Radical formation in individual aqueous solutions of some unsaturated fatty acids and in their mixtures

This study examines oxidizability in individual aqueous solutions of oleic acid, linoleic acid, α-linolenic acid, γ-linolenic acid and arachidonic acid, and in their mixtures. We used electron spin resonance (ESR), high performance liquid chromatography-electron spin resonance (HPLC-ESR) and high performance liquid chromatography-electron spin resonance-mass spectrometries (HPLC-ESR-MS). We detected 4-carboxybutyl radical derived from γ-linolenic acid, ethyl and 7-carboxyheptyl radicals derived from α-linolenic acid, and pentyl and 7-carboxyheptyl radicals derived from linoleic acid. HPLC-ESR analyses for the individual aqueous solutions of linoleic acid, α-linolenic acid, γ-linolenic acid and arachidonic acid showed less radical form for polyunsaturated fatty acids with more double bonds. On the other hand, HPLC-ESR peak height of 4-carboxybutyl radical, which form through hydrogen atom abstraction at the carbon close to the carboxy end, increased for linoleic acid/γ-linolenic acid, α-linolenic acid/γ-linolenic acid, and γ-linolenic acid/oleic acid mixtures compared to before mixing. Conversely, HPLC-ESR peak heights of ethyl, 7-carboxyheptyl and pentyl radicals, which form through hydrogen atom abstraction at the carbons close to the methyl end, decreased for linoleic acid/α-linolenic acid, linoleic acid/γ-linolenic acid, linoleic acid/oleic acid, linoleic acid/arachidonic acid, α-linolenic acid/γ-linolenic acid, and α-linolenic acid/oleic acid mixtures compared to before mixing.