REACTION OF HYPOCHLOROUS ACID WITH HYDROGEN-PEROXIDE AND TERT-BUTYL HYDROPEROXIDE - H-1-NMR SPECTROSCOPY AND CHEMILUMINESCENCE ANALYSES

In contrast to the well-known reaction of hypochlorous acid with hydro gen peroxide, no singlet oxygen is formed as the result of reaction be tween hypochlorous acid and tert-butyl hydroperoxide. The reaction wit h hydrogen peroxide yielded a quadratic dependence of light intensity on reactant concentration, a drastic enhancement of luminescence yield using D2O as solvent and only an emission of red light, that are typi cal characteristics of emission resulting from two molecules of delta singlet oxygen. Other chemiluminescence properties were observed using tert-butyl hydroperoxide. There was a linear dependence of light inte nsity on reactant concentration using tert-butyl hydroperoxide in exce ss with a decline of emission at higher concentrations. H-1-NMR spectr oscopic analysis revealed di-tert-butyl peroxide, tert-butanol and als o tert-butyl hypochlorite, acetone and acetate as products of the reac tion between hypochlorous acid and tert-butyl hydroperoxide. The forma tion of di-tert-butyl pel oxide is only possible assuming a tert-butyl oxy radical as primary intermediate product of this reaction. Our resu lts demonstrate that alkoxy radicals derived from organic hydroperoxid es can participate in lipid peroxidation induced by hypochlorous acid. On the other hand, singlet oxygen did not influence the yield of pero xidation products. Changing H2O for D2O in suspension of egg yolk phos phaditylcholine no differences in accumulation of thiobarbituric acid reactive products were observed.