Cited by 142Redox biology and oxidative stressFree Radicals and AntioxidantsSulfur Compounds in Biology

One- and two-electron oxidation of thiols: mechanisms, kinetics and biological fates

Trujillo, Madia, Alvarez, Beatriz, Radi, Rafael·2016·Free Radical Research

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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Crossref · 10.3109/10715762.2015.1089988

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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].”

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Authors
Trujillo, M., Alvarez, B., & Radi, R.
Affiliations
Universidad de la República de Uruguay (UY)
Corresponding author
Trujillo, Madia
Venue
Free Radical Research
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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