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Kinetics of oxidation of iron(II) ions with lipid hydroperoxides

One of the pathways for excessive production of free radicals is the decomposition of lipid hydroperoxides catalyzed by iron. A number of hydroperoxides of unsaturated fatty acids (LOOH), some prepared in our laboratory and others extracted from biological materials, were used to determine the rate constants of Fe2+ oxidation by measuring the formation rate of Fe3+ ions in the presence of simple unidentate ligands, chloride, and thiocyanate as the [FeCl]2+ and [FeNCS]2+ complexes, in a deoxygenated dichloromethane:methanol (2:1, v/v) mixture. The rates of Fe2+ oxidation with prepared LOOHs via the [FeNCS]2+ complex were approximately the same the average second-order reaction rate constant was 1390 ± 340 dm3 mol−1 s−1 ; the rate constants of LOOHs from different biological materials were in the same range. The rates measured as the [FeNCS]2+ complex were somewhat higher than the rates measured as the [FeCl]2+ complex, indicating that ligands could interact in the transition state, thus affecting the disruption of the intermediate complex. Since there were no significant differences in the activation thermodynamic parameters for reactions within the reaction series of studied hydroperoxides, it was assumed that the oxidation proceeded by an inner sphere mechanism, considering that the breakdown of the successor inner sphere complex with the homolytic cleavage of peroxide bonds of hydroperoxides forming reactive alkoxyl radicals was the rate-limiting step. Based on this research, an indirect spectrophotometric method for quantitative determination of LOOH was reestimated. The microprocedure proposed for the lipid hydroperoxide assay could be applied to follow the early stages of lipid peroxidation processes in real biological samples.

iron ; lipid hydroperoxides ; lipid peroxidation ; oxidation ; unsaturated fatty acids

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