奎宁-冠醚组合型手性固定相直接拆分氨基酸的机理  

Separation mechanism of chiral stationary phase based on quinine and crown ether for the direct stereoselective separation of amino acids

作　　者：吴海霞[1] 王东强[1] 赵见超 柯燕雄[1] 梁鑫淼[1,2] 

机构地区：[1]华东理工大学药学院,上海200237 [2]中国科学院大连化学物理研究所,辽宁大连116023

出　　处：《色谱》2016年第1期62-67,共6页Chinese Journal of Chromatography

基　　金：国家自然科学基金项目(21375038)~~

摘　　要：合成了一种新型奎宁-冠醚组合型手性固定相(QN-CR CSP)并用于氨基酸手性对映体的直接拆分,该固定相对12种氨基酸对映体有良好的手性拆分能力。基于氨基酸手性识别中离子交换和络合的协同作用,建立了一种新型的等温吸附模型。通过迎头特殊点洗脱法(FACP)测定色氨酸(Trp)在不同金属离子添加剂条件下的等温吸附线,验证了模型的合理性。流动相中的Li+、Na+、K+等金属离子与氨基酸竞争固定相中的冠醚络合位点,随着金属离子与冠醚的络合作用力和络合吸附平衡常数增大,固定相对Trp的手性拆分能力下降。该模型的建立对理解氨基酸在此类固定相中的手性保留行为以及固定相结构的进一步优化具有重要意义。A novel chiral stationary phase combining quinine and crown ether （QN-CR CSP） was developed to separate amino acid enantiomers. This CSP showed good enantioselectivity for some amino acids. Since the synergistic effect of ion exchange and complexation in chiral recognition of amino acids, a new adsorption isotherm was built. Using the method of frontal analysis by characteristic point （ FACP）, the adsorption isotherms of tryptophan （Trp） under different mobile phase conditions were determined and fitted the proposed adsorption isotherm model well. With the increase of the competition between metal cationic and amino to crown ether, the equilibrium constant of complexing adsorption was found increased. The chiral sepa- ration ability was decreased. The adsorption isotherm improved the understanding of the reten- tion behavior of amino acids on QN-CR CSP, which was also benefit to optimize the structure of the stationary phase.

关 键 词：手性固定相 奎宁 冠醚 离子交换 络合 等温吸附线 氨基酸 手性拆分 

分 类 号：O658[理学—分析化学]