Issue 17, 2025

The reaction of sulfenic acids with OH and HO2 radicals in different environments

Abstract

Sulfenic acids are involved in major chemical processes occurring in the atmosphere, in food chemistry and in biological systems. In these diverse environments, oxidation reactions caused by reactive oxygen species, especially hydroxyl (OH) and hydroperoxyl (HO2) radicals, are very important, but their mechanisms remain poorly understood. To address this question, in this paper we present high-level theoretical results on selected reactions in gas phase and in aqueous solution. The study shows that the abstraction of the acidic hydrogen by OH or HO2 is the most important process in all cases. It leads to the formation of sulfinyl radicals and H2O or H2O2, respectively, following a proton-coupled electron transfer (pcet) mechanism. The associated rate constants depend on sulfenic acid derivative when the oxidizing species is HO2, but all processes are diffusion controlled in the case of reaction with OH. From structurally simple systems to a cysteine-derived model peptide, this work provides a systematic study that contributes to a comprehensive understanding of the reactivity of sulfenic acids with radicals.

Graphical abstract: The reaction of sulfenic acids with OH and HO2 radicals in different environments

Supplementary files

Article information

Article type
Paper
Submitted
25 Oct 2024
Accepted
31 Mar 2025
First published
02 Apr 2025
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2025,27, 8856-8867

The reaction of sulfenic acids with OH and HO2 radicals in different environments

J. M. Anglada, R. Crehuet, M. T. C. Martins-Costa, J. S. Francisco and M. F. Ruiz-López, Phys. Chem. Chem. Phys., 2025, 27, 8856 DOI: 10.1039/D4CP04106B

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements