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Autoxidation of polyunsaturated triacylglycerols. III. Synthetic triacylglycerols containing linoleate and linolenate

  • Published:
Lipids

Abstract

Four triacylglycerols containing linoleate (L) and linolenate (Ln) in specific positions were synthesized to determine the effect of fatty acid position on their relative rates and products of autoxidation. Analyses by reversedphase high performance liquid chromatography (HPLC) showed that autoxidation of L- and Ln-containing triacylglycerols form monohydroperoxides and hydroperoxy epidioxides as the main products. The peroxyl radicals of internal 12- and 13-mono-hydroperoxides of Ln triacylglycerol components cyclized rapidly and their relative triacylglycerol position had no influence on their rates of cyclization. A good linear relation was obtained between total HPLC peak areas (detected at 235 nm) of the main oxidation products and peroxide values. Reversed phase HPLC analyses thus provide a useful method to estimate oxidation of polyunsaturated triacylglycerols. The ratios of Ln to L mono-hydroperoxides were twice the ratios of Ln to L in the triacylglycerol substrates. Ln triacylglycerol components, therefore, oxidized twice as much as the L components. At 40°C, LnLnL oxidized slightly faster than LnLLn with respective induction periods of 45 and 47 hr. LLnL oxidized faster than LLLn with respective induction periods of 56 and 60 hr. Dilinolenoyl-linoleoylglycerols are, therefore, slightly less stable to oxidation when Ln is in the 1,2- than the 1,3-triacylglycerol position. Dilinoleoyl-linolenoylglycerols are less stable when L is in the 1,3- than the 1,2-triacylglycerol position.

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Abbreviations

HPLC:

high performance liquid chromatography

TLC:

thin layer chromatography

GC:

gas chromatography

GC-MS:

gas chromatography-mass spectrometry

NMR:

nuclear magnetic resonance

UV:

ultraviolet

FI:

flame ionization

TMS:

trimethylsilyl

O:

oleate

S:

saturated compounds

U:

unsaturated compounds

P:

palmitate

L:

linoleate

Ln:

linolenate

LLL:

trilinoleoylglycerol

LnLnLn:

trilinoleoylglycerol

LnLL:

1-linolenoyl-2,3-dilinoleoylglycerol

LLnL:

2-linolenoyl-1,3-dilinoleoylglycerol

LLnLn:

1-linoleoyl-2,3-dilinolenoylglycerol

LnLLn:

2-linoleoyl-1,3-dilinolenoylglycerol

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Author notes

  1. K. Miyashita

    Present address: Hokkaido University, Hakodate, Japan

  2. E. N. Frankel

    Present address: Department of Food Science and Technology, University of California, 95616, Davis, CA

Authors and Affiliations

  1. Northern Regional Research Center, Agricultural Research Service, U.S. Department of Agriculture, 1815 North University St., 61604, Peoria, IL

    K. Miyashita, E. N. Frankel, W. E. Neff & R. A. Awl

Authors
  1. K. Miyashita
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  2. E. N. Frankel
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  3. W. E. Neff
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  4. R. A. Awl
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Miyashita, K., Frankel, E.N., Neff, W.E. et al. Autoxidation of polyunsaturated triacylglycerols. III. Synthetic triacylglycerols containing linoleate and linolenate. Lipids 25, 48–53 (1990). https://doi.org/10.1007/BF02562427

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  • DOI: https://doi.org/10.1007/BF02562427

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