Dissociation of proton-bound complexes reveals geometry and arrangement of double bonds in unsaturated lipids

Pham, Huong T., Prendergast, Matthew B., Dunstan, Christopher W., Trevitt, Adam J., Mitchell, Todd W., Julian, Ryan R., & Blanksby, Stephen J. (2015) Dissociation of proton-bound complexes reveals geometry and arrangement of double bonds in unsaturated lipids. International Journal of Mass Spectrometry, 390, pp. 170-177.

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Double bond position and stereochemistry in unsaturated lipids can have profound impact on biological properties and activities but the assignment of these features by mass spectrometry is frequently challenging. Conventional techniques for lipid identification rely on collision-induced dissociation (CID) and are most often unable to differentiate between lipid isomers, particularly those involving double bond position and geometry (i.e., cis and trans). In this study, CID performed on proton-bound complexes of fatty acid methyl esters and iodoaniline (and related reagents) reveals unusual fragmentation patterns. CID products are shown to result from proton transfer and are associated with specific structures of the unsaturated lipids. Notably, CID of these complexes can not only distinguish cis- and trans-fatty acid methyl esters, but also differentiate conjugated double bond arrangements from non-conjugated analogs. Herein, the mechanisms underpinning this unique CID behavior are investigated by stable isotope labeling and are proposed to involve both carbene and free radical intermediates.

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ID Code: 96428
Item Type: Journal Article
Refereed: Yes
Keywords: Carbenes, Collision-induced dissociation, Isomers, Lipids, Non-covalent complex, Radicals
DOI: 10.1016/j.ijms.2015.07.006
ISSN: 1387-3806
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > ANALYTICAL CHEMISTRY (030100)
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 2015 Elsevier
Copyright Statement: Licensed under the Creative Commons Attribution; Non-Commercial; No-Derivatives 4.0 International. DOI: 10.1016/j.ijms.2015.07.006
Deposited On: 30 Jun 2016 05:01
Last Modified: 20 Jul 2016 04:21

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