2007
DOI: 10.1021/ja0737218
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Reactive Sulfur Species:  Kinetics and Mechanisms of the Oxidation of Cysteine by Hypohalous Acid to Give Cysteine Sulfenic Acid

Abstract: Cysteine sulfenic acid has been generated in alkaline aqueous solution by oxidation of cysteine with hypohalous acid (HOX, X = Cl or Br). The kinetics and mechanisms of the oxidation reaction and the subsequent reactions of cysteine sulfenic acid have been studied by stopped-flow spectrophotometry between pH 10 and 14. Two reaction pathways were observed: (1) below pH 12, the condensation of two sulfenic acids to give cysteine thiosulfinate ester followed by the nucleophilic attack of cysteinate on cysteine th… Show more

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Cited by 166 publications
(115 citation statements)
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“…Two additional products having accurate mass values and adducts consistent with empirical formulae C 4 H 9 NO 3 S and C 4 H 8 O 4 S were identified by LC-TOFMS. Although these formulae are compatible with structures such as the previously unreported homocysteine sulphenic acid and 2-hydroxy-4-sulphenobutanoic acid; sulphenic acids are normally found to be highly reactive transient compounds that are difficult to detect and isolate unless stabilized by steric hindrance 44 or intramolecular H-bonding involving a seven-membered ring 45 . However, in view of the known instability of most sulphenic acids 44 , much stronger evidence will be required before the structures for the minor products can be confirmed and thus they are not shown as decay products in Fig.…”
Section: Resultsmentioning
confidence: 66%
“…Two additional products having accurate mass values and adducts consistent with empirical formulae C 4 H 9 NO 3 S and C 4 H 8 O 4 S were identified by LC-TOFMS. Although these formulae are compatible with structures such as the previously unreported homocysteine sulphenic acid and 2-hydroxy-4-sulphenobutanoic acid; sulphenic acids are normally found to be highly reactive transient compounds that are difficult to detect and isolate unless stabilized by steric hindrance 44 or intramolecular H-bonding involving a seven-membered ring 45 . However, in view of the known instability of most sulphenic acids 44 , much stronger evidence will be required before the structures for the minor products can be confirmed and thus they are not shown as decay products in Fig.…”
Section: Resultsmentioning
confidence: 66%
“…Both methods gave similar rate constants, suggesting that Reaction 1 (between H 2 O 2 and C p ) was being measured, and not Reaction 2 (which is expected to be rapid) (19,20). A potential complication is that the Prx dimer bands on the gels represent both the single and double disulfide-bonded isoforms of the protein.…”
Section: Reactions 1 Andmentioning
confidence: 98%
“…The RSOH pKa is expected to be lower than the pK a of the corresponding thiol [4] . In aqueous solution, the pKa for the sulfenyl group of CysOH is found to be between 6 and 10 [29] . Since the sulfenic acid pK a is determined to be 6.1 in Salmonella typhimurium AhpC [30] , and 6.6 in Mycobacterium tuberculosis AhpE [31] , and given the hydrogen bond network around Cys51-SO -, the Cys51…”
Section: Factors That Control the Cys51 Oxidation In Human Prx: Resulmentioning
confidence: 99%