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• W4213426750 endingPage "721" @default.
• W4213426750 startingPage "714" @default.
• W4213426750 abstract "Intrachain modifications of membrane glycerophospholipids (GPLs) due to formation of the carbon-carbon double bond (C═C), cyclopropane ring, and methyl branching are crucial for bacterial membrane homeostasis. Conventional collision-induced dissociation (CID) of even-electron ions of GPL favors charge-directed fragmentation channels, and thus little structurally informative fragments can be detected for locating intrachain modifications. In this study, we report a radical-directed dissociation (RDD) approach for characterization of the intrachain modifications within phosphoethanolamines (PEs), a major lipid component in bacterial membrane. In this method, a radical precursor that can produce benzyl or pyridine methyl radical upon low-energy CID at high efficiency is conjugated onto the amine group of PEs. The carbon-centered radical ions subsequently initiate RDD along the fatty acyl chain, producing fragment patterns key to the assignment and localization of intrachain modifications including C═C, cyclopropane rings, and methyl branching. Besides intrachain fragmentation, RDD on the glycerol backbone produces fatty acyl loss as radicals, allowing one to identify the fatty acyl chain composition of PE. Moreover, RDD of lyso-PEs produces radical losses for distinguishing the sn-isomers. The above RDD approach has been incorporated onto a liquid chromatography-mass spectrometry workflow and applied for the analysis of lipid extracts from Escherichia coli and Bacillus subtilis." @default.
• W4213426750 created "2022-02-25" @default.
• W4213426750 creator A5000523534 @default.
• W4213426750 creator A5048485729 @default.
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• W4213426750 date "2022-02-23" @default.
• W4213426750 modified "2023-10-13" @default.
• W4213426750 title "Localization of Intrachain Modifications in Bacterial Lipids Via Radical-Directed Dissociation" @default.
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• W4213426750 doi "https://doi.org/10.1021/jasms.2c00011" @default.
• W4213426750 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/35195000" @default.
• W4213426750 hasPublicationYear "2022" @default.
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