基于离子淌度质谱与从头算分子动力学模拟的质子互变异构体结构研究  

Structure Study of Proton Tautomers Based on Ion Mobility Mass Spectrometry and Ab Initio Molecular Dynamics Calculations

作　　者：傅达理 王昊东 郝保康 韩晔华 FU Da-Li;WANG Hao-Dong;HAO Bao-Kang;HAN Ye-Hua(State Key Laboratory of Heavy Oil Processing,College of Chemical Engineering and Environment,China University of Petroleum(Beijing),Beijing 102249,China)

机构地区：[1]中国石油大学(北京)化学工程与环境学院,重质油全国重点实验室,北京102249

出　　处：《分析化学》2024年第1期138-144,共7页Chinese Journal of Analytical Chemistry

基　　金：国家重点研发计划项目(No.2021YFA1501201)资助。

摘　　要：研究质子互变异构体的结构对于理解有机反应和生物化学过程具有重要意义。本研究提出了一种离子淌度质谱与从头算分子动力学模拟相结合的方法准确确定质子互变异构体的结构。不同的质子互变异构体先经离子淌度谱分离,再通过碰撞诱导解离,得到每个异构体结构对应的二级质谱图。通过从头算分子动力学计算模拟不同质子互变异构体的碎裂过程,得到每个异构体的理论二级质谱图。将实验结果和理论计算相互印证获得准确异构体结构,解决了质子互变异构体难以鉴定的难题,为质谱电离及碎裂机理和有机反应过程研究提供了重要参考。Investigating the structural characteristics of proton tautomers is of great significance for understanding organic reactions and biochemical processes.In this study,a method based on ion mobility mass spectrometry combined with ab initio molecular dynamics calculations was proposed.The structures of proton tautomers were determined by comparing the experimental and theoretical collision-induced dissociation(CID)mass spectrograms of different proton tautomers.Ion mobility mass spectrometry was used to separate proton tautomerism produced during ionization.The CID mass spectra of each isomer could be obtained after mobility separation.The quantum chemical mass spectrometry(QCXMS)program based on ab initio molecular dynamics calculations was used to calculate the fragmentation process and obtain the theoretical CID mass spectra.The results of experiment and calculation showed that this method effectively solved the issue of difficult identification of proton tautomers.This method was also of great significance for the study of ionization mechanism and organic reaction process using mass spectrometry.

关 键 词：离子淌度质谱 质子互变异构体 碰撞诱导解离 从头算分子动力学模拟 

分 类 号：O657.63[理学—分析化学] O621.25[理学—化学]