Structural Characterization of Phosphatidylcholines Using 193 nm Ultraviolet Photodissociation Mass Spectrometry.
Structural Characterization of Phosphatidylcholines Using 193 nm Ultraviolet Photodissociation Mass Spectrometry.
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DOI：
10.1021/acs.analchem.6b03353
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发表时间：
2017-02-07
影响因子：
7.4
通讯作者：
Brodbelt JS
中科院分区：
文献类型：
--
作者：
Klein DR;Brodbelt JS
质谱技术的进步使其成为甘油磷脂结构表征的首选工具。通常在商业仪器上实施的碰撞活化方法不提供允许阐明某些结构特征的断裂模式，包括甘油主链上的酰基链位置和酰基链内的双键位置。在目前的工作中，193 nm的紫外光解离（UVPD）的轨道阱质谱仪上实现的用于本地化磷脂酰胆碱（PC）的酰基链内的双键位置。邻近双键的碳-碳键的断裂提供了24 Da的诊断质量差，并能够区分双键位置异构体。UVPD方法扩展到表征PC在牛肝提取物通过鸟枪策略。正模式高能碰撞解离（HCD）和UVPD，负模式HCD进行了互补的方式来确定物种的PC和本地化的双键，分别。
Advances in mass spectrometry have made it a preferred tool for structural characterization of glycerophospholipids. Collisional activation methods commonly implemented on commercial instruments do not provide fragmentation patterns that allow elucidation of certain structural features, including acyl chain positions on the glycerol backbone and double bond positions within acyl chains. In the present work, 193 nm ultraviolet photodissociation (UVPD) implemented on an Orbitrap mass spectrometer is used to localize double bond positions within phosphatidylcholine (PC) acyl chains. Cleavage of the carbon-carbon bonds adjacent to the double bond provides a diagnostic mass difference of 24 Da and enables differentiation of double-bond positional isomers. The UVPD method was extended to the characterization of PCs in a bovine liver extract via a shotgun strategy. Positive mode higher energy collisional dissociation (HCD) and UVPD, and negative mode HCD were undertaken in a complementary manner to identify species as PCs and to localize double bonds, respectively.