Role of Superoxide Anions in the Redox Changes Affecting the Physiologically Occurring Cu(I)-Glutathione Complex
The physiologically occurring copper-glutathione complex, [Cu(I)-[GSH]2], has the ability to react continually with oxygen, generating superoxide anions (O2•−). We addressed here the effects that superoxide removal has on the redox state of Cu(I) and GSH present in such complex and assessed the form...
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| Format: | Article |
| Language: | English |
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Wiley
2011-01-01
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| Series: | Bioinorganic Chemistry and Applications |
| Online Access: | http://dx.doi.org/10.1155/2011/674149 |
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| author | Hernán Speisky Camilo López-Alarcón Claudio Olea-Azar Cristian Sandoval-Acuña Margarita E. Aliaga |
| author_facet | Hernán Speisky Camilo López-Alarcón Claudio Olea-Azar Cristian Sandoval-Acuña Margarita E. Aliaga |
| author_sort | Hernán Speisky |
| collection | DOAJ |
| description | The physiologically occurring copper-glutathione complex, [Cu(I)-[GSH]2], has the ability to react continually with oxygen, generating superoxide anions (O2•−). We addressed here the effects that superoxide removal has on the redox state of Cu(I) and GSH present in such complex and assessed the formation of Cu(II)-GSSG as a final oxidation product. In addition, we investigated the potential of a source of O2•−
external to the Cu(I)-[GSH]2 complex to prevent its oxidation. Removal of O2•−
from a Cu(I)-[GSH]2-containing solution, whether spontaneous or Tempol-induced, led to time-dependent losses in GSH that were greater than those affecting the metal. The losses in GSH were not accompanied by increments in GSSG but were largely accounted for by the cumulative formation of Cu(II)-GSSG molecules. Notably, the redox changes in Cu(I) and GSH were totally prevented when Cu(I)-[GSH]2 was coincubated with hypoxanthine/xanthine oxidase. Data suggest that the generation of O2•−
by Cu(I)-[GSH]2 implies the obliged formation of an intermediate whose subsequent oxidation into Cu(II)-GSSG or back reduction into Cu(I)-[GSH]2 is favoured by either the removal or the addition of O2•−, respectively. |
| format | Article |
| id | doaj-art-451a1b9a6a35450c86f2a5ec7a3e45a6 |
| institution | OA Journals |
| issn | 1565-3633 1687-479X |
| language | English |
| publishDate | 2011-01-01 |
| publisher | Wiley |
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| series | Bioinorganic Chemistry and Applications |
| spelling | doaj-art-451a1b9a6a35450c86f2a5ec7a3e45a62025-08-20T02:37:47ZengWileyBioinorganic Chemistry and Applications1565-36331687-479X2011-01-01201110.1155/2011/674149674149Role of Superoxide Anions in the Redox Changes Affecting the Physiologically Occurring Cu(I)-Glutathione ComplexHernán Speisky0Camilo López-Alarcón1Claudio Olea-Azar2Cristian Sandoval-Acuña3Margarita E. Aliaga4Nutrition and Food Technology Institute, University of Chile, Santiago 7830489, ChileFacultad de Química, Pontificia Universidad Católica de Chile, Santiago 6094411, ChileFaculty of Chemical and Pharmaceutical Sciences, University of Chile, Santiago 8380492, ChileNutrition and Food Technology Institute, University of Chile, Santiago 7830489, ChileFacultad de Química, Pontificia Universidad Católica de Chile, Santiago 6094411, ChileThe physiologically occurring copper-glutathione complex, [Cu(I)-[GSH]2], has the ability to react continually with oxygen, generating superoxide anions (O2•−). We addressed here the effects that superoxide removal has on the redox state of Cu(I) and GSH present in such complex and assessed the formation of Cu(II)-GSSG as a final oxidation product. In addition, we investigated the potential of a source of O2•− external to the Cu(I)-[GSH]2 complex to prevent its oxidation. Removal of O2•− from a Cu(I)-[GSH]2-containing solution, whether spontaneous or Tempol-induced, led to time-dependent losses in GSH that were greater than those affecting the metal. The losses in GSH were not accompanied by increments in GSSG but were largely accounted for by the cumulative formation of Cu(II)-GSSG molecules. Notably, the redox changes in Cu(I) and GSH were totally prevented when Cu(I)-[GSH]2 was coincubated with hypoxanthine/xanthine oxidase. Data suggest that the generation of O2•− by Cu(I)-[GSH]2 implies the obliged formation of an intermediate whose subsequent oxidation into Cu(II)-GSSG or back reduction into Cu(I)-[GSH]2 is favoured by either the removal or the addition of O2•−, respectively.http://dx.doi.org/10.1155/2011/674149 |
| spellingShingle | Hernán Speisky Camilo López-Alarcón Claudio Olea-Azar Cristian Sandoval-Acuña Margarita E. Aliaga Role of Superoxide Anions in the Redox Changes Affecting the Physiologically Occurring Cu(I)-Glutathione Complex Bioinorganic Chemistry and Applications |
| title | Role of Superoxide Anions in the Redox Changes Affecting the Physiologically Occurring Cu(I)-Glutathione Complex |
| title_full | Role of Superoxide Anions in the Redox Changes Affecting the Physiologically Occurring Cu(I)-Glutathione Complex |
| title_fullStr | Role of Superoxide Anions in the Redox Changes Affecting the Physiologically Occurring Cu(I)-Glutathione Complex |
| title_full_unstemmed | Role of Superoxide Anions in the Redox Changes Affecting the Physiologically Occurring Cu(I)-Glutathione Complex |
| title_short | Role of Superoxide Anions in the Redox Changes Affecting the Physiologically Occurring Cu(I)-Glutathione Complex |
| title_sort | role of superoxide anions in the redox changes affecting the physiologically occurring cu i glutathione complex |
| url | http://dx.doi.org/10.1155/2011/674149 |
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