Studying the chemistry of cationized triacylglycerols using electrospray ionization mass spectrometry and density functional theory computations

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DOIResolve DOI: http://doi.org/10.1007/s13361-014-0917-9
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TypeArticle
Journal titleJournal of the American Society for Mass Spectrometry
ISSN1044-0305
Volume25
Issue8
Pages14211440; # of pages: 20
SubjectBinding efficiencies of cations to triacylglycerols; Breakdown curves; Lithiated triglycerides; MS/MS/MS product ions; Solvent-cation interactions in ESI
AbstractAnalysis of triacylglycerols (TAGs), found as complex mixtures in living organisms, is typically accomplished using liquid chromatography, often coupled to mass spectrometry. TAGs, weak bases not protonated using electrospray ionization, are usually ionized by adduct formation with a cation, including those present in the solvent (e.g., Na+). There are relatively few reports on the binding of TAGs with cations or on the mechanisms by which cationized TAGs fragment. This work examines binding efficiencies, determined by mass spectrometry and computations, for the complexation of TAGs to a range of cations (Na+, Li+, K+, Ag+, NH 4 +). While most cations bind to oxygen, Ag+ binding to unsaturation in the acid side chains is significant. The importance of dimer formation, [2TAG + M]+ was demonstrated using several different types of mass spectrometers. From breakdown curves, it became apparent that two or three acid side chains must be attached to glycerol for strong cationization. Possible mechanisms for fragmentation of lithiated TAGs were modeled by computations on tripropionylglycerol. Viable pathways were found for losses of neutral acids and lithium salts of acids from different positions on the glycerol moiety. Novel lactone structures were proposed for the loss of a neutral acid from one position of the glycerol moiety. These were studied further using triple-stage mass spectrometry (MS3). These lactones can account for all the major product ions in the MS3 spectra in both this work and the literature, which should allow for new insights into the challenging analytical methods needed for naturally occurring TAGs.
Publication date
PublisherSpringer International Publishing
LanguageEnglish
AffiliationNational Research Council Canada; Aquatic and Crop Resource Development; Measurement Science and Standards
Peer reviewedYes
NRC numberNRC-ACRD-56074
NPARC number21272923
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Record identifierf2b7c569-50ea-4cf9-9f6e-a83849b5aeb7
Record created2014-12-03
Record modified2016-05-09
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