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Photosensitized oxidation of methyl linoleate: Secondary and volatile thermal decomposition products

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Lipids

Abstract

Studies of photosensitized oxidation of methyl linoleate show that the greater relative concentration of 9- and 13-hydroperoxides than 10- and 12-hydroperoxides is characteristic of singlet oxygenation and not due to either simultaneous autoxidation or type 1 photosensitized oxidation. Cyclization of the internal 10- and 12-hydroperoxides accounts for their lower relative concentrations. Secondary products separated by silicic acid and high pressure liquid chromatography were characterized spectrally (IR, UV,1H-NMR,13C-NMR, GC-MS). Major secondary products included diastereomeric pairs of 13-hydroperoxy-10,12-epidioxy-trans-8-octadecenote (I and III) and 9-hydroperoxy-10,12-epidioxy-trans-13-octadecenoate (II and IV); minor secondary products included hydroperoxy oxy genated and epoxy esters. Thermal decomposition of the hydroperoxy cyclic peroxides produced hexanal and methyl 10-oxo-8-decenoate as major volatiles from I and III and methyl 9-oxo-nonanoate and 2-heptenal from II and IV. Hydroperoxy cyclic peroxides may be important sources of volatile decomposition products of photooxidized fats.

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Authors and Affiliations

  1. Nothern Regional Research Center, Agricultural Research, U.S. Department of Agriculture, 61604, Peoria, IL

    E. N. Frankel, W. E. Neff, E. Selke & D. Weisleder

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  1. E. N. Frankel
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  2. W. E. Neff
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  3. E. Selke
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  4. D. Weisleder
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Frankel, E.N., Neff, W.E., Selke, E. et al. Photosensitized oxidation of methyl linoleate: Secondary and volatile thermal decomposition products. Lipids 17, 11–18 (1982). https://doi.org/10.1007/BF02535116

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  • DOI: https://doi.org/10.1007/BF02535116

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