title: Direct ESR detection of pentadienyl radicals and peroxyl radicals in lipid peroxidation: mechanistic insight into regioselective oxygenation in lipoxygenases.
abstract: Well-resolved ESR spectra of free pentadienyl radicals have been observed under photoirradiation of di-tert-butylperoxide (Bu(t)OOBu(t)) and polyunsaturated fatty acids in the absence of O(2), allowing us to determine the hfc values. The hfc values of linoleyl radical indicate that the spin density is the largest at the C-11 position. The linoleyl radical is readily trapped by O(2) to produce the peroxyl radical (11-HPO.) in which O(2) is added mainly at the C-11 position of the pentadienyl radical as indicated by the comparison of the ESR spectra of peroxyl radicals derived from linoleic acid and [11,11-(2)H(2)]linoleic acid. The peroxyl radical (13-HPO.), which is initially formed by the hydrogen abstraction from 13-(S)-hydroperoxy-9(Z),11(E)-octadecadienoic acid (13-HPOD) by Bu(t)O., is found to isomerize to 11-HPO. via removal of O(2) from 13-HPO. and addition of O(2) to linoleyl radical to produce 11-HPO. . This finding supports an idea of O(2) entering via a specific protein channel, which determines the stereo- and regiochemistry of the biradical combination between O(2) and linoleyl radical in lipoxygenases.
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: D000466:Alkadienes / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals / Q000737:chemistry; D019787:Linoleic Acid / Q000737:chemistry; D015227:Lipid Peroxidation; D008084:Lipoxygenase / Q000737:chemistry* / Q000378:metabolism*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D010545:Peroxides / Q000737:chemistry*; D013379:Substrate Specificity
chemical_list: D000466:Alkadienes; D005609:Free Radicals; D010545:Peroxides; C111570:di-tert-butyl peroxide; C049375:perhydroxyl radical; D019787:Linoleic Acid; D008084:Lipoxygenase; D010100:Oxygen