用于区分和相对定量异构醚键磷脂酰胆碱的 Radical-Directed Dissociation Mass Spectrometry 方法

IF 5.7 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta Pub Date : 2024-10-18 DOI:10.1016/j.aca.2024.343337

Xiaohui Zhang , Qinhua Chen , Lun Wu , Wenpeng Zhang , Xue Zhao

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引用次数: 0

摘要

背景醚键磷脂酰胆碱（PCs）包括plasmanyl和plasmmenyl PCs，它们分别在sn-1连接位上含有一个醚键或一个乙烯基醚键。由于脂质体中通常存在异构体和同分异构体，因此利用准确的结构信息来分析和定量醚类 PC 具有挑战性。研究结果本研究研究了醚类 PC 的碳酸氢盐阴离子加合物碰撞诱导解离（CID）产生的自由基定向解离（RDD），以区分和相对定量醚类 PC。烷基和烯基多氯联苯具有诊断性的特征碎片模式，可以对其进行可靠的识别和异构体区分。此外，Sn 位特异性产物离子已被证明可有效地对醚多氯化萘及其异构体多氯化萘进行相对定量。利用这种方法，我们成功地在人体血浆脂质提取物中鉴定出了 30 种 PC-O、21 种 PC-P（链组成水平）和 22 种异构 PC（sn-位置水平）。定量分析结果显示，人血浆中脂肪酰基链为 20:4 的醚型多氯联苯含量相对较高。最后，与正常对照组相比，2 型糖尿病（T2D）组中的醚型多氯化萘的分布显示 PC-O 18:1/20:5 显著减少。我们还发现，在 T2D 组别中呈下降趋势的是含有 17 碳脂肪酰基链的 PC 种类，而不是它们的异位醚 PC。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Radical-directed dissociation mass spectrometry for differentiation and relative quantitation of isomeric ether-linked phosphatidylcholines

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Radical-directed dissociation mass spectrometry for differentiation and relative quantitation of isomeric ether-linked phosphatidylcholines

Background

Ether-linked phosphatidylcholines (PCs) include both plasmanyl and plasmenyl PCs, which contain an ether or a vinyl ether bond at the sn-1 linkage position, respectively. Profiling and quantifying ether PCs with accurate structural information is challenging because of the common presence of isomeric and isobaric species in a lipidome.

Results

In the present study, radical directed dissociation (RDD) from collision-induced dissociation (CID) of the bicarbonate anion adduct of ether PCs has been investigated to differentiate and relatively quantify ether PCs. Alkyl- and alkenyl- PCs give diagnostic characteristic fragment patterns that enable their confident identification and isomer differentiation. Additionally, the sn-position specific product ions have proven effective for relative quantitation among isomers in ether PCs and their isobaric PC species. Using this methodology, we successfully identified a total of 30 PC-O species, 21 PC-P species at the chain composition level, and 22 species of isobaric PC at the sn-position level in the human plasma lipid extract. The quantitative analysis revealed that ether PCs with a 20:4 fatty acyl chain are relatively more abundant in human plasma. Finally, the profile of ether PCs in type 2 diabetic (T2D) groups compared to normal control groups revealed a significant decrease in PC-O 18:1/20:5. We also found it is the PC species containing a 17-carbon fatty acyl chain, rather than their isobaric ether PCs, that shows a decreasing trend in the T2D groups.

Significance

ether-linked PCs are firstly investigated by RDD mass spectrometry.

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来源期刊

Analytica Chimica Acta 化学-分析化学

CiteScore

10.40

自引率

6.50%

发文量

1081

审稿时长

38 days

期刊介绍： Analytica Chimica Acta has an open access mirror journal Analytica Chimica Acta: X, sharing the same aims and scope, editorial team, submission system and rigorous peer review. Analytica Chimica Acta provides a forum for the rapid publication of original research, and critical, comprehensive reviews dealing with all aspects of fundamental and applied modern analytical chemistry. The journal welcomes the submission of research papers which report studies concerning the development of new and significant analytical methodologies. In determining the suitability of submitted articles for publication, particular scrutiny will be placed on the degree of novelty and impact of the research and the extent to which it adds to the existing body of knowledge in analytical chemistry.