量子化学计算解析手性共价有机框架材料6色谱固定相的手性拆分机理

引用本文: 胡园园, 张忠杰, 黄露. 量子化学计算解析手性共价有机框架材料6色谱固定相的手性拆分机理[J]. 色谱, 2020, 38(12): 1449-1455. doi: 10.3724/SP.J.1123.2020.05009 shu

Citation: HU Yuanyuan, ZHANG Zhongjie, HUANG Lu. Quantum chemical calculations for elucidating chiral resolution mechanism of chiral covalent organic frameworks 6 chromatographic stationary phase[J]. Chinese Journal of Chromatography, 2020, 38(12): 1449-1455. doi: 10.3724/SP.J.1123.2020.05009 shu

量子化学计算解析手性共价有机框架材料6色谱固定相的手性拆分机理

闽江学院海洋学院化学工程系, 福建福州 350108

通讯作者: 黄露, E-mail:luhuang@mju.edu.cn

基金项目:
福建省自然科学基金项目（2017J01418）；国家大学生创新创业训练计划项目（103952018023）.

摘要: 为探究手性共价有机框架材料6（Chiral Covalent Organic Frameworks 6，CCOF6）色谱固定相的手性拆分机理，首先运用ORCA程序对CCOF6及4对手性对映体进行结构优化，然后使用AutoDock程序对CCOF6及各对映体分子进行分子对接，获得CCOF6与对映体相互作用的初始构型；采用ORCA程序（B3LYP泛函，带DFT-D3校正，轨道基组为def2-TZVP，def2/J作为RI-J的辅助基组，RIJCOSX用来加速计算）对初始构型进行能量计算，以最终确定CCOF6与对映体的相互作用构型，并获得相应的结合自由能和结合自由能差；使用Multiwfn程序对ORCA结果进行独立梯度模型分析，并应用视觉分子动力学程序可视化展示CCOF6与对映体的弱相互作用。结果表明：①在计算结合自由能方面，考虑了溶剂效应的ORCA计算方法比不考虑溶剂效应的ORCA以及AutoDock计算方法更为精确；②CCOF6色谱固定相与对映体之间的结合自由能差绝对值越大，对映体的选择性因子也越大，然而对映体的分离度不一定会越大；③除S-1-苯基-1-丙醇是以羟基和CCOF6的醚键发生相互作用外，其他对映体皆为羟基与CCOF6的羰基发生相互作用，且S-1-苯基-1-丙醇与CCOF6的结合力最弱；④结合对映体的出峰时间和其与CCOF6的结合自由能大小可以推断，正己烷/异丙醇流动相对1-苯基-1-丙醇的洗脱能力最弱，正己烷/异丙醇流动相对1-苯基-2-丙醇的洗脱能力次弱；⑤除了S-1-苯基-1-丙醇出峰时间迟于R-1-苯基-1-丙醇，其余对映体均为R型出峰时间迟于S型。

关键词:

English

Quantum chemical calculations for elucidating chiral resolution mechanism of chiral covalent organic frameworks 6 chromatographic stationary phase

Department of Chemical Engineering, Ocean College, Minjiang University, Fuzhou 350108, China

Corresponding author: HUANG Lu, luhuang@mju.edu.cn

Received Date: 10 May 2020
Fund Project:
Natural Science Foundation of Fujian Province (No. 2017J01418)

Abstract: With the aim of exploring the chiral resolution mechanism of the chiral covalent organic frameworks 6 (CCOF6) chromatographic stationary phase, the ORCA program was used to optimize the structures of CCOF6 and four pairs of enantiomers. Then the molecular docking of CCOF6 with each enantiomer was performed by AutoDock program to obtain the initial interaction configurations of CCOF6 with four pairs of enantiomers. Energy calculations of the initial configurations were performed by ORCA program (B3LYP functional with DFT-D3 correction, def2-TZVP orbital basis set, def2/J auxiliary basis set, and RIJCOSX used to accelerate the calculation) to determine the interaction configurations of CCOF6 with four pairs of enantiomers and to obtain the corresponding binding free energy and binding free energy difference. Wave function analyses of ORCA calculation results were performed by Multiwfn program, and the weak interactions between CCOF6 and the four pairs of enantiomers were visualized by Visual Molecular Dynamics program. The results showed the following:① for calculating the binding free energies of CCOF6 and the four pairs of enantiomers, the ORCA method with the solvation effect was more accurate than the AutoDock method as well as the ORCA method without the solvation effect; ② the greater the absolute value of the binding free energy difference between the CCOF6 stationary phase and enantiomers, the greater was the selectivity factor of the enantiomers but not the resolution of the enantiomers; ③ the hydroxyl group of S-1-phenyl-1-propanol interacted with the ether bond of CCOF6, but the hydroxyl groups of the other enantiomers all interacted with the carbonyl groups of CCOF6, and the binding force between S-1-phenyl-1-propanol and CCOF6 was the weakest; ④ from the peak time of the enantiomer and its binding free energy with CCOF6, it was confirmed that the elution ability of n-hexane/isopropanol for 1-phenyl-1-propanol was the weakest, followed by the elution ability for 1-phenyl-2-propanol; ⑤ the peak time of S-1-phenyl-1-propanol was longer than that of R-1-phenyl-1-propanol, while for the other enantiomers, the peak time of the R-enantiomers was longer than that of the S-enantiomers.

Key words:

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量子化学计算解析手性共价有机框架材料6色谱固定相的手性拆分机理

通讯作者: 黄露, E-mail:luhuang@mju.edu.cn

English

Quantum chemical calculations for elucidating chiral resolution mechanism of chiral covalent organic frameworks 6 chromatographic stationary phase

Corresponding author: HUANG Lu, luhuang@mju.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

量子化学计算解析手性共价有机框架材料6色谱固定相的手性拆分机理

通讯作者: 黄露, E-mail:luhuang@mju.edu.cn

English

Quantum chemical calculations for elucidating chiral resolution mechanism of chiral covalent organic frameworks 6 chromatographic stationary phase

Corresponding author: HUANG Lu, luhuang@mju.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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