色谱

色谱 ›› 2016, Vol. 34 ›› Issue (1): 62-67.DOI: 10.3724/SP.J.1123.2015.07015

• 研究论文 • 上一篇    下一篇

奎宁-冠醚组合型手性固定相直接拆分氨基酸的机理

吴海霞1, 王东强1, 赵见超1, 柯燕雄1, 梁鑫淼1,2   

  1. 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
  • 收稿日期:2015-07-15 出版日期:2016-01-08 发布日期:2012-08-01
  • 通讯作者: 柯燕雄
  • 基金资助:

    国家自然科学基金项目(21375038).

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

WU Haixia1, WANG Dongqiang1, ZHAO Jianchao1, KE Yanxiong1, LIANG Xinmiao1,2   

  1. 1. School of Pharmacy, East China University of Science and Technology, Shanghai 200237, China;
    2. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
  • Received:2015-07-15 Online:2016-01-08 Published:2012-08-01
  • Supported by:

    Natural Science Foundation of China (Grant No. 21375038).

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108

被引次数

2

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。

关键词: 氨基酸, 等温吸附线, 冠醚, 奎宁, 离子交换, 络合, 手性拆分, 手性固定相

Abstract:

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 separation ability was decreased. The adsorption isotherm improved the understanding of the retention behavior of amino acids on QN-CR CSP, which was also benefit to optimize the structure of the stationary phase.

Key words: adsorption isotherm, amino acids, chiral separation, chiral stationary phases, complexation, crown ether, ion exchange, quinine

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