物理化学学报 >> 2009, Vol. 25 >> Issue (07): 1273-1278.doi: 10.3866/PKU.WHXB20090713

研究论文 上一篇    下一篇

α-氯丙酸乙酯对映体与β-环糊精的主客体相互作用

施介华, 肖科科, 吕园园   

  1. 浙江工业大学药学院, 杭州 310032|浙江工业大学绿色合成技术国家重点实验室培育基地, 杭州 310032
  • 收稿日期:2009-02-10 修回日期:2009-03-12 发布日期:2009-06-26
  • 通讯作者: 施介华 E-mail:shijh@zjut.edu.cn

Host-Guest Interactions of β-Cyclodextrin with Enantiomers of Ethyl α-Chloropropionates

SHI Jie-Hua, XIAO Ke-Ke, LV Yuan-Yuan   

  1. College of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310032, P. R. China|State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Zhejiang University of Technology, Hangzhou 310032, P. R. China
  • Received:2009-02-10 Revised:2009-03-12 Published:2009-06-26
  • Contact: SHI Jie-Hua E-mail:shijh@zjut.edu.cn

摘要:

运用量子力学PM3方法模拟α-氯丙酸乙酯((R/S)-ECPA)与β-环糊(β-CD)的主客体相互作用, 探讨(R/S)-ECPA在β-CD上的手性识别机理. 结果表明, (R/S)-ECPA对映体与β-CD形成稳定结合物的结合方式完全不同, (R)-ECPA位于β-CD空腔宽口端, 形成缔合物; (S)-ECPA插入β-CD空腔内形成包结物. 而且, (S)-ECPA与β-CD的结合稳定能低于(R)-ECPA与β-CD的结合稳定能. 在(R/S)-ECPA与β-CD结合物中, (R/S)-ECPA中的手性碳接近葡萄糖单元的C2和C3. (R/S)-ECPA与β-CD之间的手性识别与葡萄糖单元的C2和C3所提供的手性环境和(R/S)-ECPA与β-CD结合的紧密程度密切相关.

关键词: PM3, α-氯丙酸乙酯, β-环糊精, 分子模拟, 手性识别

Abstract:

Host-guest interactions of β-cyclodextrin (β-CD) with enantiomers of ethyl α-chloropropionates ((R/S)-ECPA) were simulated using the quantum mechanics PM3 method. The chiral recognition mechanism of (R/S)-ECPA enantiomers on β-CD was investigated. Modeling results showed that the stabilization of complexes formed by (R/S)-ECPA enantiomers and β-CD were different. (R)-ECPA was located on the cavity wide mouth end of β-CD to form an associated molecule, but (S)-ECPAinserted into the β-CDcavity to forman inclusion molecule. The stabilization energy of the (S)-ECPA and β-CD complex was lower than that of the (R)-ECPA and β-CD complex. The chiral carbon in the ECPA of (R/S)-ECPA and β-CD complexes was close to the C2 and C3 in the glucose unit. The chiral recognition mechanism was thus closely related to the chiral environment provided by C2 and C3 in the glucose unit and the degree of (R/S)-ECPA and β-CD inclusion.

Key words: PM3, Ethyl α-chloropropionate, β-Cyclodextrin, Molecular simulation, Chiral recognization

MSC2000: 

  • O641