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The use of nicotinates and sulfoquinovosyl monoacylglycerols in the analysis of monounsaturated n-3 fatty acids by mass spectrometry

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Lipids

Abstract

Fatty acyl groups (16∶1 and 16∶0) liberated from purified sulfoquinovosyl diacylglycerols produced by the unicellular marine microalga,Heterosigma carterae (formerlyH. akashiwo), were converted to either the corresponding alcohols or methyl esters. Nicotinate derivatives of the alcohols were examined by combined gas chromatography/mass spectrometry, and the methyl esters were examined by nuclear magnetic resonance (NMR) spectroscopy after separation by high-performance liquid chromatography. Three different hexadecenoyl fatty acyl groups were identified, one of which wascis 13-hexadecenoyl (16∶1n−3). Both the configuration and the n−3 position of the double bond in thecis 13-hexadecenoyl moiety were unequivocally established by NMR analysis of the corresponding methyl ester. The nicotinate derived from the alcohol of the 16∶1n−3 fatty acyl moiety gave a characteristic fragmentation series in the electron impact msss spectrum which, by careful interpretation, was consistent with, but not unambiguous for, the assigned location of the double bond. Tandem mass spectrometry experiments on a sulfoquinovosyl monoacylglycerol containing thecis 13-hexadecenoyl group in thesn-2 position, using negative-ion liquid secondary ion mass spectrometry, also gave a fragmentation pattern which was consistent with the positional assignment of the double bond.

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Abbreviations

COSY:

correlated spectroscopy

EI:

electron impact

GC/MS:

gas chromatography/mass spectrometry

LSIMS:

liquid secondary ion mass spectrometry

MS/MS:

tandem mass spectrometry

NMR:

nuclear magnetic resonance

SQDG:

sulfoquinovosyl diacylglycerol

SQMG:

sulfoquinovosyl monoacylglycerol

TLC:

thin-layer chromatography

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Authors and Affiliations

  1. Institute for Marine Biosciences, National Research Council of Canada, 1411 Oxford Street, B3H 3Z1, Halifax, Nova Scotia, Canada

    Michael Keusgen, Jonathan M. Curtis & Stephen W. Ayer

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  1. Michael Keusgen
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  2. Jonathan M. Curtis
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  3. Stephen W. Ayer
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Keusgen, M., Curtis, J.M. & Ayer, S.W. The use of nicotinates and sulfoquinovosyl monoacylglycerols in the analysis of monounsaturated n-3 fatty acids by mass spectrometry. Lipids 31, 231–238 (1996). https://doi.org/10.1007/BF02522625

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  • DOI: https://doi.org/10.1007/BF02522625

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