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Mechanism of Thiol Oxidation by the Superoxide Radical.

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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
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Header DbId: egs
DbLabel: Engineering Source
An: 28043700
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
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  Data: Mechanism of Thiol Oxidation by the Superoxide Radical.
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  Data: <searchLink fieldCode="AR" term="%22Bruno+Cardey%22">Bruno Cardey</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Sarah+Foley%22">Sarah Foley</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Mironel+Enescu%22">Mironel Enescu</searchLink><relatesTo>1</relatesTo>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+A%22">Journal of Physical Chemistry A</searchLink>. Dec2007, Vol. 111 Issue 50, p13046-13052. 7p.
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  Data: <searchLink fieldCode="DE" term="%22Thiols%22">Thiols</searchLink><br /><searchLink fieldCode="DE" term="%22Oxidation%22">Oxidation</searchLink><br /><searchLink fieldCode="DE" term="%22Superoxides%22">Superoxides</searchLink><br /><searchLink fieldCode="DE" term="%22Physical+%26+theoretical+chemistry%22">Physical & theoretical chemistry</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: 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]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>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.</i> (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
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      – Type: doi
        Value: 10.1021/jp0731102
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      – Code: eng
        Text: English
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      Pagination:
        PageCount: 7
        StartPage: 13046
    Subjects:
      – SubjectFull: Thiols
        Type: general
      – SubjectFull: Oxidation
        Type: general
      – SubjectFull: Superoxides
        Type: general
      – SubjectFull: Physical & theoretical chemistry
        Type: general
    Titles:
      – TitleFull: Mechanism of Thiol Oxidation by the Superoxide Radical.
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            NameFull: Bruno Cardey
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            NameFull: Sarah Foley
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            NameFull: Mironel Enescu
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            – D: 20
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              Text: Dec2007
              Type: published
              Y: 2007
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              Value: 111
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              Value: 50
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            – TitleFull: Journal of Physical Chemistry A
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