Detection and identification of the oxidizing species generated from the physiologically important Fenton-like reaction of iron(II)-citrate with hydrogen peroxide.
Arch Biochem Biophys
; 668: 39-45, 2019 06 15.
Article
em En
| MEDLINE
| ID: mdl-31100219
ABSTRACT
The Fenton-like reaction of iron(II)-citrate with hydrogen peroxide is physiologically important because it is associated with the oxidative stress and pathological processes induced by the redox-active iron pool in vivo. However, the oxidizing species generated from this reaction at neutral pH has not been convincingly identified because two extremely unstable and hard-to-differentiate species, the hydroxyl radical (â¢OH) and iron(IV) (ferryl) species, can be produced. Identifying this species is essential for understanding the reaction mechanism. Although there were few data that reported the detection of â¢OH from this reaction by using the EPR and fluorescence techniques, most of these data were obtained without the necessary assessment with a â¢OH scavenger. Furthermore, these two techniques may not be able to differentiate the â¢OH and iron(IV) species. Thus, these reported data cannot lead to a convincing conclusion that the â¢OH, not the iron(IV) species, was generated. Therefore, in the study reported herein, we carried out systematic investigations first by using the EPR and fluorescence techniques combined with a â¢OH scavenger to detect the oxidizing species generated from this Fenton-like reaction. Then we utilized NMR spectroscopy and for the first time obtained convincing evidence to demonstrate that this oxidizing species is the â¢OH rather than iron(IV) species. We also determined the second-order rate constant of the reaction, 3.6â¯×â¯103â¯M-1s-1 (pH7.0, 25⯰C), by using the stopped-flow spectrophotometry. On the basis of these findings, a scheme is proposed for the mechanism of this physiologically important Fenton-like reaction.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Compostos Ferrosos
/
Radical Hidroxila
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Peróxido de Hidrogênio
Tipo de estudo:
Diagnostic_studies
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Prognostic_studies
Idioma:
En
Ano de publicação:
2019
Tipo de documento:
Article