Oxidation Of Thiols By Copper(II)
- 1 May 1994
- journal article
- research article
- Published by Taylor & Francis Ltd in Phosphorus, Sulfur, and Silicon and the Related Elements
- Vol. 90 (1-4), 147-154
- https://doi.org/10.1080/10426509408016396
Abstract
Thiols were oxidized by Cu(II) in a reaction that had two phases. There was an immediate reaction between thiol and Cu(II) with loss of thiol, measured by its reaction with 5,5′-dithio-bis(2-nitrobenzoic acid), and formation of Cu(I), measured by its reaction with bathocuproinedisulfonic acid. With equal molar concentrations of thiols and Cu(II), only the first phase was observed and thiols were oxidized in less than 15 sec. When the concentration of Cu(II) was limiting (200 μM thiol and 10 to 160 μM Cu(II)), the second phase of the reaction was observed; this phase was much slower for glutathione (GSH) than it was for cysteine and accounts for previous reports that GSH is oxidized by Cu(II) at a slower rate than cysteine. It is proposed that Cu(II) reacts with thiols to form Cu(II)-thiol complexes, Cu(II) is reduced to Cu(I), and the thiols are oxidized to the corresponding radicals. Two of the radicals react to form a disulfide and Cu(I) reacts with a second thiol to form a Cu(I)-thiol complex in which the Cu(I) is oxidized to Cu(II) by oxygen. The rate of reoxidation of Cu(I) is dependent on the R group of the thiol and is the rate limiting step of the reaction.Keywords
This publication has 25 references indexed in Scilit:
- KINETICS OF Cu(II) CATALYSED-OXIDATION OF CYSTEINE HYDROCHLORIDE BY METHYLENE BLUE IN ACIDIC MEDIUMPhosphorus, Sulfur, and Silicon and the Related Elements, 1992
- Inhibition by thiols of copper(II)-induced oxidation of oxyhemoglobinChemico-Biological Interactions, 1992
- Copper(II) (3,5-diisopropylsalicylate)2 oxidizes thiols to symmetrical disulfides and oxidatively converts mixtures of 5-thio-2-nitrobenzoic acid and nonsymmetrical 5-thio-2-nitrobenzoic acid disulfides to symmetrical disulfidesJournal of Inorganic Biochemistry, 1991
- Antioxidant properties of 2-imidazolones and 2-imidazolthionesBiochemical Pharmacology, 1987
- Reaction of urates and other antioxidants with galvinoxylMicrochemical Journal, 1985
- Interaction of Galvinoxyl Radical with Ascorbic Acid, Cysteine, and Glutathione in Homogeneous Solution and in Aqueous DispersionsBulletin of the Chemical Society of Japan, 1985
- The production of free radicals during the autoxidation of cysteine and their effect on isolated rat hepatocytesBiochimica et Biophysica Acta (BBA) - General Subjects, 1982
- Comparison of the catalytic oxidation of cysteine and o-dianisidine by cupric ion and ceruloplasminJournal of Inorganic Biochemistry, 1982
- Catalytic oxidation of sulfhydryl groups by o-phenanthroline copper complexBiochimica et Biophysica Acta (BBA) - General Subjects, 1968
- Cuprous Ion Formation in Cupric Ion Catalyzed Oxidations1,2Journal of the American Chemical Society, 1957