PuSH - Publication Server of Helmholtz Zentrum München: Determining carbon-carbon double bond position of unsaturated glycerophospholipids in human plasma NIST® SRM® 1950 by electron impact excitation of ions from organics-tandem mass spectrometry (EIEIO-MS/MS).

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Martinez, S.* ; Gradillas, A.* ; Cermakova, H.* ; Witting, M. ; Barbas, C.*

Determining carbon-carbon double bond position of unsaturated glycerophospholipids in human plasma NIST® SRM® 1950 by electron impact excitation of ions from organics-tandem mass spectrometry (EIEIO-MS/MS).

J. Pharm. Biomed. Anal. 266, 10:117081 (2025)

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Understanding the structural diversity and biological functions of unsaturated fatty acyl chains (FAC) esterified in complex lipids -such as glycerolipids (GL), glycerophospholipids (GP) or sphingolipids (SP)- requires precise knowledge of the degree of unsaturation, location, and geometrical isomerism of the carbon-carbon double bonds (CC). However, the complex isomeric nature of lipids, combined with the inherent limitations of conventional tandem mass spectrometry (MS/MS) in structural elucidation, remains a major challenge in accurate CC elucidation. To overcome this, advanced MS/MS strategies, such as electron impact excitation of ions from organics (EIEIO) have emerged, generating diagnostic fragment ions that enable unambiguous CC localization. In the present study, we conducted a qualitative structural analysis of the CC positions in esterified FAC of GP present in NIST® Human Plasma Standard Reference Material, SRM 1950, employing RP-UHPLC-ESI(+)-EIEIO-QTOF-MS/MS. Interpretation of ESI(+)-EIEIO-MS/MS spectra enabled CC determination in 120 unsaturated GP, revealing a predominance of ω-6 and ω-3 FAC. These results offer new insights into the FAC distribution of this reference material, enhancing the structural annotation confidence level. By integrating such detailed molecular information, EIEIO-MS/MS proves to be a powerful approach for in-depth lipid structural elucidation in complex biological matrices, thereby contributing to methodological advancements and supporting its future application in translational lipidomics.

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Publication type Article: Journal article

Document type Scientific Article

Corresponding Author

Keywords Double Bond Position ; Electron Impact Excitation Of Ions From Organics (eieio) ; Electron-induced Dissociation (eid) ; Lipid Annotation ; Lipidomics ; Ms/ms Fragmentation ; Nist Srm 1950; Isomers; Lipids; Acid

ISSN (print) / ISBN 0731-7085

e-ISSN 0731-7085

Journal Journal of Pharmaceutical and Biomedical Analysis : JPBA

Quellenangaben Volume: 266, Pages: 10, Article Number: 117081

Publisher Elsevier

Publishing Place Radarweg 29, 1043 Nx Amsterdam, Netherlands

Non-patent literature Publications

Reviewing status Peer reviewed

Institute(s) CF Metabolomics & Proteomics (CF-MPC)

Grants European Regional Development Fund FEDER
La Caixa Foundation