Decomposition of S-nitrosocysteine via S- to N-transnitrosation.
S-nitrosothiols are thought to be important intermediates in nitric oxide signaling pathways. These compounds are unstable, in part, through their ability to donate NO. One model S-nitrosothiol, S-nitrosocysteine, is particularly unstable. Recently, it was proposed that this compound decomposed via intra and intermolecular transfer of the NO group from the sulfur to the nitrogen to form N-nitrosocysteine. This primary nitrosamine is expected to rapidly rearrange to ultimately form a reactive diazonium ion intermediate. To test this hypothesis, we demonstrated that thiirane-2-carboxylic acid is formed during the decomposition of S-nitrosocysteine at neutral pH. Acrylic acid was another product of this reaction. These results indicate that a small but significant amount of S-nitrosocysteine decomposes via S- to N-transnitrosation. The formation of a reactive intermediate in this process indicates the potential for this reaction to contribute to the toxicological properties of nitric oxide.
Peterson
Lisa A
LA
Division of Environmental Health Sciences and the Cancer Center, University of Minnesota, Minneapolis, Minnesota 55455, USA. peter431@umn.edu
Wagener
Tanja
T
Sies
Helmut
H
Stahl
Wilhelm
W
D000179:Acrylates / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry; D003545:Cysteine / Q000031:analogs & derivatives* / Q000737:chemistry; D006571:Heterocyclic Compounds / Q000737:chemistry; D020030:Nitric Oxide Donors / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D015538:Nitrosation; D026403:S-Nitrosothiols / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*
D000179:Acrylates; D002264:Carboxylic Acids; D006571:Heterocyclic Compounds; D020030:Nitric Oxide Donors; D026403:S-Nitrosothiols; C419887:thiirancarboxylic acid; D013455:Sulfur; C021315:S-nitrosocysteine; C036658:acrylic acid; D003545:Cysteine; D009584:Nitrogen