Functional group selective derivatization and gas-phase fragmentation reactions of plasmalogen glycerophospholipids.
Functional group selective derivatization and gas-phase fragmentation reactions of plasmalogen glycerophospholipids.
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DOI：
10.5702/massspectrometry.s0015
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发表时间：
2013-01-01
期刊：
影响因子：
--
通讯作者：
Reid, Gavin E
中科院分区：
文献类型：
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作者：
Fhaner, Cassie J;Liu, Sichang;Reid, Gavin E
一种反应策略，包括使用碘和甲醇对含血浆烯基醚的脂质中的O-烯基醚双键进行官能团选择性修饰，以及使用新的（13）C1-S，S ′-二甲基硫代丁酰基羟基琥珀酰亚胺酯（（13）C1-DMBNHS）试剂对含胺脂质进行官能团选择性衍生，改进了用于全面脂质组分析的“鸟枪式”高分辨率/精确质谱的能力。重要的是，由于这些衍生反应而引入的特征质量变化使得能够从粗复杂脂质提取物中解析和明确识别含有同量异序浆基和浆基醚的脂质物质，而无需在分析之前进行色谱分离或额外的脂质提取步骤。此外，含有甘油磷酸胆碱和甘油磷酸乙醇胺脂质的衍生化的血浆烯基醚的正离子化模式串联质谱裂解行为显示出产生丰富的特征产物离子，其直接使得能够分配其分子脂质身份。
A reaction strategy involving functional group selective modification of the O-alkenyl-ether double bond within plasmenyl ether containing lipids using iodine and methanol, in conjunction with functional group selective derivatization of amine-containing lipids using a novel (13)C1-S,S'-dimethylthiobutanoylhydroxysuccinimide ester ((13)C1-DMBNHS) reagent, is shown to improve the capabilities of 'shotgun' high resolution/accurate mass spectrometry for comprehensive lipidome analysis. Importantly, the characteristic mass shifts introduced as a result of these derivatization reactions enables the resolution and unambiguous identification of isobaric mass plasmenyl- and plasmanyl-ether containing lipid species from within crude complex lipid extracts, without need for chromatographic fractionation or additional lipid extraction steps prior to analysis. Additionally, the positive ionization mode tandem mass spectrometry fragmentation behavior of the derivatized plasmenyl ether containing glycerophosphocholine and glycerophosphoethanolamine lipids are shown to yield abundant characteristic product ions that directly enable the assignment of their molecular lipid identities.