The hydrolytic autoxidation of 1,4-naphthoquinone-2-potassium sulphonate: Implications for 1,4-naphthoquinone-2-potassium sulphonate-induced oxidative stress in the red blood cell

Abstract

1,4-Naphthoquinone-2-potassium sulphonate (NQKS) undergoes an autoxidation reaction in aqueous solution under physiological conditions to produce 3-hydroxy-1,4-naphthoquinone-2-potassium sulphonate (NQKS-OH). Intermediates of dioxygen reduction, superoxide radicals, hydrogen peroxide and hydroxyl radicals, are also detected. The kinetics of the autoxidation of NQKS show a first order dependence on NQKS and hydroxide ion concentration and a zeroth order dependence on oxygen concentration. For the rate equation r = − d[O 2]/ dt = k obs., [NQKS][ −OH], k obs. = (6.4 ± 0.6) × 10 2 M −1 s −1 at 37°C. Hydroxide ion attack on NQKS appears to be the rate determining step. The reaction may be conveniently described as a ‘hydrolytic autoxidation’. The hydrolytic autoxidation of NQKS occurs in NQKS-treated red blood cells; the hydroxylated quinone NQKS-OH is produced and hydroxyl radical formation is stimulated. The importance of this reaction in NQKS-induced oxidative stress in red blood cells is discussed. The hydrolytic autoxidation of quinones bearing one or more unsubstituted (hydrogen) positions on the quinone centre is a novel mechanism by which such quinones may induce oxidative stress in cellular systems.