Multiple- stage linear ion- trapwith high resolution mass spectrometry towards complete structural characterization of phosphatidylethanolamines containing cyclopropane fatty acyl chain in Leishmania infantum
Multiple- stage linear ion- trapwith high resolution mass spectrometry towards complete structural characterization of phosphatidylethanolamines containing cyclopropane fatty acyl chain in Leishmania infantum
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DOI：
10.1002/jms.3327
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发表时间：
2014-03-01
影响因子：
2.3
通讯作者：
Beverley, Stephen M.
中科院分区：
文献类型：
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作者：
Hsu, Fong-Fu;Kuhlmann, F. Matthew;Beverley, Stephen M.
婴儿利什曼原虫磷脂酰乙醇胺（PE）的结构是独特的，因为它们由一个罕见的含环丙烷脂肪酸（CFA）的PE亚家族组成，包括含CFA的缩醛磷脂（PE）种类。在这篇论文中，我们应用多级线性离子阱结合高分辨质谱来确定被解吸为[M-H]（-）和[M-H + 2Li]（+）离子的PE的结构。由MSn产生的关于两种分子种类的结构信息是互补的，允许完全确定PE结构，包括脂肪酸取代基的身份及其在甘油主链上的位置，更重要的是，脂肪酸链的双键和环丙烷链的位置，从而实现先前报道的CFA生物合成途径。我们还发现了一个次要的二甲基-PE亚类的存在下，还没有以前在L。婴儿这种LIT MSn质谱方法导致了PE分子的明确鉴定，包括复杂混合物中的许多异构体，否则使用其他分析方法将非常难以定义。版权所有（c）2014约翰威利父子有限公司
The structures of phosphatidylethanolamine (PE) in Leishmania infantum are unique in that they consist of a rare cyclopropane fatty acid (CFA) containing PE subfamily, including CFA-containing plasmalogen PE species. In this contribution, we applied multiple-stage linear ion-trap combined with high-resolution mass spectrometry to define the structures of PEs that were desorbed as [M - H](-) and [M - H + 2Li](+) ions by ESI, respectively. The structural information arising from MSn on both the molecular species are complimentary, permitting complete determination of PE structures, including the identities of the fatty acid substituents and their location on the glycerol backbone, more importantly, the positions of the double bond(s) and of the cyclopropane chain of the fatty acid chain, directing to the realization of the CFA biosynthesis pathways that were reported previously. We also uncovered the presence of a minor dimethyl-PE subclass that has not been previously reported in L. infantum. This LIT MSn mass spectrometric approach led to unambiguous identification of PE molecules including many isomers in complex mixture that would otherwise be very difficult to define using other analytical approaches. Copyright (c) 2014 John Wiley & Sons, Ltd.