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Studying the Chemistry of Cationized Triacylglycerols Using Electrospray Ionization Mass Spectrometry and Density Functional Theory Computations

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Journal of The American Society for Mass Spectrometry

Abstract

Analysis 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+, NH4 +). 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.

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Acknowledgments

Felix Kannemann provided invaluable advice on the computations. The authors thank Karen MacDougall, Sue Penny, and Robert L. White for assistance and gratefully acknowledge access to computational facilities at the ACEnet Regional High Performance Computing Consortium for universities in Atlantic Canada, funded by the Canada Foundation for Innovation, the Atlantic Canada Opportunities Agency, and the provinces of Newfoundland and Labrador, Nova Scotia and New Brunswick.

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Authors and Affiliations

  1. National Research Council Canada, Halifax, Nova Scotia, B3H 3Z1, Canada

    J. Stuart Grossert, Lisandra Cubero Herrera, Louis Ramaley & Jeremy E. Melanson

  2. Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4R2, Canada

    J. Stuart Grossert & Louis Ramaley

  3. Measurement Science and Standards, National Research Council Canada, Ottawa, Ontario, K1A 0R6, Canada

    Jeremy E. Melanson

  4. Canadian Food Inspection Agency, 1992 Agency Drive, Dartmouth, Nova Scotia, B3B 1Y9, Canada

    Lisandra Cubero Herrera

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  1. J. Stuart Grossert
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Correspondence to J. Stuart Grossert.

Electronic supplementary material

Two files of Supplementary Information are provided. File JSG_LR_LCH_JEM_supp1 contains the additional figures mentioned in this paper, plus selected xyz coordinates for the structures described in this file. File JSG_LR_LCH_JEM_supp2 contains selected xyz coordinates for structures in this paper.

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Grossert, J.S., Herrera, L.C., Ramaley, L. et al. Studying the Chemistry of Cationized Triacylglycerols Using Electrospray Ionization Mass Spectrometry and Density Functional Theory Computations. J. Am. Soc. Mass Spectrom. 25, 1421–1440 (2014). https://doi.org/10.1007/s13361-014-0917-9

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