高效液相色谱手性流动相添加法拆分阿替洛尔对映体

采用C18固定相,以磺丁基醚-β-环糊精为手性流动相添加剂,提出了阿替洛尔对映体的高效液相色谱拆分方法。选用KromasilC18色谱柱(250mm×4.6mm,5μm),流动相为含20mmol.L-1磺丁基醚-β-环糊精的pH8.2的10mmol.L-1磷酸盐缓冲溶液-甲醇-乙腈(60+35+5),紫外检测波长275nm,柱温为25℃,进样量20μL,流量为0.5mL·min-1时,分离度达到1.63。     

高效液相色谱法分离药物对映体中手性流动相添加剂的应用

综述了近年来手性流动相添加剂在高效液相色谱拆分对映体中的应用,阐述了各类手性流动相添加剂的拆分机理及其在药物分析中的应用,引用文献52篇.     

Chiralcel OD-RH手性柱拆分卡维地洛对映体

采用Ch iralcelOD-RH(纤维素3,5-二甲基苯基氨基甲酸酯)手性固定相高效液相色谱法研究了乙腈-高氯酸钠缓冲盐体系对卡维地洛的手性拆分情况,讨论了流动相的各个因素(有机相的种类和比例、缓冲盐浓度、酸度等)对手性拆分的影响。在乙腈-高氯酸钠缓冲盐(pH 5.5,50 mmol/L)的体积比为35∶65的色谱条件下,卡维地洛对映体获得了基线分离。     

Separation of Enantiomers of Isochromene Derivatives by HPLC Using Cyclodextrin-Based Stationary Phases

Twenty chiral isochromene derivatives have been chromatographed on native and derivatized cyclodextrin stationary phases using HPLC. The most effective CSPs for the enantioresolution of these analytes in the reverse phase mode are the hydroxypropyl--cyclodextrin (Cyclobond RSP), the 2,3-dimethyl--cyclodextrin (Cyclobond DM), and the -cyclodextrin (Cyclobond II) stationary phases. The -cyclodextrin (Cyclobond III), -cyclodextrin (Cyclobond I), acetyl--cyclodextrin (Cyclobond AC), S-1-naphthylethyl carbamate--cyclodextrin (Cyclobond SN), and 3,5-dimethylphenyl carbamate--cyclodextrin (Cyclobond DMP) stationary phases also show enantioselectivities for some analytes. No enantioseparations were observed in the polar organic mode and only a few separations were found in the normal phase mode. The Cyclobond RSP CSP provided the best overall separations of these analytes in the reverse phase mode. The pH of the mobile phase and the nature of organic modifiers have little effect on the enantioresolution. The substituents on the isochromene ring greatly affect the chiral recognition.     

高效液相色谱手性流动相添加剂法拆分头孢羟氨苄对映体

以羟丙基-β-环糊精(HP-β-CD)为手性流动相添加剂,提出了头孢羟氨苄对映体的高效液相色谱拆分方法。选用SinoChromODS-BP色谱柱(4.6mm×200mm,5μm),含16mmol.LHP-β-CD的甲醇-乙腈-水(10+10+80)混合溶液为流动相,pH为4.93,流速为0.30mL·min-1,紫外检测波长为232nm,进样量为10μL。试验结果表明:该法可使头孢羟氨苄的两对对映体得到良好的分离,分离度分别为1.51,1.53。     

高效液相色谱-手性流动相添加法拆分高精氨酸对映体

以L-苯丙氨酸-铜(Ⅱ)络合物作为流动相的手性添加剂,提出了高精氨酸对映体的高效液相色谱拆分方法。选用Waters Atlantis C_(18)色谱柱,流动相为pH 2.8的含0.71mmol·L~(-1)L-苯丙氨酸-0.351mmol·L~(-1)硫酸铜的甲醇-水(20+80)溶液,紫外检测波长为200nm,进样量20μL,流量为0.5 mL·min~(-1)时,高精氨酸对映体得到良好的分离,分离度达到1.8。L-高精氨酸和D-高精氨酸的峰面积与其质量浓度分别在2.00～72.05mg·L~(-1)和3.00～60.23mg·L~(-1)范围内呈线性关系,检出限(3S/N)分别达到1.0mg·L~(-1)和1.5mg·L~(-1)。     

纤维素类手性固定相高效液相色谱法拆分三唑类手性化合物

采用纤维素-三(3,5-二甲基苯基氨基甲酸酯)手性固定相(Chiralcel OD)和纤维素-三(4-甲基苯基甲酸酯)手性固定相(Chiralcel OJ),在正相高效液相(N-HPLC)模式下,基线拆分了两个系列共13个结构类似的三唑类手性化合物,结果发现,当手性固定相(Chiral Stationary Phase,CSP)可以与溶质分子之间形成较强氢键时,Chiralcel OD的手性识别能力明显优于Chiraleel OJ,当手性固定相(CSP)与溶质分子之间不能或难于形成氢键时,两种CSP的手性拆分能力相似;提高流动相中极性改性剂的极性有利于手性化合物的拆分。在反相高效液相(R-HPLC)模式下,共基线拆分了8个三唑类手性化合物,实验发现,OJ-CSP的手性拆分能力明显优于OD-CSP．它们对对映体分子的选择性主要受CSP与溶质分子间的π-π相互作用的影响。     

Chiral Separation of 4-Iminoflavan Derivatives on Several Polysaccharide-Based Chiral Stationary Phases by HPLC

The HPLC enantiomeric separation of seven 4-iminoflavans was successfully accomplished in the normal phase mode using six polysaccharide-based chiral stationary phases namely, Chiralcel^®OD-H, Chiralcel^®OD, Chiralcel^®OJ, Chiralpak^®AD, Chiralpak^®IA and Chiralpak^®IB under normal and polar organic phase modes. The resolution depended on nature and concentration of alcoholic modifier. The results demonstrate clearly that the chromatographic system based on the coated and immobilized type Chiralpak^®IB and Chiralcel^®OD-H CSPs provide a powerful analytical tool for enantiomeric separation of all the 4-iminoflavans used in this study.

     

Chiral Separation of 4-Iminoflavan Derivatives on Several Polysaccharide-Based Chiral Stationary Phases by HPLC

The HPLC enantiomeric separation of seven 4-iminoflavans was successfully accomplished in the normal phase mode using six polysaccharide-based chiral stationary phases namely, Chiralcel^®OD-H, Chiralcel^®OD, Chiralcel^®OJ, Chiralpak^®AD, Chiralpak^®IA and Chiralpak^®IB under normal and polar organic phase modes. The resolution depended on nature and concentration of alcoholic modifier. The results demonstrate clearly that the chromatographic system based on the coated and immobilized type Chiralpak^®IB and Chiralcel^®OD-H CSPs provide a powerful analytical tool for enantiomeric separation of all the 4-iminoflavans used in this study.     

反式第一菊酸对映体的手性选择剂立体选择性分离

研究反式第一菊酸(trans-CA)对映体在含有手性选择剂酒石酸酯的水-有机相双相体系中的萃取分配行为,考察有机相的种类、酒石酸酯烷基链长度、水相的pH值和酒石酸酯的浓度对分配系数K和分配因子α的影响.研究结果表明:1,2-二氯乙烷作为有机相效果较好,D-酒石酸酯与( )-反式第一菊酸对映体形成的复合物稳定性比与(-)-反式第一菊酸对映体形成的复合物稳定性要大,而L-酒石酸酯的萃取性能与此相反,它与(-)-反式第一菊酸对映体形成的复合物稳定性比与( )-反式第一菊酸对映体形成的复合物稳定性要大.酒石酸酯取代烷基链长对分配系数K和分离因子α有很大影响;分配系数K和分离因子α均随pH的升高而降低;分配系数K随着酒石酸酯浓度的增大而增大,分离因子α先随浓度增大而稳定上升,后随浓度增大而缓慢下降.     

键合型纤维素-苯基氨基甲酸酯手性固定相的制备及用于对映异构体拆分

采用化学键合法,利用4,4′-二苯基甲基二异氰酸酯作间隔臂,通过纤维素葡萄糖单元上2、3或6-位上的羟基将纤维素衍生物键合在氨丙基硅胶上,制备了键合型纤维素-苯基氨基甲酸酯手性固定相.同时,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,并以未修饰的硅胶为载体,制备了涂敷型纤维素-三苯基氨基甲酸酯手性固定相.分别对键合型和涂敷型两类手性固定相进行了表征,并首次在纤维素-苯基氨基甲酸酯手性柱上拆分了安息香.     

键合型纤维素—苯基氨基甲酸酯手性固定相的制备及用于对映异构？…

采用化学键合法,利用４,４′－二苯基甲基二异氰酸酯作间隔臂,通过纤维素葡萄糖单元上２、３或６－位上的羟基将纤维素衍生物键合在氨丙基硅胶上,制备了键合型纤维素－苯基氨基甲酸酯手性固定相。同时,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,并以未修饰的硅胶为载体,制备了涂敷型纤维素－三苯基氨基甲酸酯手性固定相。分别对键合型和涂敷型两类手性固定相进行了表征,并首次在纤维素－苯基氨基甲     

手性化合物的毛细管胶束电动色谱分离研究

以4种不同的N-长链烷酰-L-氨基酸胶束为手性选择剂,对3种不同性质的手性化合物(α-氯代丙酰替苯胺,2-氨基-3-对硝基苯基-1,2-丙二醇和华法林)的毛细管胶束电动色谱分离进行研究.结果表明,手性表面活性剂中不同的氨基酸残基和烷基链的长度对分离影响较大;随手性表面活性剂浓度增加,溶质保留时间增大,分离度增加,不同溶质的最佳分离浓度在100～150mmol/L之间;pH对电中性手性化合物分离影响不大,但对酸性或碱性手性化合物的分离影响较大.在选定的条件下,3种样品均在20min内完全分离,分离柱效达1×10⁵理论板数/m.     

联萘类对映体的手性薄层色谱拆分

以β－环糊精／硅胶键合相作薄层色谱的手性固定相,石油醚／乙酸乙酯／甲醇和石油醚／乙酸乙酯／乙腈溶剂系统为流动相,分离联萘类化合物对映体,在紫外光下或碘蒸汽中观察样品斑眯的位置。１２对联萘类化合物得到良好的分离,相对比移植为１．１６－１．６５。     

二氧异丙嗪对映体的毛细管电泳分离

本文报道一种以β－环糊精为手性分离试剂，毛细管电泳分离二氧异丙嗪对映体的新方法，详细研究了溶液ｐＨ值，β－环糊精浓度和电解质浓度等对二氧异丙嗪对异体分离的影响。     

丙吡胺对映异构体的毛细管电泳手性拆分

目前市场上销售的手性合成药物,大多以外消旋体形式面市。但在药物外消旋体的两个对映体中,只有一个对映体对生物体具有活性和治疗作用,另一个对映体则是非活性或具有毒副作用,表现出不同的疗效和毒理学性能,因而手性化合物的拆分在药物、临床及生命科学中具有十分重要的意义。丙吡胺(分子结构见图1),又称双异丙吡胺、吡二丙胺、达舒平,是广谱抗心律失常药。其电生理、血流动力学和抗心律失常作用与奎尼丁相似,     

涂敷纤维素类手性固定相对甲霜灵中间体的高效液相色谱拆分

通过在自制的球形氨丙基硅胶上涂敷纤维素－三（3，5－二甲基苯基氨基甲酸酯）（CDMPC）制备了手性固定相，并采用该手性固定相成功地对甲霜灵中间体进行了高效液相色谱拆分；考察了由不同比例的正己烷和异丙醇组成的流动相对甲霜灵中间体分离效果的影响。     

Chiral HPLC Separation on Derivatized Cyclofructan Versus Cyclodextrin Stationary Phases

Cyclodextrins (CDs) and cyclofructans (CFs) are chiral cyclic oligosaccharides. While β-CD is composed of seven glucopyranose units forming rigid cavity, hydrophobic inside, CF6 and CF7, contain six and seven fructofuranose units, respectively, creating a polar crown ether core. These basic structures can be easily derivatized to form even more potential chiral selectors that enable enantioselective separation of various chiral compounds. Chiral stationary phases (CSPs) based on CFs and CDs that were derivatized with the same derivatization group, either dimethylphenyl or R-naphthylethyl, were compared. A set of analytes with different interaction possibilities was used for characterization of retention and enantioseparation abilities of these CSPs in normal separation mode of HPLC. The results showed that both cyclic oligosaccharide structure and derivatization group influenced the retention/separation behavior of analytes. Complementary enantioseparations were obtained for some analytes.     

Analytical Separation of Closantel Enantiomers by HPLC

Closantel is an antiparasitic drug marketed in a racemic form with one chiral center. It is meaningful to develop a method for separating and analyzing the closantel enantiomers. In this work, two enantiomeric separation methods of closantel were explored by normal-phase high-performance liquid chromatography. The influences of the chiral stationary phase (CSP) structure, the mobile phase composition, the nature and proportion of different mobile phase modifiers (alcohols and acids), and the column temperature on the enantiomeric separation of closantel were investigated in detail. The two enantiomers were successfully separated on the novel CSP of isopropyl derivatives of cyclofructan 6 and n-hexane-isopropanol-trifluoroacetic acid (97:3:0.1, v/v/v) as a mobile phase with a resolution (Rs) of about 2.48. The enantiomers were also well separated on the CSP of tris-carbamates of amylose with a higher Rs (about 3.79) when a mixture of n-hexane-isopropanol-trifluoroacetic acid (55:45:0.1, v/v/v) was used as mobile phase. Thus, the proposed separation methods can facilitate molecular pharmacological and biological research on closantel and its enantiomers.