RESEARCH ARTICLE

 

Kinetics and mechanism of formation of S-nitrosocysteine

 

 

Sovathana Ly; Moshood K. Morakinyo; Reuben H. Simoyi^*

Department of Chemistry, Portland State University, Portland, OR 97207-0751, USA

 

 

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ABSTRACT

The kinetics and mechanism of the nitrosation of cysteine by nitrous acid has been studied in acidic medium. The stoichiometry of the reaction is strictly 1:1, with the formation of one mole of S-nitrosocysteine (CySNO) from one mole of nitrous acid. Only two nitrosating agents were detected: nitrous acid itself and protonated nitrous acid which is the hydrated form of the nitrosonium cation, NO⁺. Nitric oxide itself was not detected as a nitrosant. The bimolecular rate constant for the direct nitrosation of cysteine by nitrous acid was determined to be 6.4 ± 1.1 L mol^-1 s^-1, while nitrosation by the nitrosonium cation has a rate constant of 6.8 x 10³ L mol^-1 s^-1. CySNO is short-lived, and decomposes completely to cystine and nitric oxide within 100 s in the presence of micromolar quantities of Cu(II) ions. Since the physiological environment contains many metal ions and metalloenzymes, it is unlikely that CySNO will be an effective carrier of NO.

Keywords: Cysteine, nitric oxide, nitrosothiol

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Acknowledgement

This work was supported by Research Grant Number 0619224 from the National Science Foundation.

 

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Received 8 December 2009
Accepted 18 November 2010

 

 

* To whom correspondence should be addressed. E-mail: rsimoyi@pdx.edu