Characterization of glycerophospholipids at multiple isomer levels via Mn(II)-catalyzed epoxidation.

Characterization of glycerophospholipids at multiple isomer levels via Mn(II)-catalyzed epoxidation.
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DOI:
10.1039/d2an01174c
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发表时间:
2022-10-24
期刊:
影响因子:
4.2
通讯作者:
Yan, Xin
Yan, Xin
中科院分区:
化学2区
文献类型:
--
作者:
Chen, Xi;Tang, Shuli;Freitas, Dallas;Hirtzel, Erin;Cheng, Heyong;Yan, Xin

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甘油磷脂异构体的表征是非常重要的,因为它们在生理和病理过程中发挥不同的作用。在这项工作中,我们提出了一种新的和双功能的衍生化方法,利用锰(II)催化的环氧化反应,同时确定碳-碳双键(C=C键)和立体编号(SN)的位置异构体的磷脂酰胆碱。Mn(II)与吡啶甲酸配位并催化过氧乙酸对不饱和脂质的环氧化。环氧化物的碰撞诱导解离(CID)产生可用于定位C=C键位置的诊断离子。同时,CID的Mn(II)离子-脂质复合物产生的特征离子测定Sn的位置。这种双功能衍生化在几秒钟内发生,CID中产生的诊断离子清晰且易于解释。此外,实现了C=C键和Sn-位置异构体的相对定量。使用脂质标准品和来自复杂生物样品的脂质提取物显示了该方法在多种异构体水平下鉴定脂质的能力。
Characterization of glycerophospholipid isomers is of significant importance as they play different roles in physiological and pathological processes. In this work, we present a novel and bifunctional derivatization method utilizing Mn(II)-catalyzed epoxidation to simultaneously identify carbon-carbon double bond (C=C bond)- and stereonumbering (sn)-positional isomers of phosphatidylcholine. Mn(II) coordinates with picolinic acid and catalyzes epoxidation of unsaturated lipids by peracetic acid. Collision-induced dissociation (CID) of the epoxides generates diagnostic ions that can be used to locate C=C bond positions. Meanwhile, CID of Mn(II) ion-lipid complexes produces characteristic ions for determination of sn positions. This bifunctional derivatization takes place in seconds, and the diagnostic ions produced in CID are clear and easy to interpret. Moreover, relative quantification of C=C bond-and sn-positional isomers was achieved. The capability of this method in identifying lipids at multiple isomer levels was shown using lipid standards and lipid extracts from complex biological samples.
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