自由基化学-串联质谱用于脂质精细结构解析的研究进展  

Research Progress of Free Radical Chemistry-Tandem Mass Spectrometry for Fine Structure Analysis of Lipids

作　　者：简瑞君 瑕瑜 JIAN Rui-jun;XIA Yu(MOE Key Laboratory of Bioorganic Phosphorus Chemistry,Department of Chemistry,Tsinghua University,Beijing 100084,China)

机构地区：[1]清华大学化学系,生命有机磷化学及化学生物学教育部重点实验室,北京100084

出　　处：《质谱学报》2024年第1期57-68,I0002,共13页Journal of Chinese Mass Spectrometry Society

基　　金：国家自然科学基金面上项目(22074075);国家杰出青年科学基金(22225404)。

摘　　要：脂质作为六大营养素之一,与细胞膜构建、信号传导和能量代谢等多种生物学过程密切相关。然而,脂质分子结构多样性给分析带来了挑战。基于碰撞诱导解离(collision-induced dissociation,CID)的传统串联质谱(tandem mass spectrometry,MS/MS)技术仅可以鉴定分子种类和脂肪酰基链组成,难以分析C C位置、sn-位置、官能团取代及位置等精细结构。近年来,在多种结构层次上分辨脂质异构体的质谱方法迅速发展,其中,自由基的引入在脂质气相离子活化和引发化学反应等方面发挥着独特作用。本文综述了近10年来自由基化学结合串联质谱技术在脂质精细结构解析方面的应用进展,主要包括气相的自由基诱导解离(radical-induced dissociation,RID)和自由基参与反应的衍生化-串联质谱技术。As one of the six major nutrients,lipids play important roles in various biological processes,including cell membrane construction,signal transduction,and energy metabolism.The diverse functions of lipids are intricately linked to the distinct structures.More than 48000 molecular lipid structures have been curated in the database which can be further categorized into 8 categories and more than one hundred lipid classes and subclasses.The diverse structures of lipids pose challenges for their lipidomic analysis,especially the co-existence of isomers and isobar.Traditional tandem mass spectrometry(MS/MS)techniques based on collision-induced dissociation(CID)can provide the informations of molecular species and acyl chain composition of various types of lipids in a sensitive fashion.However,they typically fall short in providing detailed structural information,including C C positions,sn-positions,functional group substitutions and their locations on the fatty acyl chains.In recent years,mass spectrometry methods capable of distinguishing lipid isomers at various structural levels have been developed,among which radical chemistry plays important role in both gas-phase ion activation and chemical derivatization.This article summarized the MS/MS techniques for lipid structural analysis at detailed structural levels via harnessing the power of both radical chemistry and tandem mass spectrometry in the past decade.Radical-induced dissociation(RID)refers to a group of gas-phase dissociation methods which can generate intrachain C—C cleavages in the fatty acyl chain and thus produce fragmentation patterns useful for identification of chain modification.Ultraviolet photodissociation(UVPD)and CID triggered radical-directed dissociation,and electron impact excitation of ions from organics(EIEIO)are the major RID methods.By coupling RID with separation methods,such as reversed-phase liquid chromatography(RPLC),identification and quantitation of lipid isomers consisting of methyl branching,hydroxy group,and cyclopropane modif

关 键 词：脂质精细结构 自由基化学 串联质谱 自由基诱导解离 

分 类 号：O657.63[理学—分析化学]