Kinetic and spectrophotometric studies of binding of iron(III) by glutathione

Abstract

In this report, determination of unbound aquo iron species is accomplished by a kinetic method involving reaction with sulfosalicylic acid (SSA) on a time scale which is very short with respect to reaction of SSA with the glutathione complexes of iron. The data are used to calculate conditional binding constants for Fe(III) to glutathione. Binding constants in 0.1 M ionic strength media were obtained between pH 1 and 2.4 by the kinetic method, and near pH = 3 by spectrophotometry and by examination of the ratio of rate of complex formation and dissociation. The conditional binding 'constant' between pH 1 and 3 is represented as pK = −1.96 – 0.50pH. This is consistent with the importance of reactions involving only very limited proton release. Spectrophotometric data show that the —OH group on Fe(OH)2+ is lost on glutathione complexing. Kinetics of the complex formation reaction between aquo iron(III) species and glutathione are slower than rates of reaction of iron(III) with simple ligands.The glutathione system is regarded as a model system important to natural water chemistry because it is a widely distributed biological sulfur-containing chelating agent.