title: Nitrosylmyoglobin as antioxidant--kinetics and proposed mechanism for reduction of hydroperoxides.
abstract: Nitrosylmyoglobin (MbFe(II)NO), which is believed to have a protective role during ischemia and reperfusion injury, was oxidized by tert-butyl hydroperoxide (t-BuOOH), and by hydrogen peroxide (H(2)O(2)) to the nitrite anion and metmyoglobin (MbFe(III)). Further characterization of the reaction of MbFe(II)NO with excess of t-BuOOH was investigated with respect to reaction stoichiometry, temperature and pH dependence. It was found that the reaction between MbFe(II)NO with excess of t-BuOOH followed a simple stoichiometry and had moderate pH and temperature dependence with the activation parameters DeltaH(double dagger) = 57.4 +/- 1.4 kJ mol(- 1) and DeltaS(double dagger) = - 112.0 +/- 5.1 J mol(- 1) K(- 1), which is consistent with an associative reaction mechanism. Moreover, t-BuOOH-induced oxidation of MbFe(II)NO did not result in any detectable formation of the hypervalent myoglobin (Mb) species, i.e. perferrylmyoglobin, (( radical)MbFe(IV) = O) or ferrylmyoglobin (MbFe(IV) = O), and hereby differed from H(2)O(2)-induced oxidation of MbFe(II)NO, which results in the formation of MbFe(IV) = O. Based on the obtained results and on published data, different mechanisms for the reaction of the MbFe(II)NO with t-BuOOH and H(2)O(2) are proposed.
authors.affiliation: Department of Seafood Research, Danish Institute for Fisheries Research, Technical University of Denmark, Kgs Lyngby, Denmark.
authors.forename: Caroline P
authors.initials: CP
authors.lastname: Baron
authors.forename: Jens K S
authors.initials: JK
authors.lastname: Møller
authors.forename: Leif H
authors.initials: LH
authors.lastname: Skibsted
authors.forename: Henrik J
authors.initials: HJ
authors.lastname: Andersen
mesh_terms: D000818:Animals; D000975:Antioxidants / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D009211:Myoglobin / Q000737:chemistry*; D010084:Oxidation-Reduction; D013696:Temperature; D020122:tert-Butylhydroperoxide / Q000737:chemistry*
chemical_list: D000975:Antioxidants; D009211:Myoglobin; C031560:myoglobin nitroxide; D020122:tert-Butylhydroperoxide; D006861:Hydrogen Peroxide