Abstract:
The kinetics of reduction of soluble polymeric Mn02 by cysteine and glutathione has been studied in the pH range of 4.0-9.0. The concentration of thiols was varied between 1 and 2 mM, while the Mn02 concentration was varied between 2 and 12 μM. In this pH range, the reaction products were identified as MN(II) and the corresponding disulfides (cystine and glutathione disulfide). Cysteic or cysteinesulfonic acid was formed only when pH < 2. Experimental data indicate that the rate law over the pH range of 4-9 is first-order in both Mn02 and thiol concentration. Eyring plots for both thiols reacting with Mn02 indicate that the reaction is associative (ΔS‡∼ -160 J mol-1 K-1) and proceeds via an inner-sphere redox process. The reaction proceeds via the formation of two different inner-sphere complexes ≡MnIVSR- and ≡MnIVSR and their further reaction to products. Both surface species are linked to each other via acid-base equilibria, and the rate constant decreases as pH increases, The presence of two ligand surface species is determined using surface complexation modeling, A reaction mechanism in agreement with the experimental results is proposed.
Registro:
Documento: |
Artículo
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Título: | Oxidation of cysteine and glutathione by soluble polymeric MnO2 |
Autor: | Herszage, J.; Dos Santos Afonso, M.; Luther III, G.W. |
Filiación: | Depto. Quim. Inorg., Analit./Q. F., Universidad de Buenos Aires, Ciudad Universitaria Pabellon II, (C1428EHA) Buenos Aires, Argentina College of Marine Studies, University of Delaware, Lewes, DE 19956, United States
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Palabras clave: | Concentration (process); Manganese compounds; Oxidation; pH; Reaction kinetics; Redox reactions; Reaction products; Environmental engineering; cysteic acid; cysteine; cystine; glutathione; manganese dioxide; manganese oxide; protein; reaction kinetics; aquatic environment; article; bioavailability; chemical reaction kinetics; complex formation; disulfide bond; electrochemistry; oxidation; polymerization; protein degradation; reaction analysis; water sampling; Cysteine; Glutathione; Hydrogen-Ion Concentration; Manganese Compounds; Oxidation-Reduction; Oxides; Solubility; Water Pollutants |
Año: | 2003
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Volumen: | 37
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Número: | 15
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Página de inicio: | 3332
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Página de fin: | 3338
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DOI: |
http://dx.doi.org/10.1021/es0340634 |
Título revista: | Environmental Science and Technology
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Título revista abreviado: | Environ. Sci. Technol.
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ISSN: | 0013936X
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CODEN: | ESTHA
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CAS: | cysteic acid, 13100-82-8, 498-40-8; cysteine, 4371-52-2, 52-89-1, 52-90-4; cystine, 24645-67-8, 56-89-3, 6020-39-9; glutathione, 70-18-8; manganese dioxide, 1313-13-9; Cysteine, 52-90-4; Glutathione, 70-18-8; Manganese Compounds; manganese dioxide, 1313-13-9; Oxides; Water Pollutants
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Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_0013936X_v37_n15_p3332_Herszage |
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Citas:
---------- APA ----------
Herszage, J., Dos Santos Afonso, M. & Luther III, G.W.
(2003)
. Oxidation of cysteine and glutathione by soluble polymeric MnO2. Environmental Science and Technology, 37(15), 3332-3338.
http://dx.doi.org/10.1021/es0340634---------- CHICAGO ----------
Herszage, J., Dos Santos Afonso, M., Luther III, G.W.
"Oxidation of cysteine and glutathione by soluble polymeric MnO2"
. Environmental Science and Technology 37, no. 15
(2003) : 3332-3338.
http://dx.doi.org/10.1021/es0340634---------- MLA ----------
Herszage, J., Dos Santos Afonso, M., Luther III, G.W.
"Oxidation of cysteine and glutathione by soluble polymeric MnO2"
. Environmental Science and Technology, vol. 37, no. 15, 2003, pp. 3332-3338.
http://dx.doi.org/10.1021/es0340634---------- VANCOUVER ----------
Herszage, J., Dos Santos Afonso, M., Luther III, G.W. Oxidation of cysteine and glutathione by soluble polymeric MnO2. Environ. Sci. Technol. 2003;37(15):3332-3338.
http://dx.doi.org/10.1021/es0340634