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Structural characterization and analysis of different epimers of neutral glycosphingolipid LcGg4 by ion mobility spectrometry-mass spectrometry
Analyst ( IF 3.6 ) Pub Date : 2022-06-02 , DOI: 10.1039/d2an00224h
Tianqi Gao 1 , Aneirin A Lott 2, 3 , Fanran Huang 1 , Rajendra Rohokale 1 , Qingjiang Li 1 , Hernando J Olivos 4 , Sixue Chen 2, 3 , Zhongwu Guo 1
Affiliation  

LcGg4, a neutral glycosphingolipid (GSL) and cancer antigen, its epimers GalNAc-LcGg4 and GlcNAc-LcGg4, and three lipid forms of GalNAc-LcGg4 were studied by mass spectrometry (MS). It was found that different forms of GalNAc-LcGg4 carrying homologous (d16:1/18:0) and (d18:1/18:0) lipids were easily separated and identified using liquid chromatography (LC)-MS. In addition, like gangliosides, homologous lipid forms of GalNAc-LcGg4 showed the same fragmentation pattern, except for a uniform shift of their glycolipid product ions by a certain m/z number determined by the varied lipid structure. It was also disclosed that LcGg4 and its epimers GalNAc-LcGg4 and GlcNAc-LcGg4, which are different only in the C4-configuration of their non-reducing end sugar residues, gave the same MS/MS product ions in similar relative intensities, as well as the same LC retention time, suggesting the challenge to differentiate epimeric GSLs by LC-MS. However, ion mobility spectrometry (IMS)-MS was able to efficiently separate and distinguish these epimers. This study has demonstrated the promise of IMS-MS for isomeric GSL characterization and the IMS-MS and LC-MS/MS combination for natural GSL analysis.

中文翻译:

离子迁移谱-质谱法对中性鞘糖脂 LcGg4 不同差向异构体的结构表征和分析

通过质谱 (MS) 研究了中性鞘糖脂 (GSL) 和癌症抗原 LcGg4、其差向异构体 GalNAc-LcGg4 和 GlcNAc-LcGg4 以及 GalNAc-LcGg4 的三种脂质形式。研究发现,携带同源 (d16:1/18:0) 和 (d18:1/18:0) 脂质的不同形式的 GalNAc-LcGg4 很容易使用液相色谱 (LC)-MS 进行分离和鉴定。此外,与神经节苷脂一样,GalNAc-LcGg4 的同源脂质形式显示出相同的碎裂模式,除了其糖脂产物离子按一定的m / z均匀移动之外。数量由不同的脂质结构决定。还公开了 LcGg4 及其差向异构体 GalNAc-LcGg4 和 GlcNAc-LcGg4(仅其非还原端糖残基的 C4 构型不同)也以相似的相对强度给出相同的 MS/MS 产物离子。相同的 LC 保留时间,表明通过 LC-MS 区分差向异构体 GSL 存在挑战。然而,离子迁移谱 (IMS)-MS 能够有效分离和区分这些差向异构体。这项研究证明了 IMS-MS 用于异构 GSL 表征以及 IMS-MS 和 LC-MS/MS 组合用于天然 GSL 分析的前景。
更新日期:2022-06-02
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