S-nitrosocysteine and cystine from reaction of cysteine with nitrous acid. A kinetic investigation.
The formation of the S-nitrosocysteine (CySNO) in aqueous solution starting from cysteine (CySH) and sodium nitrite is shown to strongly depend on the pH. Experiments conducted within the pH range 0.5-7.0 show that at pH below 3.5 the NO+ (or H2NO 2 +) is the main nitrosating species, while at higher pH (>3.5) the nitrosating species is most likely the N2O3. A kinetic study provided a general kinetic equation, V(CySNO) = k1[HNO2][CySH]eq [H+] + k2[HNO2]2. The first term of this equation is predominant at pH lower than 3.5, in agreement with the literature for the direct nitrosation of thiols with nitrous acid; the value for the third-order rate constant, k(1) = 7.9 x 10(2) L(2) mol(-2) min(-1), was calculated. For experiments at pH higher than 3.5, the second term becomes prevalent and the second-order rate constant k(2) = (3.3 +/- 0.1) x 10(3) L mol(-1) min(-1) was calculated. A competitive oxidation process leading to the direct formation of cystine (CySSCy) has been also found. Most likely also for this process two different mechanisms are involved, depending on the pH, and a general kinetic equation, V(CySSCy) = k3[CySH](eq)[HNO2][H+] + k3'[CySH]eq[HNO2], is proposed.
Grossi
Loris
L
Dipartimento di Chimica Organica "A. Mangini", Università di Bologna, Viale Risorgimento 4, I-40136 Bologna, Italy.
Montevecchi
Pier Carlo
PC
D003545:Cysteine / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry*; D003553:Cystine / Q000138:chemical synthesis*; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D008956:Models, Chemical; D015538:Nitrosation; D009608:Nitrous Acid / Q000737:chemistry*; D010084:Oxidation-Reduction; D026403:S-Nitrosothiols / Q000138:chemical synthesis*; D014867:Water
D026403:S-Nitrosothiols; D014867:Water; D003553:Cystine; C021315:S-nitrosocysteine; D003545:Cysteine; D009608:Nitrous Acid