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A more recent version of this article appeared on April 1, 2007

Papers In Press, published online ahead of print January 16, 2007
J. Lipid Res., doi:10.1194/jlr.M600446-JLR200
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Submitted on October 6, 2006
Revised on January 16, 2007
Accepted on January 16, 2007

Intramolecular rearrangement of linolenate peroxyl radicals in lipoxygenase reactions at lower oxygen content

Tokuko Takajo, Kazunori Tsuchida, Tsuyoshi Murahashi, Koichi Ueno, and Ichiro Koshiishi

Faculty of Pharmaceutical Sciences, Nihon Pharmaceutical University, Saitama 362-0806

Corresponding Author: ikoshi{at}nichiyaku.ac.jp

Variation of tissue oxygen content is thought to be a possible factor in determining the structural diversity of hydroperoxy fatty acids. In the present study, we evaluated the structural diversity of intermediate carbon-centered radicals at lower oxygen content. When the buffered solution (pH 7.4) containing 1.0 mM alpha -linolenic acid (LnA), 1.0 mu M soybean 15-lipoxygenase and 1.0 mM nitroxyl radical (3-carbamoyl-2,2,5,5-tetramethyl-3-pyrroline-N-oxyl; Cmdelta P), which selectively traps carbon-centered radicals, was incubated in a sealed vial, the generation of linolenate hydroperoxide was completed within one minute. In the subsequent reaction at lower oxygen content, the production of the [LnA-H+O2]-Cmdelta P adduct was ascertained by LC-MS/MS with precursor ion scanning. Furthermore, HPLC analysis with photodiode array detection showed that the adduct exhibits an absorption maximum at 278 nm, indicating a conjugated triene moiety. Based on these facts, the structure of the adduct was speculated to be C2H5-CH(Cmdelta P)-CH=CH-CH=CH-CH=CH-CH(OOH)-C7H14-COOH. We proposed a possible reaction pathway as follows: a linolenate 9-peroxyl radical generated in the lipoxygenase reaction might be converted into C2H5-CH-CH=CH-CH=CH-CH=CH-CH(OOH)-C7H14-COOH through an intramolecular rearrangement. This intermediate radical may give rise to hydroperoxy fatty acids with structural diversity.


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T. Takajo, K. Tsuchida, K. Ueno, and I. Koshiishi
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J. Lipid Res., June 1, 2007; 48(6): 1371 - 1377.
[Abstract] [Full Text] [PDF]


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