Lin Chun, Fan Jun, Liu Wen-na, Tan Yi, Zhang Wei-guang
School of Chemistry and Environment, South China Normal University, Guangzhou 510006, China.
School of Chemistry and Environment, South China Normal University, Guangzhou 510006, China.
J Pharm Biomed Anal. 2014 Sep;98:221-7. doi: 10.1016/j.jpba.2014.05.032. Epub 2014 May 29.
Two new cyclodextrin-derived chiral stationary phases with multiple urea linkages were prepared through the Staudinger reactions between aminopropyl silica gel and cyclodextrin derivatives, namely, heptakis(6-azido-6-deoxy-2,3-di-O-3,5-dimethylphenylcarbamoylated)-β-cyclodextrin and heptakis(6-azido-6-deoxy-2,3-di-O-3,5-dichlorophenylcarbamoylated)-β-cyclodextrin, respectively. HPLC separation behaviors toward 46 chiral analytes have been investigated under multimodal elution. They exhibited good separation performances for these analytes and also showed some complimentary enantioselectivity to each other, due to different electron-donating (methyl)/withdrawing (chlorine) groups in the phenylcarbamate moieties. Among these analytes, aromatic alcohols and N-(2,4-dinitrophenyl)-derived carboxylic acids were better resolved on the π-basic chiral stationary phase than the π-acidic. The proton pump inhibitors, the 5-hydroxytryptamine receptor antagonists, and the analytes with carbonyl groups easily formed stereoselective interactions with the π-acidic chiral stationary phase, further leading to better enantioseparation. Elution order reversal for palonosetron and N-(2,4-dinitrophenyl) glutamine was observed in three chiral stationary phases, probably induced by the difference of phenylcarbamate groups. Moreover, mobile phase effects on retention behaviors of analytes have been studied in detail.
通过氨丙基硅胶与环糊精衍生物（即分别为七（6-叠氮基-6-脱氧-2,3-二-O-3,5-二甲基苯基氨基甲酰化）-β-环糊精和七（6-叠氮基-6-脱氧-2,3-二-O-3,5-二氯苯基氨基甲酰化）-β-环糊精）之间的施陶丁格反应，制备了两种具有多个脲键的新型环糊精衍生手性固定相。研究了在多模式洗脱条件下，这两种固定相对46种手性分析物的HPLC分离行为。由于苯基氨基甲酸酯部分中不同的供电子（甲基）/吸电子（氯）基团，它们对这些分析物表现出良好的分离性能，并且彼此之间还表现出一些互补的对映体选择性。在这些分析物中，芳香醇和N-（2,4-二硝基苯基）衍生的羧酸在π-碱性手性固定相上的分离效果比在π-酸性固定相上更好。质子泵抑制剂、5-羟色胺受体拮抗剂以及带有羰基的分析物容易与π-酸性手性固定相形成立体选择性相互作用，从而进一步实现更好的对映体分离。在三种手性固定相中观察到帕洛诺司琼和N-（2,4-二硝基苯基）谷氨酰胺的洗脱顺序发生了反转，这可能是由苯基氨基甲酸酯基团的差异引起的。此外，还详细研究了流动相对分析物保留行为的影响。
