Kansas State University
Publishes on Free Radicals and Antioxidants, Electron Spin Resonance Studies, Electrochemical Analysis and Applications. 18 papers and 3k citations.
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Kinetic data for the superoxide radical (HO2⇄O−2 +H+, pK=4.8) in aqueous solution have been critically assessed. Rate constants for reactions of O−2 and HO2 with more than 300 organic and inorganic ions, molecules and other transient species have been tabulated.
The reaction of perhydroxyl radical (HO2) with linoleic, linolenic, and arachidonic acids has been studied in aqueous ethanolic solutions by the stopped flow technique. The corresponding rate constants are 1.2 x 10(3), 1.7 x 10(3), and 3.0 x 10(3) M-1 S-1, respectively. While kinetic results suggest that the HO2 radical reacts with the double allylic H atom of the polyunsaturated fatty acids, thermodynamic approximations indicate that the reaction is exothermic by approximately 10 kcal/mol. The relevance of this reaction to membrane damage observed in biological systems that have been exposed to HO2/O2- radicals is discussed.
To permit kinetic studies of the reactivity of unsaturated fatty acids towards oxygen radicals, it is essential to remove traces of hydroperoxides and other conjugated lipid impurities commonly present in commercial samples. Removal of these impurities has been satisfactorily achieved for oleic and linoleic acids by anaerobic low temperature recrystallization from acetonitrile. The UV spectra of commercial and purified samples are compared.