Gas-phase stabilization of Cu(II) reveals phosphatidylcholine isomeric features by ESI and MALDI-MS - Archive ouverte HAL Accéder directement au contenu
Poster De Conférence Année : 2023

Gas-phase stabilization of Cu(II) reveals phosphatidylcholine isomeric features by ESI and MALDI-MS

Résumé

Glycerophospholipids (GPLs) are amphiphilic metabolites that make up most of the lipidbilayer in mammalian cells. literature has pointed out the significant implications of doublebond (DB) positions and linkage positions on the glycerol moiety in the chemical, biochemical,and biophysical roles of lipids.1 Currently, derivatization or instrumental modifications are re-quested to highlight these isomeric features in GPLs.Copper-adducted fatty acid proved to be efficient in localizing DB in aliphatic chains. However,the driving force of this fragmentation mechanism was attributed to the presence of the freecarboxylic acid function that is lacking in GPLs. We recently demonstrated that radical-drivenfragmentation could be obtained from quaternary copper complexes of GPLs. The CID MS/MSfragmentation of such species yields both DB and stereo-numbering (sn) locations in a singleexperiment.In this work, we will present our mechanistic hypothesis for phosphatidylcholine analogs basedon MS/MS and MSn experiments. Different isomers and classes of GPLs were used to confirmthe unambiguous location of stereoisomers and the role of the polar head. In addition, thismethod was applied to generate Cu(II) quaternary PC complexes by MALDI-MS.We tried different MALDI matrixes to characterize the quaternary Cu(II)-based complex. Forthis purpose, 1,5 DAN, 9-AA, DCTB, DHB, and THAP were tested to ionize this complex.DCTB was the only matrix that allowed to keep the +II oxidation state of Cu, suggesting highcomplex stability.3 MALDI-TOF/TOF experiments were performed on these complexes and al-lowed to locate the double bonds.
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Dates et versions

hal-04429210 , version 1 (31-01-2024)

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  • HAL Id : hal-04429210 , version 1

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Vincent Guerineau, Jean-Yves Salpin, Salomé Poyer. Gas-phase stabilization of Cu(II) reveals phosphatidylcholine isomeric features by ESI and MALDI-MS. JFSM 2023, Sep 2023, Marseille, France. ⟨hal-04429210⟩
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