title: Electron-transfer oxidation properties of unsaturated fatty acids and mechanistic insight into lipoxygenases.
abstract: Rate constants of photoinduced electron-transfer oxidation of unsaturated fatty acids with a series of singlet excited states of oxidants in acetonitrile at 298 K were examined and the resulting electron-transfer rate constants (k(et)) were evaluated in light of the free energy relationship of electron transfer to determine the one-electron oxidation potentials (E(ox)) of unsaturated fatty acids and the intrinsic barrier of electron transfer. The k(et) values of linoleic acid with a series of oxidants are the same as the corresponding k(et) values of methyl linoleate, linolenic acid, and arachidonic acid, leading to the same E(ox) value of linoleic acid, methyl linoleate, linolenic acid, and arachidonic acid (1.76 V vs SCE), which is significantly lower than that of oleic acid (2.03 V vs SCE) as indicated by the smaller k(et) values of oleic acid than those of other unsaturated fatty acids. The radical cation of linoleic acid produced in photoinduced electron transfer from linoleic acid to the singlet excited state of 10-methylacridinium ion as well as that of 9,10-dicyanoanthracene was detected by laser flash photolysis experiments. The apparent rate constant of deprotonation of the radical cation of linoleic acid was determined as 8.1 x 10(3) s(-1). In the presence of oxygen, the addition of oxygen to the deprotonated radical produces the peroxyl radical, which has successfully been detected by ESR. No thermal electron transfer or proton-coupled electron transfer has occurred from linoleic acid to a strong one-electron oxidant, Ru(bpy)3(3+) (bpy = 2,2'-bipyridine) or Fe(bpy)3(3+). The present results on the electron-transfer and proton-transfer properties of unsaturated fatty acids provide valuable mechanistic insight into lipoxygenases to clarify the proton-coupled electron-transfer process in the catalytic function.
authors.affiliation: Department of Material and Life Science, Graduate School of Engineering, Osaka University, SORST, Japan Science and Technology Agency (JST), Suita, Osaka 565-0871, Japan.
authors.forename: Hironori
authors.initials: H
authors.lastname: Kitaguchi
authors.forename: Kei
authors.initials: K
authors.lastname: Ohkubo
authors.forename: Seiji
authors.initials: S
authors.lastname: Ogo
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
mesh_terms: D002384:Catalysis; D004579:Electron Transport; D005231:Fatty Acids, Unsaturated / Q000737:chemistry*; D007700:Kinetics; D019787:Linoleic Acid / Q000737:chemistry; D008084:Lipoxygenase / Q000378:metabolism*; D010084:Oxidation-Reduction; D010782:Photolysis
chemical_list: D005231:Fatty Acids, Unsaturated; D019787:Linoleic Acid; D008084:Lipoxygenase