Fhaner Cassie J, Liu Sichang, Zhou Xiao, Reid Gavin E
Department of Chemistry.
Department of Chemistry ; Department of Biochemistry and Molecular Biology, Michigan State University.
Mass Spectrom (Tokyo). 2013;2(Spec Iss):S0015. doi: 10.5702/massspectrometry.S0015. Epub 2013 Apr 15.
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.
一种反应策略显示，其可提高“鸟枪法”高分辨率/精确质量质谱用于全面脂质组分析的能力。该策略涉及使用碘和甲醇对含缩醛磷脂的脂质中的O-烯基醚双键进行官能团选择性修饰，同时使用新型（13）C1-S，S'-二甲基硫代丁酰羟基琥珀酰亚胺酯（（13）C1-DMBNHS）试剂对含胺脂质进行官能团选择性衍生化。重要的是，这些衍生化反应导致的特征性质量位移能够从粗制复杂脂质提取物中分辨并明确鉴定含等压质量缩醛磷脂和缩醛磷脂醚的脂质种类，而无需在分析前进行色谱分离或额外的脂质提取步骤。此外，经衍生化的含甘油磷酸胆碱和甘油磷酸乙醇胺的缩醛磷脂醚在正离子模式串联质谱中的碎裂行为显示会产生大量特征性产物离子，这直接有助于确定它们的分子脂质身份。
