Structural Elucidation of Phosphatidylcholines via Radical-Directed Dissociation of [M + CuII + Anion]+ Ion Types.

IF 2.7 2区 化学 Q2 BIOCHEMICAL RESEARCH METHODS
Zunaira Naeem, Tingting Yan, Julia R Bonney, Troy R Scoggins, Boone M Prentice
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引用次数: 0

Abstract

Tandem mass spectrometry (MS/MS) is frequently used in phospholipid characterization to determine lipid class, fatty acyl chain length, and degree of unsaturation. However, conventional MS/MS methods are limited in characterizing isomeric lipids resulting from variants in double bond and sn-positions within the fatty acyl chains. This limitation is due to the fact that conventional collision induced dissociation (CID) of even-electron lipid precursor ions does not generate highly efficient product ions from intrachain fragmentation of the fatty acyl substituents. Herein, we have developed a workflow that leverages a new lipid ion type to facilitate radical-directed dissociation (RDD). Briefly, low-energy CID of [M + CuII + anion]+ ion types results in a radical cation, and subsequent activation of the radical cation results in highly efficient intrachain fragmentation of fatty acyl chains. This method provides abundant diagnostic fragment ions that are associated with the double bond and fatty acyl chain positions on the glycerol backbone and thus can be used to differentiate isomeric phosphatidylcholines (PCs). The incorporation of an anionic ligand in the [PC + CuII + anion]+ ion type is key to this chemistry. Specifically, the major fragmentation channel for the [PC + CuI]+ ion type is neutral loss of phosphocholine headgroup but shifts to RDD for [PC + CuII + anion]+ ion types containing strongly electronegative anions.

通过[M + CuII +阴离子]+离子类型的自由基定向解离研究磷脂酰胆碱的结构。
串联质谱法(MS/MS)经常用于磷脂表征,以确定脂类,脂肪酰基链长度和不饱和程度。然而,传统的质谱/质谱方法在表征由脂肪酸酰基链中的双键和sn位置变异引起的同分异构体脂质方面受到限制。这种限制是由于传统的碰撞诱导解离(CID)的偶电子脂质前体离子不能从脂肪酸取代基的链内断裂中产生高效的产物离子。在这里,我们开发了一个工作流程,利用一种新的脂质离子类型来促进自由基定向解离(RDD)。简而言之,[M + CuII +阴离子]+离子类型的低能CID导致自由基阳离子,随后自由基阳离子的激活导致脂肪酰基链的高效链内断裂。该方法提供了大量与甘油主链上的双键和脂肪酰基链位置相关的诊断片段离子,因此可用于区分异构体磷脂酰胆碱(PCs)。阴离子配体在[PC + CuII +阴离子]+离子类型中的结合是这种化学反应的关键。具体来说,[PC + CuI]+离子类型的主要破碎通道是磷酸胆碱头基的中性损失,而含有强电负性阴离子的[PC + CuII +阴离子]+离子类型则转向RDD。
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来源期刊
CiteScore
5.50
自引率
9.40%
发文量
257
审稿时长
1 months
期刊介绍: The Journal of the American Society for Mass Spectrometry presents research papers covering all aspects of mass spectrometry, incorporating coverage of fields of scientific inquiry in which mass spectrometry can play a role. Comprehensive in scope, the journal publishes papers on both fundamentals and applications of mass spectrometry. Fundamental subjects include instrumentation principles, design, and demonstration, structures and chemical properties of gas-phase ions, studies of thermodynamic properties, ion spectroscopy, chemical kinetics, mechanisms of ionization, theories of ion fragmentation, cluster ions, and potential energy surfaces. In addition to full papers, the journal offers Communications, Application Notes, and Accounts and Perspectives
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