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Elution factors of synthetic oxotriacylglycerols as an aid in identification of peroxidized natural triacylglycerols by reverse-phase high-performance liquid chromatography with electrospray mass spectrometry

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Lipids

Abstract

Selected elution factors were determined for model oxotriacylglycerols as an aid in identification of the peroxidation products of natural triacylglycerols by reverse-phase high-performance liquid chromatography (HPLC) with electrospray mass spectrometry (LC/ES/MS). For this purpose synthetic triacylglycerols of known structure were converted to hydroperoxides, hydroxides, epoxides, and core aldehydes and their dinitrophenylhydrazones by published procedures. The oxotriacylglycerols were resolved by normal-phase thin-layer chromatography and reverse-phase HPLC, and the identities of the oxotriacylglycerols confirmed by LC/ES/MS. Elution factors of oxotriacylglycerols were determined in relation to a homologous series of saturated triacylglycerols, ranging from 24 to 54 acylcarbons, and analyzed by reverse-phase HPLC, using a gradient of 20–80% isopropanol in methanol as eluting solvent and an evaporative light-scattering detector. It was shown that the elution times varied with the nature of the functional group and its regiolocation in the triacylglycerol molecule. A total of 31 incremental elution factors were calculated from chromatography of 33 oxygenated and nonoxygenated triacylglycerol species, ranging in carbon number from 36 to 54 and in double-bond number from 0 to 6.

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Abbreviations

DNPH:

2,4-dinitrophenylhydrazine

ECN:

equivalent carbon number

ES:

electrospray

F i :

correction factor

HPLC:

high-performance liquid chromatography

LC:

liquid chromatography

M:

molecular ion

MS:

mass spectrometry

TBHP:

tert-butyl hydroperoxide

TCN:

theoretical carbon number

TLC:

thin-layer chromatography

TPP:

triphenylphosphine

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Authors and Affiliations

  1. Department of Biochemistry and Food Chemistry, University of Turku, FIN-20014, Turku, Finland

    Olli Sjövall

  2. Banting and Best Department of Medical Research, University of Toronto, Charles H. Best Institute, 112 College St., M5G 1L6, Toronto, Ontario, Canada

    Olli Sjövall, Arnis Kuksis, Lajos Marai & John J. Myher

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  1. Olli Sjövall
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  2. Arnis Kuksis
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  3. Lajos Marai
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  4. John J. Myher
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Correspondence to Arnis Kuksis.

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Sjövall, O., Kuksis, A., Marai, L. et al. Elution factors of synthetic oxotriacylglycerols as an aid in identification of peroxidized natural triacylglycerols by reverse-phase high-performance liquid chromatography with electrospray mass spectrometry. Lipids 32, 1211–1218 (1997). https://doi.org/10.1007/s11745-997-0155-4

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  • DOI: https://doi.org/10.1007/s11745-997-0155-4

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