溶剂效应对手性咪唑衍生物对映异构体与固定相相互作用的影响  

Influence of Solvent Effect on Interaction Between Chiral Imidazole Derivates Enantiomer and Stationary Phase

作　　者：胡桂香[1] 骆成才[1] 殷开梁[2] 邹建卫[1] 俞庆森[1] 

机构地区：[1]浙江大学宁波理工学院生物与化学工程学院,宁波315100 [2]常州大学石油化工学院计算中心,常州213164

出　　处：《高等学校化学学报》2013年第6期1497-1504,共8页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21002088)资助

摘　　要：采用分子模拟方法研究了两类手性咪唑衍生物的对映异构体与多糖类手性固定相纤维素-三(4-甲基苯甲酸酯)(商品名称为Chiralcel OJ)的相互作用,结果表明,溶剂效应对两者的相互作用有显著影响.在强极性溶剂(溶剂A)条件下,与化合物的S型异构体相比,化合物的R型异构体与固定相间形成的复合物更稳定,即S型先出峰,R型后出峰,与文献报道的拆分实验结果完全吻合;在弱极性溶剂(溶剂B)条件下,两个化合物的R/S型异构体与固定相相结合的结合能差别不大,无法进行有效分离.模拟结果表明,对映体与固定相之间存在远程互相排斥作用,在强极性溶剂作用下,远程静电作用减弱,有利于对对映体与固定相立体相互作用的不同进行区分,从而区分对映异构体.能量分析结果显示,分子间的范德华能,尤其是其中色散能的大小决定了对映体在固定相上是否可有效分离.The interaction between the enantiomers of two chiral imidazole derivates and polysaccharide-based chiral stationary phase cellulose tris（4-methylbenzoate）（Chiralcel OJ） was studied via molecular simulation.The result shows that the solvent effect has significant influence on the interaction.In the solvent A with strong polarity,the complexes between R-enantiomer of the compounds and the stationary phase are more stable than those of S-enantiomer,which leads to S-enantiomer eluting firstly and R-enantiomer following.The result is accordant with the separation experiment reported in the reference.Under the condition of solvent B with weak polarity,the binding energies are similar between R and S enantiomers of the two compounds and the stationary phase,which can not make R and S enantiomers separated effectively.The analysis on the simulation result demonstrates that the enantiomers and the stationary phase repulse each other under long-distance effect.In the strong polar solvent,the long-distance electrostatic interaction is weakened,which is beneficial to distinguish the difference of the steric interaction between the enantiomers and the stationary phase and further separate the enantiomers.The analysis of energy shows that the intermolecular van der Waals energy,especially dispersion energy determines whether the enantiomers separated effectively or not on the stationary phase.

关 键 词：对映异构体 纤维素-三(4-甲基苯甲酸酯)(Chiralcel OJ) 相互作用 分子模拟 洗脱顺序 

分 类 号：O641[理学—物理化学]