One- and two-electron oxidation of thiols: mechanisms, kinetics and biological fates
Abstract
The oxidation of biothiols participates not only in the defense against oxidative damage but also in enzymatic catalytic mechanisms and signal transduction processes. Thiols are versatile reductants that react with oxidizing species by one- and two-electron mechanisms, leading to thiyl radicals and sulfenic acids, respectively. These intermediates, depending on the conditions, participate in further reactions that converge on different stable products. Through this review, we will describe the biologically relevant species that are able to perform these oxidations and we will analyze the mechanisms and kinetics of the one- and two-electron reactions. The processes undergone by typical low-molecular-weight thiols as well as the particularities of specific thiol proteins will be described, including the molecular determinants proposed to account for the extraordinary reactivities of peroxidatic thiols. Finally, the main fates of the thiyl radical and sulfenic acid intermediates will be summarized.
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Formation of cysteine thiyl radical and sulfenic acid is a reversible process; both intermediates are highly unstable and serve as precursors for several oxidized cysteine modifications.
“Formation of cysteine thiyl radical and sulfenic acid is a reversible process and both intermediates are highly unstable. Both serve as precursors for several oxidized cysteine modifications (Fig. 1A) [16].”
From Protein oxidation - Formation mechanisms, detection and relevance as biomarkers in human diseases (2021) · cites this paper as [16]
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- Authors
- Trujillo, M., Alvarez, B., & Radi, R.
- Affiliations
- Universidad de la República de Uruguay (UY)
- Corresponding author
- Trujillo, Madia
- ORCID
- Trujillo, Madia
- Venue
- Free Radical Research
- Publisher
- Informa UK Limited
- Published
- 2015-11-11
- Volume
- 50
- Issue
- 2
- Pages
- 150-171
- ISSN
- 1029-2470 (ISSN-L)
- 1071-5762
- OpenAlex
- W1957064683
- Cited by
- 142
- References
- 254
- Citations by year
- 2026: 8 · 2025: 10 · 2024: 14 · 2023: 10 · 2022: 17 · 2021: 13 · 2020: 13 · 2019: 12 · 2018: 19 · 2017: 14 · 2016: 11 · 2015: 1
- FWCI
- 1.45
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Free Radical Research (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Institute of Allergy and Infectious Diseases (R01AI095173)
- Topics
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Redox biology and oxidative stress
- Physical Sciences › Chemistry › Organic Chemistry › Free Radicals and Antioxidants
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Biochemistry › Sulfur Compounds in Biology
- Keywords
- thiol oxidation, one-electron oxidation, two-electron oxidation, thiyl radicals, sulfenic acid, oxidation mechanism, reaction kinetics, thiol proteins, enzyme catalysis, signal transduction, thiol reductants
- MeSH terms
- Animals, Bacteria, Free Radicals, Humans, Kinetics, Oxidation-Reduction, Sulfenic Acids, Sulfhydryl Compounds, Eukaryota
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