Abstract
Considerable controversy surrounds the nature of the mechanisms involved in the copper-catalysed decomposition of hydrogen peroxide, and it seems likely that a very wide range of mechanistic types is implicated — including non-radical mechanisms, those which involve oxygen-centred radicals (possibly in Fenton-type chemistry), and the reactions of high-valent copper (CuIII) and copper-peroxo species [1]. Thus it has been suggested that CuII-H2O2 reactions involve the hydroxyl radical (formed via CuI and H2O2 [2]); other workers have claimed that copper complexes [3] or [4] CuIIIare involved and, at least for certain ligands and substrates, it is proposed that copper-catalysed decomposition of hydrogen peroxide does not involve free radicals [5]. The precise mechanism followed is likely to be critically dependent on the reaction conditions (e.g. solvent, ligand and substrate) and on the nature of any added potential one-electron reductants.
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References
Weser,U., Steinkuhler, C. and Rotilio, G. (1996) Copper complexes and free radicals, in G. Berthon (ed.), Handbook of Metal-Ligand Interactions in Biological Fluids, Marcel Dekker, Part 4, Chapter 3, pp. 867–875.
Goldstein, S. and Czapski, G. (1983) Mechanisms of the dismutation of superoxide catalysed by the copper(II) phenanthroline complex by oxygen in aqueous solution, J. Am. Chem. Soc., 105, 7276–7280.
Masarwa, M., Cohen, H., Meyerstein, D., Hickman, D. L., Bakac A. and Espenson, J. H. (1988) Reactions of low-valent transition-metal complexes with hydrogen peroxide. Are they “Fenton-like” or not? 1. The case of Cu*(aq) and Cr2+(aq), J. Am. Chem. Soc., 110, 4293–4297.
Johnson, G. R. A., Nazhat, N. B. and Saadalla-Nazhat, N. A. (1988) Reaction of the aquacopper(I) ion with hydrogen peroxide–evidence for a Cu(III) (cupryl) intermediate, J. Chem. Soc. Faraday Trans. 1, 84, 501–510; Johnson, G. R. A. and Nazhat, N. B. (1987) Kinetics and mechanism of the reaction of the bis(1,10-phenanthroline) copper(I) ion with hydrogen peroxide in aqueous solution, J. Am. Chem. Soc, 109, 1990–1994.
See e.g. Sigel, H., Flierl, C. and Griesser, R. (1969) On the kinetics and mechanism of the decomposition of hydrogen peroxide, catalysed by the Cue2+-2, 2′-bipyridyl complex, J. Am. Chem. Soc., 91, 1061–1064.
Yamamoto, K. and Kawanishi, S. (1989) Hydroxyl free radical is not the main active species in site-specific DNA damage induced by copper(II) ion and hydrogen peroxide, J. Biol. Chem., 264, 1543515440.
Stoewe, R. and Prütz, W. A. (1987) Copper-catalysed DNA damage by ascorbate and hydrogen peroxide: kinetics and yield, Free Rad. Biol. Med., 3, 97–105.
Mukherjee, U. and Chatterjee, S. N. (1995) Oxidative damage of DNA and benzoate by chelated and non-chelated copper in the presence of hydrogen peroxide, Indian J. Biochem. Biophys., 32, 32–36.
Ozawa, T., Hanaki, A., Onodera, K. and Kasai, M. (1992) Reactions of copper(II)-N-polycarboxylate complexes with hydrogen peroxide in the presence of biological reductants: ESR evidence for the formation of hydroxyl radical, Biochem. International, 26, 477–483; see also Ozawa, T., Ueda, J. and Hanaki, A. (1993) Copper(II)-albumin complex can activate hydrogen peroxide in the presence of biological reductants: first ESR evidence for the formation of hydroxyl radical, Biochem. Mol. Biol. Int., 29, 247–253.
Reed, C. J. and Douglas, K. T. (1989) Single-strand cleavage of DNA by Cu(II) and thiols: a powerful chemical DNA-cleaving system, Biochem. Biophys. Res. Comm., 162, 1111–1117; Reed, C. J. and Douglas, K. T. (1991) Chemical cleavage of plasmid DNA by glutathione in the presence of Cu(II) ions, Biochem. J., 275, 601–608.
Hanna, P. M. and Mason, R. P. (1992) Direct evidence for inhibition of free radical formation from Cu(I) and hydrogen peroxide by glutathione and other potential ligands using the EPR spin-trapping approach, Arch. Biochem. Biophys., 295, 205.
Milne, L., Nicotera, P., Orrenius, S. and Burkitt, M. (1993) Effects of glutathione and chelating agents on copper-mediated DNA oxidation: pro-oxidant and antioxidant properties of glutathione, Arch. Biochem. Biophys.,304, 102–109..
Ferreira, A. M. C. and Toma, H. E. (1988) Further studies on the kinetics and mechanism of the copper imidazole catalysed decomposition of hydrogen peroxide, J. Coord. Chem., 18, 351–359.
Byrnes, R. W., Mohan, M., Antholine, W. E., Xu, R. X. and Petering, D. H. (1990) Oxidative systems induced by a copper-thiosemicarbazide complex, Biochem., 29, 7046–7053.
Saryan, L. A., Mailer, K., Krishnamurti, C., Antholine, W. and Petering, D. H. (1981) Interaction of 2formylpyridine thiosemicarbazonato copper(II) with Ehrlich ascites tumour cells, Biochem. Pharm., 30, 1595–1604.
Steinkühler, C., Mavelli, I., Rossi, L., Pederson, J. Z., Melino, G., Weser, U. and Rotilio, E. (1990) Cytotoxicity of a low molecular weight Cu2Zn2 superoxide dismutase active centre analogue in human erythroleukemia cells, Biochem. Pharm., 39, 1473–1479.
Shinar, E., Rachmilewitz, E. A., Shifter, A., Rahamin, E. and Saltman, P. (1989) Oxidative damage to human red cells induced by copper and iron complexes in the presence of ascorbate, Biochim Biophys Acta, 1014, 66–72.
Burkitt, M. J., Tsang, S. Y., Tam; S. C. and Bremner, I. (1995) Generation of 5,5-dimethyl-l-pyrroline N-oxide hydroxyl and scavenger radical adduct from copper/H2O2 mixtures: effects of metal ion chelation and the search for high-valent metal-oxygen intermediates, Arch. Biochem. Biophys., 323, 6370.
Gilbert, B. C., Scrivens, G. and Lee, T. C. P. (1995) EPR studies of the copper-catalysed oxidation of thiols with peroxides J. Chem. Soc. Perkin Trans. 2,995–963.
Davis, F. J., Gilbert, B. C., Norman, R. O. C. and Symons, M. C. R. (1983) ESR studies part 66. Characterisation of copper(II) complexes in the oxidation of D-penicillamine, L-cysteine and related sulphur-containing compounds, J. Chem. Soc. Perkin Trans. 2, 1763–1771.
Gunther, M. R., Hanna, P. M., Mason, R. P. and Cohen, M. S. (1995) Hydroxyl radical formation from cuprous ion and hydrogen peroxide: a spin-trapping study, Arch. Biochem. Biophys., 316, 515–522.
Smith, R. C., Reed, V. D. and Hill, W. E. (1994) Oxidation of thiols by copper(II), Phosphorus, Sulphur and Silicon, 90, 147–154.
McConnell, H. and Davison, N. (1950) Optical interaction between the chloro-complexes of copper(I) and copper(II) in solutions of unit ionic strength, J. Am. Chem. Soc., 72, 3168–3173.
Laurie, S. H., Lund, T. and Raynor, J. B. (1975) Electronic absorption and electron spin resonance studies on the interaction between the biologically relevant copper(II) glycylglycine and L-histidine complexes with D-penicillamine, J. Chem. Soc. Dalton Trans., 1389–1394; Kaim, W. and Schwederski, B. (1994) Bioinorganic Chemistry: Inorganic Elements in the Chemistry of Life, John Wiley and Sons Ltd, Chichester, UK.
Bard, A. J.,Parsons, R. and Jordan, J. (1985) Standard Potentials in Aqueous Solution,Marcel Dekker Inc, New York.
Creighton, J. A. and Lippincot, E. R. (1963) Raman spectra and solvent extractions of cuprous halides, J. Chem. Soc., 5134–5136; Specker, H. and Pappert, W. (1965) Extracted halo compounds of Cu, Ag, Au and TI, Z. Anorg. Allgem. Chem., 341, 287–292.
Gill, J. T., Mayerle, J. J., Welcker, P. S., Lewis, D. F., Ucko, D. A., Barton, D. J., Stowens, D. and Lippard, S. J. (1976) Structural determinations of four mono-and binuclear tertiary phosphine and arsine complexes of copper(I) chloride, Inorg. Chem., 15, 1155–1168.
Nicol, M. J. (1982) Kinetics of the oxidation of copper(I) by hydrogen peroxide in acidic chloride solutions, S. Afr. J. Chem., 35, 77–79.
Gilbert, B. C., Norman, R. O. C. and Sealy, R. C. (1975) Electron spin resonance studies part XLIV. The formation of alkyl-sulphonyl radicals by the oxidation of aliphatic sulphoxides with the hydroxyl radical and by the reaction of alkyl radicals with sulfur dioxide, J. Chem. Soc. Perkin Trans. 2, 308312; Gilbert, B. C. Laue, H. A. H., Norman, R. O. C. and Sealy. R. C. (1975) Electron spin resonance studies part XLVI. Oxidation of thiols and disulphides in aqueous solution: formation of RS., RSO., RSO2., RSSR• and carbon radicals, J. Chem. Soc. Perkin Trans. 2, 892–900.
Erben-Russ, M., Michel, C., Bors, W. and Saran, M.. (1987) Absolute rate constants of alkoxyl radical reactions in aqueous solution, J. Phys. Chem., 91, 2362–2365.
Bors, W., Michel, C. and Stettmaier, K. (1992) Radical species produced from the photolytic and pulseradiolytic degradation of tert-butyl hydroperoxide. An EPR spin-trapping investigation, J Chem Soc. Perkin Trans. 2, 1513–1517.
R. C. Weast (ed) (1977) CRC Handbook of Chemistry and Physics,58th Edition, CRC Press, D171.
Martell, A. E. and Smith, R. M. (1979) Critical Stability Constants, Plenum Press, 3, 264.
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Gilbert, B.C., Harrington, G., Scrivens, G., Silvester, S. (1997). EPR Studies of Fenton-Type Reactions in Copper- Peroxide Systems. In: Minisci, F. (eds) Free Radicals in Biology and Environment. NATO ASI Series, vol 27. Springer, Dordrecht. https://doi.org/10.1007/978-94-017-1607-9_4
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DOI: https://doi.org/10.1007/978-94-017-1607-9_4
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