高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (5): 988.

• 研究论文 • 上一篇    下一篇

三元非对映异构体复合物的直接实验证据及其在对映体手性分离中的作用

于擎, 曹洁, 张成根   

  1. 中国科学院研究生院化学与化学工程学院, 北京100049
  • 收稿日期:2008-07-14 出版日期:2009-05-10 发布日期:2009-05-10
  • 通讯作者: 曹洁, 女, 博士, 副教授, 主要从事手性拆分及识别的质谱研究, E-mail: jcao@gucas.ac.cn
  • 基金资助:

    教育部科学技术研究重点项目(批准号: 106064)资助.

Direct Experimental Evidence of Ternary Diastereomeric Complexes in Chiral Separations of Phenylglycine Enatiomers with Chiral Mobile Phase by RP-HPLC

YU Qing, CAO Jie*, ZHANG Cheng-Gen   

  1. College of Chemistry and Chemical Engineering, Graduate University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2008-07-14 Online:2009-05-10 Published:2009-05-10
  • Contact: CAO Jie, E-mail: jcao@gucas.ac.cn

摘要:

以含L-苯丙氨酸铜配位络合物的溶液作为手性流动相, 采用反相高效液相色谱法拆分了非衍生苯甘氨酸对映体, 使用质谱对拆分组分进行了结构鉴定, 得到了拆分组分的化学结构, 用量子化学计算预测了该结构的最稳定构象. 质谱实验结果表明, 拆分组分是一对铜混合配体复合物离子, 其中的一个配体是提供手性环境的流动相添加物(L-苯丙氨酸), 另一配体是待拆分物质的某一构型对映体, 这对铜混合配体复合物离子本质上属于非对映异构体. 在色谱分离实验中还考察了手性流动相pH值、甲醇含量以及L-苯丙氨酸与Cu2+ 的摩尔比等因素对分离效果的影响.

关键词: 手性流动相, 反相高效液相色谱法, 苯甘氨酸, 质谱, 理论计算

Abstract:

Chiral separation of D-,L-phenylglycine by RP-HPLC was accomplished by adding a complex of optically active L-Phe-Cu2+ to the mobile phase. Chiral separation mechanism was further elucidated in light of unambiguously assigning the structure of the elutents from RP-HPLC by taking advantage of tandem mass spectrometry due to its unique capability of structural identification of the unknows. Mass spectrometry results revealed that the pair of eluents respresented a pair of ternary copper complexes with mixed ligands, providing the first experimental evidence. These complexes are diastereoisomer in nature. The optimized configuration of the diastereoisomer was predicted by theoretical calculation. In addition, the effects of the ratio of Cu2+ to L-Phe, pH of chiral mobile phase as well as the concentrations of methanol were investigated.

Key words: Chiral mobile phase, RP-HPLC, Phenylglycin, Mass spectrometry, Theoretical calculation

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