Composition and catalase-like activity of Mn(II)-bicarbonate complexes

The composition and catalase-like activity of Mn2+ complexes with bicarbonate were investigated with voltammetry and kinetic methods (by the rate of O2 production from H2O2). Three linear sections were revealed on the dependence of the reduction potential of Mn2+ on logarithm of bicarbonate concentration (logC(NaHCO3)) having slopes equal to 0 mV/logC(NaHCO3), -14 mV/logC(NaHCO3), and -59 mV/logC(NaHCO3), corresponding to Mn2+ aqua complex (Mn2+(aq)) and to Mn2+-bicarbonate complexes of the composition [Mn2+(HCO3(-))]+ (at concentration of HCO3(-) 10-100 mM) and [Mn2+(HCO3(-))2]0 (at concentration of HCO3(-) 100-600 mM). Comparison of HCO3(-) concentration needed for the catalase-like activity of Mn2+ with the electrochemical data showed that only electroneutral complex Mn2+(HCO3(-))2 catalyzed decomposition of H2O2, whereas positively charged Mn2+(aq) complex and [Mn2+(HCO3(-))]+ were not active. The catalase-like activity of Mn2+ did not appear upon substitution of anions of carbonic acids (acetate and formate) for HCO3(-). The rate of O2 production in the system Mn2+-HCO3(-)-H2O2 (pH 7.4) is proportional to the second power of Mn2+ concentration and to the fourth power of HCO3(-) concentration that indicates simultaneous involvement of two Mn2+(HCO3(-))2 complexes in the reaction of H2O2 decomposition.