Abstract
Based on the understanding of lipid peroxidation as a free radical chain reaction, over 50 yr ago the three primary products of linoleic acid autoxidation were predicted to be the 9-, 11-, and 13-hydroperoxides. The 9- and 13-hydroperoxides were found at the time, but formation of 11-hydroperoxylinoleate or any other bis-allylic fatty acid hydroperoxide has not been reported hetetofore as a product of lipid peroxidation reactions. In vitamin E-controlled autoxidation of methyl linoleate, the 11-hydroperoxy derivative was identified as the next most prominent primary peroxidation product after the 9-and 13-hydroperoxides. It was present in approximately 5–10% of the abundance of the 9- or 13-hydroperoxide. The structures of 11-hydroperoxylinoleate and its 11-hydroxy derivative were established by high-pressure liquid chromatography, ultraviolet spectroscopy, gas chromatography-mass spectroscopy, and 1H nuclear magnetic resonance spectroscopy. The 11-hydroperoxide was not detectable in the absence of α-tocopherol, indicating that efficient trapping of the 11-peroxyl radical as the hydroperoxide is critical to permitting its accumulation.
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Abbreviations
- GC-MS:
-
gas chromatography-mass spectrometry
- HETE:
-
hydroxyeicosatetraenoic acid
- NMR:
-
nuclear magnetic resonance
- RP-HPLC:
-
reversed-phase high-pressure liquid chromatography
- SP-HPLC:
-
straight-phase HPLC
- TMS:
-
trimethylsilyl
- UV:
-
ultraviolet
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Brash, A.R. Autoxidation of methyl linoleate: Identification of the bis-allylic 11-hydroperoxide. Lipids 35, 947–952 (2000). https://doi.org/10.1007/s11745-000-0604-0
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DOI: https://doi.org/10.1007/s11745-000-0604-0