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Detailed mechanistic investigation into the S-nitrosation of cysteamine.

Authors
Morakinyo-MK; Chipinda-I; Hettick-J; Seigel-PD; Abramson-J; Strongin-R; Martincigh-BS; Simoyi-RH
Source
Can J Chem 2012 Sep; 90(9):724-738
NIOSHTIC No.
20041534
Abstract
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.
Keywords
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
Contact
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
CODEN
CJCHAG
Publication Date
20120901
Document Type
Journal Article
Email Address
mkm2002ng@yahoo.com
Fiscal Year
2012
NTIS Accession No.
NTIS Price
Identifying No.
B10152012
Issue of Publication
9
ISSN
0008-4042
NIOSH Division
HELD
Source Name
Canadian Journal of Chemistry
State
WV; OR
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