Effect of Dr-Nb(III) on the kinetics for peroxynitrite isomerization, at pH 5.8 and 22.0 °C. (A) Averaged time courses of the Dr-Nb(III)-catalyzed isomerization of peroxynitrite in the absence of CO2. The time course analysis, according to Equation (1), allowed us to determine the following values of kobs: trace a, 3.1 s−1, R = 0.998; trace b, 7.6 s−1, R = 0.998. The Dr-Nb(III) concentration was: trace a, 1.0×10−5 M; trace b, 3.0 × 10−5 M. (B) Averaged time courses of the Dr-Nb(III)-catalyzed isomerization of peroxynitrite in the presence of CO2. The time course analysis, according to Equation (1), allowed us to determine the following values of kobs: trace a, 7.4 s−1, R = 0.999; trace b, 1.3 × 101 s−1, R = 0.998. The Dr-Nb(III) concentration was: trace a, 1.0 × 10−5 M; trace b, 3.0 × 10−5 M. The CO2 concentration was 1.2 × 10−3 M. (C) Dependence of kobs on the concentration of Dr-Nb(III) in the absence of CO2. Data were analyzed according to Equation (2) with kon = 2.2 × 105 M−1 s−1 and k0 = 8.1 × 10−1 s−1; R = 0.989, p = 0.0006. (D) Dependence of kobs on the concentration of Dr-Nb(III) in the presence of CO2. Data obtained were analyzed according to Equation (2) with kon = 2.8 × 105 M−1 s−1 and k0 = 4.1 s−1; R = 0.991, p = 0.0005. (E) Averaged time courses of peroxynitrite isomerization by apo-Dr-Nb in the absence of CO2. The time course analysis, according to Equation (1), allowed us to determine the following values of kobs: trace a, 8.3 × 10−1 s−1; trace b, 7.7 × 10−1 s−1. The apo-Dr-Nb concentration was: trace a, 1.0 × 10−5 M; trace b, 3.0 × 10−5 M. For clarity, trace b has been up-shifted of 0.3 units. (F) Averaged time courses of peroxynitrite isomerization by apo-Dr-Nb in the presence of CO2. The time course analysis, according to Equation (1), allowed us to determine the following values of kobs: trace a, 4.3 s−1; trace b, 3.9 s−1. The apo-Dr-Nb concentration was: trace a, 1.0 × 10−5 M; trace b, 3.0 × 10−5 M. For clarity, trace b has been up-shifted of 0.3 units. The CO2 concentration was 1.2 × 10−3 M. (G) Dependence of kobs on the concentration of apo-Dr-Nb in the absence of CO2. The symbol on the ordinate indicates the value of k0: 8.0 × 10−1 s−1. The average value of kobs obtained in the presence of apo-Dr-Nb is: 8.1 × 10−1 s−1. (H) Dependence of kobs on the concentration of apo-Dr-Nb in the presence of CO2. The symbol on the ordinate indicates the value of k0: 4.1 s−1. The average value of kobs obtained in the presence of apo-Dr-Nb and CO2 is: 4.1 s−1. In panels G and H, the differences among the kobs values are not statistically significant. The peroxynitrite concentration was 2.0 × 10−4 M. The HCO3− concentration was 5.0 × 10−1 M. Where not shown, the standard deviation is smaller than the symbol.