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

Kirschbaum, C., Greis, K., Gewinner, S., Schöllkopf, W., Meijer, G., Helden, G. v., et al. (2022). Cryogenic infrared spectroscopy provides mechanistic insight into the fragmentation of phospholipid silver adducts. Analytical and Bioanalytical Chemistry, 414(18), 5275-5285. doi:10.1007/s00216-022-03927-6.

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Kirschbaum2022_Article_CryogenicInfraredSpectroscopyP.pdf (Publisher version), 2MB
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 Creators:
Kirschbaum, Carla1, 2, Author              
Greis, Kim1, 2, Author              
Gewinner, Sandy2, Author              
Schöllkopf, Wieland2, Author              
Meijer, Gerard2, Author              
Helden, Gert von2, Author              
Pagel, Kevin1, 2, Author              
Affiliations:
1Institut für Chemie und Biochemie, Freie Universität Berlin, 14195, Berlin, Germany, ou_persistent22              
2Molecular Physics, Fritz Haber Institute, Max Planck Society, ou_634545              

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Free keywords: Infrared spectroscopy; Tandem mass spectrometry; Lipidomics; Glycerophospholipids; Isomers; Silver
 Abstract: 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.

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Language(s): eng - English
 Dates: 2021-11-222022-01-252022-02-112022-07
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1007/s00216-022-03927-6
 Degree: -

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Project name : GlycoSpec - Unravelling Glycochemistry with Ion Mobility Spectrometry and Gas-Phase Spectroscopy
Grant ID : 863934
Funding program : Horizon 2020 (H2020)
Funding organization : European Commission (EC)

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Title: Analytical and Bioanalytical Chemistry
  Abbreviation : Anal. Bioanal. Chem.
Source Genre: Journal
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Publ. Info: Heidelberg : Springer-Verlag
Pages: 11 Volume / Issue: 414 (18) Sequence Number: - Start / End Page: 5275 - 5285 Identifier: ISSN: 1618-2642
CoNE: https://pure.mpg.de/cone/journals/resource/111006469468428