title: Kinetics and mechanism of the oxidation of glutathione by hexacyanoferrate (III) in aqueous solution.
abstract: A detailed kinetic study of the oxidation of glutathione by Fe(CN)6(3)- was performed as a function of pH, temperature, and pressure. The pH profile indicates a maximum pH independent rate in the pH range 5 to 8, which is ascribed to the oxidation of the monoanionic form of glutathione. The activation parameters for the oxidation process in this pH range are characterized by significantly negative delta V# (-22 cm3 mol-1) values. The latter value is in good agreement with that calculated theoretically on the basis of the Marcus-Hush-Stranks relationships, and can be ascribed to a large volume collapse associated with the outer-sphere reduction of Fe(CN)6(3-) to Fe(CN)6(4-).
authors.affiliation: Institute for Inorganic Chemistry, University of Witten/Herdecke, Germany.
authors.forename: G
authors.initials: G
authors.lastname: Stochel
authors.forename: P
authors.initials: P
authors.lastname: Martinez
authors.forename: R
authors.initials: R
authors.lastname: van Eldik
mesh_terms: D004563:Electrochemistry; D005292:Ferricyanides / Q000737:chemistry*; D005978:Glutathione / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D010084:Oxidation-Reduction; D011312:Pressure; D012996:Solutions; D013696:Temperature; D014867:Water
chemical_list: D005292:Ferricyanides; D012996:Solutions; D014867:Water; C007931:hexacyanoferrate III; D005978:Glutathione