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Collision-Induced Dissociation of Fatty Acid [M – 2H + Na]– Ions: Charge-Directed Fragmentation and Assignment of Double Bond Position

  • Research Article
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Journal of The American Society for Mass Spectrometry

Abstract

The collision-induced dissociation (CID) of cationic fatty acid–metal ion complexes has been extensively studied and, in general, provides rich structural information. In particular, charge-remote fragmentation processes are commonly observed allowing the assignment of double bond position. In a previous manuscript, we presented two methods to doubly deprotonate polyunsaturated fatty acids to form anionic fatty acid–sodium ion complexes, referred to as [M – 2H + Na] – ions. In the current manuscript, the CID behavior of these [M – 2H + Na] – ions is investigated for the first time. Significantly, we also present a deuterium-labeling experiment, which excludes the possibility that deprotonation occurs predominately at the α-carbon in the formation of fatty acid [M – H + NaF]– ions. This supports our original proposal where deprotonation occurs at the bis-allylic positions of polyunsaturated fatty acids. CID spectra of polyunsaturated fatty acid [M – 2H + Na]– ions display abundant product ions arising from acyl chain cleavages. Through the examination of fatty acid isomers, it is demonstrated that double bond position may be unequivocally determined for methylene-interrupted polyunsaturated fatty acids with three or more carbon–carbon double bonds. In addition, CID of [M – 2H + Na]– ions was applied to 18:3 isomers of Nannochloropsis oculata and three isomers were tentatively identified: ∆9,12,1518:3, ∆6,9,1218:3, and ∆5,8,1118:3. We propose that structurally-informative product ions are formed via charge-driven fragmentation processes at the site of the resonance-stabilized carbanion as opposed to charge-remote fragmentation processes, which could be inferred if deprotonation occurred predominately at the α-carbon.

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Acknowledgments

The authors acknowledge Moreton Bay Research Station (MBRS) for providing laboratory space. M.C.T. acknowledges Dr. Mei Bai (University of Melbourne) for support while preparing this manuscript. M.C.T also acknowledges Professor Stephen Blanksby (University of Wollongong) and Dr. Ben Kirk (Lawrence Berkeley National Laboratory) for their keen insights into this topic.

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Authors and Affiliations

  1. Independent Marine Biochemistry Research, Moreton Bay Research Station, Dunwich, QLD, 4183, Australia

    Michael C. Thomas, Jens Altvater, Thomas J. Gallagher & Geoffrey W. Nette

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  1. Michael C. Thomas
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  2. Jens Altvater
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  3. Thomas J. Gallagher
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Correspondence to Michael C. Thomas.

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Thomas, M.C., Altvater, J., Gallagher, T.J. et al. Collision-Induced Dissociation of Fatty Acid [M – 2H + Na]– Ions: Charge-Directed Fragmentation and Assignment of Double Bond Position. J. Am. Soc. Mass Spectrom. 25, 1917–1926 (2014). https://doi.org/10.1007/s13361-014-0966-0

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  • DOI: https://doi.org/10.1007/s13361-014-0966-0

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