Mechanism of Thiol Oxidation by the Superoxide Radical.
Saved in:
| Title: | Mechanism of Thiol Oxidation by the Superoxide Radical. |
|---|---|
| Authors: | Bruno Cardey1, Sarah Foley1, Mironel Enescu1 |
| Source: | Journal of Physical Chemistry A. Dec2007, Vol. 111 Issue 50, p13046-13052. 7p. |
| Subjects: | Thiols, Oxidation, Superoxides, Physical & theoretical chemistry |
| Abstract: | In spite of the large quantity of experimental work that deals with the oxidation of thiols by superoxide, the mechanism of this reaction is still controversial. The ab initiomolecular orbital calculations reported here predict that the main reaction pathway includes the formation of a three-electron-bonded adduct followed by the elimination of the hydroxide anion, giving the sulfinyl radical as the reaction product. The alternative reaction pathway consisting of hydrogen atom transfer from the thiol to the protonated superoxide radical involves a reaction energy barrier that is significantly higher. The difference between the two reaction energy barriers is clearly beyond the expected computational uncertainty. The systematic scanning of the potential energy surface reveals no other competitive reaction pathways. The present results provide a useful basis for the interpretation of the complex experimental data related to thiol oxidation by superoxide radical in a biological environment. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
Be the first to leave a comment!
