Abstract
In the course of an oxidative burst oxygen free radicals and hypothiocyanite (OSCN−), a transiently abundant derivative of thiocyanate (SCN−), are formed in the presence of activated polymorphonuclear leukocytes (PMNs). At the same time Cu(I)-thionein is present and the question arose whether or not thiocyanate and its oxidized form may transiently release highly Fenton active copper to improve the efficacy of the above mentioned oxidative burst. Thus, the reaction of yeast Cu-thionein with OSCN− was examined. Indeed, a release of copper from the Cu(I)-thiolate clusters of the protein was observed ex vivo. Both the chiroptic and luminescence emission signals of Cu-thionein essentially levelled off in the presence of a 15-fold molar excess of OSCN− expressed per equivalent of thionein-copper. The effective copper-releasing activity of this reagent was confirmed by equilibrium dialysis. The demetallized protein could be reconstituted under reductive conditions. SCN− did not affect the copper-thiolate bonding. It rather acts as a potent metabolic source for the transient copper release from Cu-thionein in the presence of activated PMNs.
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References
Aune TM, Thomas EL. 1977 Accumulation of hypothiocyanite ion during peroxidase-catalyzed oxidation of thiocyanate ion. Eur J Biochem 80, 209–214.
Felix K, Weser U. 1988 Release of copper from yeast copper-thionein after S-alkylation of copper-thiolate clusters. Biochem J 252, 577–581.
Felix K, Lengfelder E, Hartmann H-J, Weser U. 1993 A pulse radiolytic study on the reaction of hydroxyl and superoxide radicals with yeast Cu(I)-thionein. Biochim Biophys Acta 1203, 104–108.
Hartmann H-J, Morpurgo L, Desideri A, Rotilio G, Weser U. 1983 Reconstitution of stellacyanin as a case of direct Cu(I) transfer between yeast copper thionein and ‘blue’ copper apoproteins. FEBS Lett 152, 94–96.
Hartmann H-J, Gärtner A, Weser U. 1984 Oxidation of Cu(I)-thionein by enzymically generated H2O2. Hoppe-Seyler's Z Physiol Chem 365, 1355–1359.
Hartmann H-J, Gärtner A, Weser U. 1985 Copper dependent control of the enzymic and phagocyte induced degradation of some biopolymers, a possible link to systemic inflammation. Clin Chim Acta 152, 95–103.
Hartmann H-J, Schechinger T, Weser U. 1987 Cu(II) transfer into apo-Cu2Zn2-superoxide dismutase from Cu-thionein oxidized by activated leukocytes, Inorg Chim Acta 136, 107–110.
Hartmann H-J, Schechinger T, Weser U. 1989 Copper-thionein in leucocytes, Biol Met 2, 40–44.
Hartmann H-J, Yue-Jin L, Weser U. 1992 Analogous copper(I) coordination in metallothionein from yeast and the separate domains of the mammalian protein. BioMetals 5, 187–191.
Morpurgo L, Hartmann H-J, Desideri A, Weser U, Rotilio G. 1983 Yeast copper-thionein can reconstitute the Japanese-laquer-tree (Rhus vernicifera) laccase from the Type 2-copper depleted enzyme via a direct copper (I)-transfer mechanism Biochem J 211, 515–517.
Narula SS, Mehra RK, Winge DR, Armitage IM. 1991 Etablishment of the metal-to-cysteine connectivities in silver-substituted yeast metallothionein. J Am Chem Soc 131, 9354–9358.
Richter A, Weser U. 1988 Kinetics of the H2O2 dependent cleavage of Cu-thiolate centres in yeast Cu8-thionein. Inorg Chim Acta 151, 145–148.
Schechinger T, Hartmann H-J, Weser U. 1986 Copper transport from Cu(I)-thionein into apo-caeruloplasmin mediated by activated leucocytes, Biochem J 240, 281–283.
Steinkühler C, Pedersen JZ, Weser U, Rotilio G. 1991 Oxidative stress induced by a di-Schiff base copper complex is both mediated and modulated by glutathione. Biochem harmacol 42, 1821–1827.
Thomas EL. 1981 Lactoperoxidase-catalyzed oxidation of thiocyanate: equilibria between oxidized forms of thiocyanate. Biochemistry 20, 3273–3280.
Thomas EL. 1985 Products of lactoperoxidase-catalyzed oxidation of thiocyanate and halides. In: Pruitt KM, Tenovuo JO, eds. The Lactoperoxidase-Catalyzed Oxidation of Thiocyanate and Halides. New York: Marcel Dekker: 31–53.
Thomas EL, Fishman M. 1986 Oxidation of chloride and thiocyanate by isolated leukocytes. J Biol Chem 261, 9694–9702.
Weser U, Hartmann H-J. 1984 Copper-thiolate proteins (metallothioneins). In: Lontie R, ed. Copper Proteins and Copper Enzymes, Vol. III Boca Raton, FL: CRC Press: 151–173.
Weser U, Hartmann H-J. 1991 Purification of yeast Cu-thionein. Methods Enzymol 205, 274–278.
Weser U, Mutter W, Hartmann H-J. 1986 The role of Cu(I)-thiolate clusters during the proteolysis of Cuthionein. FEBS Lett 197, 258–262.
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Hartmann, HJ., Deters, D. & Weser, U. Copper-release from yeast Cu(I)-thionein by hypothiocyanite (OSCN−). Biometals 9, 345–349 (1996). https://doi.org/10.1007/BF00140603
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DOI: https://doi.org/10.1007/BF00140603