Coupling Headgroup and Alkene Specific Solution Modifications with Gas-Phase Ion/Ion Reactions for Sensitive Glycerophospholipid Identification and Characterization
Coupling Headgroup and Alkene Specific Solution Modifications with Gas-Phase Ion/Ion Reactions for Sensitive Glycerophospholipid Identification and Characterization
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DOI：
10.1021/jasms.0c00001
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发表时间：
2020-04-01
影响因子：
3.2
通讯作者：
McLuckey, Scott A.
中科院分区：
文献类型：
--
作者：
Franklin, Elissia T.;Shields, Samuel W. J.;McLuckey, Scott A.
霰弹枪脂组学提供了敏感和快速的脂质鉴定，而不需要色谱分离。甘油磷脂（GPs）的散弹枪分析面临的挑战包括GP类之间缺乏信号均匀性，以及无法确定不饱和物种的脂肪酰基链中的碳-碳双键（C=C）位置。采用两种不同的衍生化策略，通过使用c -13-重氮甲烷（C-13-TrEnDi）三甲基化增强GPs的电离，以及利用与丙酮的溶液中光化学反应（通过Paterno-Buchi反应）确定脂肪酰基链内双键的位置。然后通过电喷雾电离对修饰的GP进行正离子模式电离，对不同类别的GP产生均匀的电离效率。GPs通过气相离子/离子反应进行电荷反转，并通过离子阱碰撞诱导解离（CID）进行顺序碎片化。该物种的CID导致分裂产生指示C=C键位置的诊断离子。该方法能够在牛脂提取物的C=C水平上增强电离和鉴定磷脂酰胆碱和磷脂酰乙醇胺物种。
Shotgun lipidomics provides sensitive and fast lipid identification without the need for chromatographic separation. Challenges faced by shotgun analysis of glycerophospholipids (GPs) include the lack of signal uniformity across GP classes and the inability to determine the carbon-carbon double bond (C=C) location within the fatty acyl chains of an unsaturated species. Two distinct derivatization strategies were employed to both enhance the ionization of GPs, via trimethylation enhancement using C-13-diazomethane (C-13-TrEnDi), as well as determine location of double bonds within fatty acyl chains, employing an in-solution photochemical reaction with acetone (via the Paterno-Buchi reaction). The modified GPs were then subjected to positive ion mode ionization via electrospray ionization, producing uniform ionization efficiencies for different classes of GP species. The GPs were charge inverted via gas-phase ion/ion reactions and sequentially fragmented using ion trap collision-induced dissociation (CID). The CID of the species led to fragmentation producing diagnostic ions indicative of C=C bond location. The approach enabled enhanced ionization and the identification of phosphatidylcholine and phosphatidylethanolamine species at the C=C level in a bovine lipid extract.