67)，这说明我们合成的环糊精衍生物手性拆分能力要强于天然环糊精。我们还就单6-O-苯基胺甲酰基-β-环糊精对手性药物可能的拆分机理进行了探讨。     

氨氯地平对映体的高效毛细管电泳手性拆分

建立了氨氯地平对映体的高效毛细管电泳手性拆分方法。考察了背景电解质的PH值和浓度，手性选择剂浓度，有机改性剂种类及浓度对分离的影响，对分离条件进行了优化。结果表明，在含30mg/mL羟丙基-β-CD（HP－β-CD）和10％甲醇的40mmol/L Tris-H3PO4(pH2.5)体系中，对映体达到基线分离，分离度（Rs)为3．4。     

水为洗脱液在表面活性剂胶束涂层固定相上分离手性药物

讨论了手性固定相稳定的条件，以表面活性剂胶束涂层为固定相，纯水作流动相，对氨氯地平，麻黄碱，伪麻黄碱，芬必得，美西律平和扑尔敏等外消旋药物进行了手性拆分，探索了手性药物氨地平及麻黄碱，伪麻黄碱的分离条件，当流动相的PH值为5．5时分离效果最佳，在流动相中加入2.5-5mmol/L硼酸时分离因子较大。     

红霉素作为毛细管区带电泳手性选择剂拆分两种联苯双酯类药物

首次使用大环内酯类抗生素红霉素作为毛细管电泳手性选择剂,采用未涂层石英毛细管分离了两种联苯双酯类保肝药物。实验考察了背景电解质中磷酸盐缓冲液的pH值及浓度、分离电压及温度、红霉素浓度、有机添加剂甲醇含量对手性分离的影响。实验结果表明,磷酸盐浓度为50 mmol/L(pH 5.0)、分离电压为-20 kV、红霉素浓度为30 mmol/L、甲醇的体积分数为50%是最佳分离条件。同时证明红霉素可以作为手性选择剂用于毛细管电泳手性分离中。     

手性化合物

手性问题与我们的生活密切相关，它涉及到生命、动植物、药物、食品、香料、农药等诸多领域，本文介绍了手性化合物的一些性质、手性药物、手性化合物的拆分、尤其是手性化合物的现代色谱分离方法。     

涂层技术在毛细管电泳手性分离中的应用

手性是自然界的本质属性之一。手性分离分析技术对生命科学、环境科学、生物工程和药物工程等许多学科都具有十分重要的意义。当前,对不同种类手性化合物进行拆分已成为毛细管电泳技术最具特色的研究和应用领域之一。然而,被分析物(或拆分剂)在毛细管内壁的吸附是毛细管电泳手性分离中的常见问题。涂层技术就是采用不同的方法对毛细管内壁进行改性,是抑制非特异性吸附、提高分离效率及分离重现性最简便和最有效的方法。本文主要综述了近十几年来各种涂层技术在毛细管电泳手性分离领域的应用现状,并对毛细管涂层技术今后的发展进行了展望。     

新霉素作为手性选择剂对两种酸性药物的毛细管电泳手性拆分

以新霉素为手性选择剂,在硼酸盐缓冲溶液中分离了两种联苯双脂类酸性手性药物,并获得了很高的分离度;本文还通过考察手性选择剂的浓度、背景电解质的pH和有机添加剂等影响因素对两种药物手性分离的影响,优化了分离条件;实验表明,当新霉素浓度为30mmol/L,在20mmol/L、pH为7.5的硼酸盐缓冲溶液中添加10％(φ)的甲醇时,能够使两种手性药物达到最佳分离。     

高效毛细管电泳同时拆分外消旋头孢他啶及头孢曲松钠

用毛细管电泳β－环糊精（β－CD）添加剂法同时拆分外消旋头孢他啶及头孢曲松钠，主要考察了影响分离和测定的因素：（β－CD浓度，背景电解质的pH值，分离电压和毛细管的柱温。通过优化得到了毛细管电泳手性分离头孢他啶及头孢曲松钠对映体的实验方法，在280nm处进行紫外检测，分离温度为25℃，压力进样6s，分离电压为28kV，背景缓冲液含50mmol/L磷酸二氢钠、0.4mmol/Lβ－环糊精（β-CD）、3.0mmol/L（三羟甲基）氨基甲烷（Tirs),pH为7.15的条件下，头孢他啶及头孢曲松钠同时能达到基线分离。对其拆分机理进行了探讨。     

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。     

新型聚合物多孔涂层毛细管开管柱的制备及电色谱研究

以甲基丙烯酸缩水甘油酯(GMA)和乙二醇二甲基丙烯酸酯(EDMA)为前驱体制备了新型聚合物多孔涂层毛细管开管(PLOT)柱固定相。通过优化聚合反应时间、致孔剂比例及交联剂比例获得了色谱性能良好的PLOT柱,扫描电镜结果显示毛细管柱内的多孔涂层厚度适中且均匀。在毛细管电色谱模式下,PLOT柱以反相色谱分离机理有效分离了中性、酸性和碱性小分子。人血清白蛋白(HSA)共价结合的蛋白亲和PLOT柱对5对手性对映体实现了较好的分离,且其分离度远高于HSA修饰的单层聚合物毛细管开管柱。PLOT柱分离烷基苯的日内、日间和柱间的相对标准偏差分别小于1.7%、4.8%和7.8%。     

牛血清白蛋白手性毛细管整体柱的制备及对映体的分离

A silica-bonded bovine serum albumin (BSA) chiral monolithic stationary phase for capillary electrochromatography(CEC) was introduced. An inorganic-organic hybrid monolithic column was firstly prepared by sol-gel chemistry with homogeneously distributed aminopropyl groups throughout the silica matrix. Then the chiral stationary phase was synthesized by the in situ covalent immobilization of BSA on the monolithic column activated with glutaraldehyde. The effects of pH value and concentration of phosphate buffer on the separation of D,L-tryptophan were investigated. The separation factor of D,L-tryptophan reached 3.37 on CEC mode.     

温度对蛋白和β-环糊精手性固定相拆分对映体的影响

 采用三聚氯氰为活化剂分别合成了牛血清白蛋白 (BSA)、人血清白蛋白 (HSA)和 β 环糊精手性固定相 ,研究了温度在色氨酸 ,华法令 ,酮基布洛芬和丹酰化苏氨酸手性拆分中的影响。结果表明 ,在蛋白手性固定相上对映体间的熵变对色氨酸 ,华法令和酮基布洛芬的拆分有很大的影响 ,而丹酰化苏氨酸对映体在 β 环糊精手性固定相上的拆分为典型的焓控过程 ,与蛋白柱有着不同的热力学特性。由于键合方式不同 ,色氨酸在我们合成的BSA手性固定相上的最佳分离温度为 35℃左右 ,而不是文献报道的以戊二醛为活化剂的 2 4℃。     

Enantiomer separation of drugs by capillary electrophoresis using proteins as chiral selectors

The separation of drug enantiomers using proteins as the chiral selectors in capillary electrophoresis (CE) is considered in this review. The proteins used include albumins such as bovine serum albumin, human serum albumin and serum albumins from other species, glycoproteins such as alpha1-acid glycoprotein, crude ovomucoid, ovoglycoprotein, avidin and riboflavin binding protein, enzymes such as fungal cellulase, cellobiohydrolase I, pepsin and lysozyme and other proteins such as casein, human serum transferrin and ovotransferrin. Protein-based CE is carried out in two modes: in one proteins are immobilized or adsorbed within the capillary, or protein-immobilized silica gels are packed into the capillary (affinity capillary electrochromatography mode), and in the other proteins are dissolved in the running buffer (affinity CE mode). Furthermore, the advantages and limitations of the two modes and the factors affecting the chiral separations of various drugs by protein-based CE are discussed.     

Chiral separation of the β2‐sympathomimetic fenoterol by HPLC and capillary zone electrophoresis for pharmacokinetic studies

The development of methods for the separation of the enantiomers of fenoterol by chiral HPLC and capillary zone electrophoresis (CZE) is described. For the HPLC separation precolumn fluorescence derivatization with naphthyl isocyanate was applied. The resulting urea derivatives were resolved on a cellulose tris(3,5‐dimethylphenylcarbamate)‐coated silica gel column employing a column switching procedure. Detection was carried out fluorimetrically with a detection limit in the low ng/mL range. The method was adapted to the determination of fenoterol enantiomers in rat heart perfusates using liquid–liquid extraction. As an alternative a CE method was used for the direct separation of fenoterol enantiomers comparing different cyclodextrin derivatives as chiral selectors. Copyright © 2010 John Wiley & Sons, Ltd.     

手性有序无机介孔硅用作气相色谱固定相

手性介孔材料在手性分离、不对称催化、手性传感等领域具有广泛的应用价值。手性有序无机介孔硅是一类介孔结构高度有序、不含有机成分的手性材料。该文采用D-苯丙氨酸为手性源合成手性有序无机介孔硅(COIMS),将其用聚硅氧烷(OV-1701)稀释后用作固定相制备毛细管气相色谱手性柱,并对该手性柱的分离性能进行了考察,8种手性化合物在该手性柱上得到了拆分。COIMS柱对直链烷烃、醇的分离也表现出良好的选择性。该柱还具有分析时间短、在较高温度下测定稳定等优点,其具有开发成高温手性固定相的潜力。     

A chiral porous organic cage for molecular recognition using gas chromatography

Molecular organic cages as shape-persistent organic molecules with permanent and accessible cavities have attracted a lot of interest because of their importance as host-guest systems. Herein, we report a chiral porous organic cage (POC) CC9 diluted with a polysiloxane OV-1701 to fabricate a CC9-coated capillary column, which was used for the high-resolution gas chromatographic separation of organic compounds, including positional isomers and racemates. On the CC9-coated capillary column, a large number of racemic compounds such as chiral alcohols, esters, ethers and epoxides can be resolved without derivatization. By comparing the chiral recognition ability of the CC9-coated column with the commercially available β-DEX 120 column and the POC CC3-R coated column recently reported by our group, the CC9-coated column offered good resolution during the separation of some racemates, that were not separated using the β-DEX 120 column or POC CC3-R coated column. Therefore, the CC9-coated column can be complementary to the β-DEX 120 column and CC3-R coated column. The results indicated that the CC9-coated column exhibited great potential for application in the separation of positional isomers and enantiomers with great selectivity, high resolution and good reproducibility.     

A mesoporous silica nanoparticles immobilized open-tubular capillary column with a coating of cellulose tris(3,5-dimethylphenyl-carbamate) for enantioseparation in CEC

An approach of immobilizing mobile crystalline material (MCM)-41 mesoporous silica nanoparticles on the inner wall of an open-tubular (OT) capillary as the support for coating chiral selector of cellulose tris(3,5-dimethylphenyl-carbamate) (CDMPC) was carried out. By taking advantage of the improved phase ratio of OT capillary with the immobilization of MCM-41 mesoporous material, the cellulose derivative of CDMPC as the chiral selector was simply coated on the MCM-41 nanoparticle layer via the hydrogen-bonding interaction, and the enantioseparation was successively carried out. Eight pairs of acidic, neutral and basic enantiomers were resolved in capillary electrochromatography or capillary liquid chromatography mode. The concentration of CDMPC for coating was systematically investigated to obtain the optimized chromatographic properties on enantioseparation by controlling the supposed film thickness of CDMPC on MCM-41 nanoparticle layer. Comparing with a bare fused silica capillary column coated with CDMPC under the same coating procedure as MCM-41-modified capillary did, the MCM-41-modified capillary column offered much higher enantioselectivity. This result indicated the significance of using the mesoporous nanoparticles as the electrochromatographic support to enhance the phase ratio of OT capillary column in capillary electrochromatography and capillary liquid chromatography. For investigating the effect of experimental conditions on the enantioseparation with this prepared OT capillary column, the content of organic modifier acetonitrile in the mobile phase was thus extensively evaluated to achieve a better chiral separation.     

A β-cyclodextrin covalent organic framework used as a chiral stationary phase for chiral separation in gas chromatography

Chiral covalent organic frameworks(CCOFs) featuring chirality, stability, and good porosity have attracted a considerable amount of attention due to their important applications, such as asymmetric catalysis, chiral separation, and chiral recognition. In this study, a β-cyclodextrin(β-CD) covalent organic framework(β-CD-COF) diluted with polysiloxane OV-1701 was explored as a novel chiral stationary phase(CSP) for gas chromatography(GC) separation of racemates. The β-CD-COF coated capillary colu...