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化学学报
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化学学报 ›› 2001, Vol. 59 ›› Issue (2): 268-273. 上一篇    下一篇

研究论文

α－溴丙酸甲酯与β－环糊精衍生物手性识别过程的模 拟研究

聂孟言;周良模;王清海;朱道乾   

  1. 中国科学院大连化学物理研究所.大连(116012)
  • 发布日期:2001-02-15

Molecular dynamics simulations of chiral recognition of methyl α－ bromopropionate by modified cyclodextrins

Nie Mengyan;Zhou Liangmo;Wang Qinghai;Zhu Daoqian   

  1. Dalian Inst Chem Phys, CAS.Dalian(116012)
  • Published:2001-02-15

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应用分子动力学方法，模拟研究了α－溴丙酸甲酯分别与全甲基－β－环糊精(PMBCD)、七(2,6-二-O-丁基-3-O-丁酰基)-β－环糊精(DBBBCD)的手性识别过程。结果表明，α－溴丙酸甲酯对映体与PMBCD,DBBBCD的优先结合点位于环糊精空腔的内部，其对映体与所述环糊精的手性识别机理和形成腔内结合物有关；对映体在环糊精空腔内的结合并非传统意义上的紧密包合，对映体在腔内可以上下运动和转动；从对平衡构象的结构分析发现，所述对映体与环糊精衍生物的手性识别与葡萄糖单元的C(2)，C(3)所提供的手性环境密切相关。而且，分子模拟方法得到的对映体保留顺序与气相色谱实验结果是一致的。

关键词: 溴代烃, 丙酸酯, 环糊精, 卤代烃P, 对映体, 分离, 辨识, 模拟, 手征性, 分子模拟

The mechanisms of chiral recognition of methyl α－ bromopropionate by modified cyclodextrins (CDs) , permethylated β－CD (PMBCD) and heptakis (2,6-di-O-butyl-3-O-butyryl)- β-CD (DBBBCD) were investigated using molecular dynamics ( MD ) methods. It is found that the preferred binding stes for the investigated enantiomers are the interior of the modified CDs , and chiral recognition of the investigated enantiomers by PMBCD and DBBBCD is involved in the induced- fit interactions during the formation of the association complexes within the cavity of CDs. The associated enantiomers can move and rotate within the interior of the cavity, which is different from the concept "inclusion complexation". In the final conformations from MD simulations, the stereocenters of the investigated enantiomers locate near the secondary rim of the modified cyclodextrins. It is first proposed that chiral recognition is closely involed in the chiral region composed of chiral carbon C(2) and C(3) of CDs. In addition, the MD simulations can reproduce the experimental results from enantioselective gas chromatography.

Key words: BROMOHYDROCARBON, PROPIONATE, CYCLODEXTRIN, HALOHYDROCARBON P, ENANTIOMORPH, SEPARATION, IDENTIFICATION, SIMULATION, CHIRALITY

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