基于分子模拟对多糖类衍生物手性识别机理的探索

邓恩停; 毕婉莹; 刘博; 张丽丽; 沈军

doi:10.11777/j.issn1000-3304.2019.19116

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基于分子模拟对多糖类衍生物手性识别机理的探索

论文 | 更新时间：2021-01-26

- 基于分子模拟对多糖类衍生物手性识别机理的探索
- Investigation of Chiral Recognition Mechanism of Polysaccharide Derivatives Based on Molecular Simulation
- 高分子学报 2020年51卷第2期页码：214-220
- 作者机构：
  
  哈尔滨工程大学材料科学与化学工程学院高分子材料研究中心　哈尔滨 150001
- 作者简介：
  
  E-mail: zhanglili1984@hrbeu.edu.cn Li-li Zhang, E-mail: zhanglili1984@hrbeu.edu.cn
  E-mail: shenjun@hrbeu.edu.cn Jun Shen, E-mail: shenjun@hrbeu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号51673052，21474024，51603054)和黑龙江省博士后基金(基金号 LBH-Z15050)资助项目
- DOI：10.11777/j.issn1000-3304.2019.19116
  中图分类号：
- 纸质出版日期：2020-2，
  
  网络出版日期：2019-9-27，
  
  收稿日期：2019-6-12，
  
  修回日期：2019-8-5，
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邓恩停, 毕婉莹, 刘博, 张丽丽, 沈军. 基于分子模拟对多糖类衍生物手性识别机理的探索[J]. 高分子学报, 2020,51(2):214-220.

En-ting Deng, Wan-ying Bi, Bo Liu, Li-li Zhang, Jun Shen. Investigation of Chiral Recognition Mechanism of Polysaccharide Derivatives Based on Molecular Simulation[J]. Acta Polymerica Sinica, 2020,51(2):214-220.
邓恩停, 毕婉莹, 刘博, 张丽丽, 沈军. 基于分子模拟对多糖类衍生物手性识别机理的探索[J]. 高分子学报, 2020,51(2):214-220. DOI： 10.11777/j.issn1000-3304.2019.19116.

En-ting Deng, Wan-ying Bi, Bo Liu, Li-li Zhang, Jun Shen. Investigation of Chiral Recognition Mechanism of Polysaccharide Derivatives Based on Molecular Simulation[J]. Acta Polymerica Sinica, 2020,51(2):214-220. DOI： 10.11777/j.issn1000-3304.2019.19116.

摘要

采用酯化法合成纤维素-三(苯基氨基甲酸酯)(CTPC)和直链淀粉-三(苯基氨基甲酸酯)(ATPC)衍生物，并通过氢核磁共振谱(

H-NMR)确定其结构规整，取代完全. 将所合成衍生物涂覆到氨丙基硅胶表面制备手性固定相，应用高效液相色谱法(HPLC)技术评价其对手性化合物1-(9-蒽基)-2

2-三氟乙醇(Rac-1)的手性识别性能. 在此基础上应用Materials Studio模拟软件，基于分子力学和分子动力学对多糖衍生物二级结构进行分子模拟，并根据FTIR和XRD表征结果，对衍生物与Rac-1对映体之间的相互作用能进行模拟计算，获得其最优构象. 结果表明，分子模拟结果与手性识别性能及对映体洗脱顺序吻合较好，多糖衍生物与对映体分子在其手性凹槽与氨基甲酸酯侧基和芳香体系发生稳定性不等的多种协同相互作用是产生手性识别的重要原因.

Abstract

As one of the most powerful and popular chiral stationary phases (CSPs)

phenylcarbamate derivatives of cellulose and amylose exhibit high chiral recognition ability and have realized efficent enantioseparation for almost 80% chiral compounds. To develop novel enantioseparation materials with high chiral recognition ability

it is of crucial importance to elucidate the chiral recognition mechanism for CSPs. Based on this

cellulose tris(phenylcarbamate) and amylose tris(phenylcarbamate) were synthesized by traditional esterification method in this study. The structures and degrees of substitution of the polysaccharide derivatives were characterized by

H-NMR

implying that the obtained cellulose and amylose deivatives possessed regular higher order structures and almost complete substitution of phenylcarbamate pendants at three positions on the glucose units. The obtained polysaccharide derivatives were then coated on aminopropyl silica gel to prepare the chiral stationary phases (CSPs). The chiral recognition abilities of the derivatives were evaluated by the high performance liquid chromatography (HPLC) based on the separation of racemic 1-(9-anthryl)-2

2-trifluoroethanol (Rac-1). Then

based on the molecular mechanics and the molecular dynamics

molecular simulation of the higher order sturucture of polysaccharide derivatives were performed using Materials Studio software. The optimized conformation for the interaction between polysaccharide derivatives and enantiomers of Rac-1 was achieved by the molecular simulation according to the FTIR and XRD results. The molecular simulation results agreed well with the chiral recognition ability and elution order of enantiomers by HPLC. It indicated that the chiral recognition was significantly dependent on the synergistic interactions between polysaccharide derivatives and enantiomers of Rac-1 at the chiral grooves formed by the carbamate substituents and aromatic rings of the polysaccharide derivatives with different stabilities. This study may contribute to a better understanding for the chiral recognition mechanism of polymer-based CSPs.

关键词

手性识别机理手性分离分子模拟多糖

Keywords

Chiral recognition mechanismEnantioseparationMolecular simulationPolysaccharide

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