Cryogenic infrared spectroscopy provides mechanistic insight into the fragmentation of phospholipid silver adducts

Tandem mass spectrometry is arguably the most important analytical tool for structure elucidation of lipids and other metabolites. By fragmenting intact lipid ions, valuable structural information such as the lipid class and fatty acyl composition are readily obtainable. The information content of a...

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Bibliographic Details
Published in:Analytical and bioanalytical chemistry 2022-07, Vol.414 (18), p.5275-5285
Main Authors: Kirschbaum, Carla, Greis, Kim, Gewinner, Sandy, Schöllkopf, Wieland, Meijer, Gerard, von Helden, Gert, Pagel, Kevin
Format: Article
Language:English
Subjects:
Adducts
Analytical Chemistry
Biochemistry
Cations
Characterization and Evaluation of Materials
Chemistry
Chemistry and Materials Science
Computer applications
Food Science
Fragmentation
Fragments
Glycerophospholipids - chemistry
Infrared spectroscopy
Isomers
Laboratory Medicine
Lipid metabolism
Lipids
Mass spectrometry
Mass spectroscopy
Metabolites
Metal ions
Monitoring/Environmental Analysis
Paper in Forefront
Phospholipids
Phospholipids - chemistry
Physiological aspects
Promising Early-Career (Bio)Analytical Researchers
Silver
Spectrophotometry, Infrared
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Summary:Tandem mass spectrometry is arguably the most important analytical tool for structure elucidation of lipids and other metabolites. By fragmenting intact lipid ions, valuable structural information such as the lipid class and fatty acyl composition are readily obtainable. The information content of a fragment spectrum can often be increased by the addition of metal cations. In particular, the use of silver ions is deeply rooted in the history of lipidomics due to their propensity to coordinate both electron-rich heteroatoms and C = C bonds in aliphatic chains. Not surprisingly, coordination of silver ions was found to enable the distinction of sn -isomers in glycerolipids by inducing reproducible intensity differences in the fragment spectra, which could, however, not be rationalized. Here, we investigate the fragmentation behaviors of silver-adducted sn - and double bond glycerophospholipid isomers by probing fragment structures using cryogenic gas-phase infrared (IR) spectroscopy. Our results confirm that neutral headgroup loss from silver-adducted glycerophospholipids leads to dioxolane-type fragments generated by intramolecular cyclization. By combining high-resolution IR spectroscopy and computational modelling of silver-adducted fragments, we offer qualitative explanations for different fragmentation behaviors of glycerophospholipid isomers. Overall, the results demonstrate that gas-phase IR spectroscopy of fragment ions can significantly contribute to our understanding of lipid dissociation mechanisms and the influence of coordinating cations. Graphical abstract
ISSN:1618-2642
1618-2650
DOI:10.1007/s00216-022-03927-6