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Detailed mechanistic investigation into the S-nitrosation of cysteamine.
Morakinyo MK; Chipinda I; Hettick J; Seigel PD; Abramson J; Strongin R; Martincigh BS; Simoyi RH
Can J Chem 2012 Sep; 90(9):724-738
The nitrosation of cysteamine (H2NCH2CH2SH) to produce cysteamine-S-nitrosothiol (CANO) was studied in slightly acidic medium by using nitrous acid prepared in situ. The stoichiometry of the reaction was H2NCH2CH2SH + HNO2 & rarr H2NCH2CH2SNO + H2O. On prolonged standing, the nitrosothiol decomposed quantitatively to yield the disulfide, cystamine: 2H2NCH2CH 2SNO &rarr H2NCH2CH2S-SCH2CH2NH2 + 2NO. NO2 and N2O3 are not the primary nitrosating agents, since their precursor (NO) was not detected during the nitrosation process. The reaction is first order in nitrous acid, thus implicating it as the major nitrosating agent in mildly acidic pH conditions. Acid catalyzes nitrosation after nitrous acid has saturated, implicating the protonated nitrous acid species, the nitrosonium cation (NO+) as a contributing nitrosating species in highly acidic environments. The acid catalysis at constant nitrous acid concentrations suggests that the nitrosonium cation nitrosates at a much higher rate than nitrous acid. Bimolecular rate constants for the nitrosation of cysteamine by nitrous acid and by the nitrosonium cation were deduced to be 17.9 +/- 1.5 (mol/L)-1 s-1 and 6.7 × 104 (mol/L)-1 s-1, respectively. Both Cu(I) and Cu(II) ions were effective catalysts for the formation and decomposition of the cysteamine nitrosothiol. Cu(II) ions could catalyze the nitrosation of cysteamine in neutral conditions, whereas Cu(I) could only catalyze in acidic conditions. Transnitrosation kinetics of CANO with glutathione showed the formation of cystamine and the mixed disulfide with no formation of oxidized glutathione (GSSG). The nitrosation reaction was satisfactorily simulated by a simple reaction scheme involving eight reactions.
Acids; Analytical-processes; Analytical-methods; Chemical-analysis; Chemical-composition; Chemical-properties; Environmental-factors; Environmental-exposure; Exposure-levels; Author Keywords: nitric oxide; nitrosation; thiols; cysteamine; kinetics
Moshood K. Morakinyo, Allergy and Clinical Immunology Branch, Health Effects Laboratory Division, National Institute of Occupational Safety and Health, Centers for Disease Control and Prevention, 1095 Willowdale Road, Morgantown, WV 26505
Issue of Publication
Canadian Journal of Chemistry
Page last reviewed: March 25, 2022
Content source: National Institute for Occupational Safety and Health Education and Information Division