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Poster De Conférence Année : 2023

Structural characterization of phosphatidylcholine using VUVPD and ETD MS

Résumé

Lipids present a challenging analytical task, due to the number of known or potential isomers in biological samples. Currently, many analogs remain undifferentiated, and despite the many technical and methodological advances made in MS for lipid analysis, their characterization at the isomeric level still remains an analytical challenge.1 Structural characterization of glycerophospholipids (GPLs) shows particular interest since literature has pointed out the significant implications of isomeric variations in their chemical, biochemical, and biophysical roles.2 Since CID MS/MS fragmentation of protonated or sodiated GPLs does not yield structural information about the double bond (DB) or stereo-numbering (sn) locations, we will present alternative activation methods to CID to characterize phosphatidylcholines at this isomeric level. For this purpose, electron transfer dissociation (ETD) and ultraviolet photodissociation (UVPD) will be used to locate DB position, and to distinguish the aliphatic chain positions on the glycerol moiety, respectively. In this way, we have demonstrated that radical fragmentations enabling DB localization can be obtained by ETD from lithiated species. In addition, the generation of radical cations along the aliphatic chain was improved by avoiding adduction at the polar head. While photodissociation in the hundreds of nm leads to low-intensity diagnostic fragment ions of the double bond,3 UV photo-fragmentation at shorter wavelengths generates products ions specific of the aliphatic chain position on the glycerol, and more particularly intense diagnostic product ions with exclusively odd-electron sn-1 ester cleavage, and even-electron sn-2 ester cleavage ions. [1] A. Bednařík, et al., Anal. Chem. 2022, 94, 4889–4900. [2] R. Bandu, et al., Mass Spectrom Rev, 2018, 37, 107–138. [3] D. Klein and J. Brodbelt, Anal. Chem. 2017, 89, 1516–1522.
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hal-04247964 , version 1 (18-10-2023)

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  • HAL Id : hal-04247964 , version 1

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John Carlos, Jean-Yves Salpin, Alexandre Giuliani, Salomé Poyer. Structural characterization of phosphatidylcholine using VUVPD and ETD MS. 39th french days of mass spectrometry, Sep 2023, Marseille, France. ⟨hal-04247964⟩
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