Journal article
Effect of added nucleophilic species on the rate of primary amino acid nitrosation
Journal of the American Chemical Society, Vol.127(11), pp.3664-3665
2005
Abstract
The rate of primary amino acid nitrosation, both with and without the addition of nucleophilic species, has been studied using stopped-flow spectrophotometry. The rate of nitrosation in the presence of strong nucleophilic species such as thiocyanate and thiourea was shown to be much faster than nitrosation without the addition of a nucleophile. Rate constants were determined at 25 °C for reaction of the amino acids alanine, glycine, and valine with five common nitrosating agents. For the nitrosating agents nitrosyl chloride, nitrosyl bromide, and dinitrogen trioxide the rate of reaction was observed to approach the predicted encounter-controlled limit. However, for nitrosyl thiocyanate and S-nitrosothiourea nitrosation was found to be reaction-controlled. In the reaction-controlled regime, rate constants were found to increase with increasing electrophilic strength of the nitrosating agent, as measured by the parameter En, with a slope indicative of a product-like transition state. Activation energies were also measured, being around 10-30 kJ mol-1 for encounter-controlled rate constants, and 30-50 kJ mol-1 for reaction-controlled rate constants. Our results are discussed in the context of in vivo amino acid nitrosation, where it is proposed that the rate of nitrosation may be considerably greater than currently thought, due to the presence of nucleophilic species.
Details
- Title
- Effect of added nucleophilic species on the rate of primary amino acid nitrosation
- Authors/Creators
- G. da Silva (Author/Creator)E.M. Kennedy (Author/Creator)B.Z. Dlugogorski (Author/Creator)
- Publication Details
- Journal of the American Chemical Society, Vol.127(11), pp.3664-3665
- Publisher
- American Chemical Society
- Identifiers
- 991005541843907891
- Copyright
- © 2005 American Chemical Society.
- Murdoch Affiliation
- Murdoch University
- Language
- English
- Resource Type
- Journal article
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- Citation topics
- 1 Clinical & Life Sciences
- 1.117 Pharmacology & Toxicology
- 1.117.909 Mutagenicity
- Web Of Science research areas
- Chemistry, Multidisciplinary
- ESI research areas
- Chemistry