Cited by 801Redox biology and oxidative stressFree Radicals and AntioxidantsAntioxidant Activity and Oxidative Stress

Reactivity of biologically important thiol compounds with superoxide and hydrogen peroxide

Winterbourn, Christine C., Metodiewa, Diana·1999·Free Radical Biology and Medicine

Abstract

The reactivities of glutathione, cysteine, cysteamine, penicillamine, N-acetylcysteine, dithiothreitol and captopril with superoxide generated from xanthine oxidase and hypoxanthine, and with reagent hydrogen peroxide, have been investigated. Rates of thiol loss on adding hydrogen peroxide, and superoxide-dependent thiol loss and oxygen uptake were measured. The relative reactivities of the different thiols with both oxidants were inversely related to the pK of the thiol group, such that at pH 7.4, penicillamine was the most reactive. N-acetylcysteine weakly reactive and no reaction was seen with captopril. For hydrogen peroxide, the calculated rate constants for the reaction with the thiolate anion all fell within the range 18-26 M(-1) s(-1). With superoxide, our results are consistent with each thiol reacting via a short chain that consumes oxygen and regenerates superoxide. Only with some of the thiols, was the consumed oxygen recovered as hydrogen peroxide. Reported values for the rate constant for the reaction of thiols with superoxide vary over four orders of magnitude, with the highest being > 10(5) M(-1) s(-1). Due to the complexity of the chain reaction, no study so far has been able to obtain accurate values and we consider the best estimates to be in the 30 to 1000 M(-1) s(-1) range.

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Crossref · 10.1016/s0891-5849(99)00051-9

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Authors
Winterbourn, C. C., & Metodiewa, D.
Corresponding author
Winterbourn, Christine C.
Venue
Free Radical Biology and Medicine
Publisher
Elsevier BV
Published
1999-08
Volume
27
Issue
3-4
Pages
322-328
ISSN
0891-5849 (ISSN-L)
OpenAlex
W2056840435
Cited by
799
References
43
Citations by year
2026: 10 · 2025: 24 · 2024: 23 · 2023: 37 · 2022: 28 · 2021: 32 · 2020: 38 · 2019: 43 · 2018: 34 · 2017: 40 · 2016: 43 · 2015: 49 · 2014: 41 · 2013: 48 · 2012: 45
FWCI
3.99
Type
journal article
Language
en
Open access
closed
Locations
  • Free Radical Biology and Medicine (publishedVersion)
  • PubMed (publishedVersion)
Funders
Health Research Council of New Zealand
Topics
  • Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Redox biology and oxidative stress
  • Physical Sciences › Chemistry › Organic Chemistry › Free Radicals and Antioxidants
  • Health Sciences › Medicine › Biochemistry › Antioxidant Activity and Oxidative Stress
Keywords
thiol oxidation, superoxide, hydrogen peroxide, glutathione, cysteine, cysteamine, D-penicillamine, N-acetylcysteine, dithiothreitol, captopril, xanthine oxidase, thiolate anion, thiol reactivity, thiol pKa, oxygen consumption, chain reaction, rate constants
MeSH terms
Acetylcysteine, Angiotensin-Converting Enzyme Inhibitors, Captopril, Cysteamine, Cysteine, Dithiothreitol, Glutathione, Hydrogen Peroxide, Oxygen Consumption, Penicillamine, Sulfhydryl Compounds, Superoxides, Xanthine Oxidase, Reactive Oxygen Species

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