Reaction of hypochlorite with fatty acid hydroperoxide results in free radical formationстатья

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[1] Reaction of hypochlorite with fatty acid hydroperoxide results in free radical formation / A. V. Chekanov, O. M. Panasenko, A. N. Osipov et al. // Biophysics. — 2005. — Vol. 50, no. 1. — P. 8–14. The reaction of hypochlorite with linileic acid hydroperoxide was studied by chemiluminescence activated with coumarine C-525 and spin trapping techniques.The hydroperoxide was obtained by the oxidation of the acid with lipoxygenase. Spin trap used was alpha-(4-pyridyl-1-oxide)-N-tert-butyl-nitrone. The addition of hypochlorite to the incubation medium of linoleic acid with lipoxygenase was shown to be acconpanied by a flash of chemiluminescence amplified by coumarine C-525. The intensity of the flash correlated with hydroperoxide concentration in incubation medium. The analysis of electron paramagnetic resonance spectra of spin adducts resulting from hypochlorite addition to the incubation medium of linoleic acid with lipoxygenase in the presence of the spin trap showd the formation of an O-centered, most likely peroxyl, radical (hyperfine coupling constants were abH = 0.260 mT, aN = 1.662 mT). Another adduct is a C-centered pentyl radical (hyperfine coupling constants are abH = 0.238 mT, aN = 1.564 mT) resulting from the direct reaction of lipoxygenase with the fatty acid. The results indicate that hypochlorite produced in vivo in the sites of phagocyte activation can react with hydroperoxides of fatty acid chains to give O-centered free radicals, which behave as the initiators of free-radical reactions and can play an important role in the development of a number of pathological states.

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