Reactive Oxygen Species in the Aerobic Decomposition of Sodium Hydroxymethanesulfinate

Макаров, С. В.; Mundoma, Claudius; Svarovsky, Serge A.; Shi, Xianglin; Gannett, Peter M.; Simoyi, Reuben H.

doi:10.1006/abbi.1999.1264

Cited by 28 publications

(40 citation statements)

References 12 publications

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“…Both the protonated and unprotonated forms of DMAIMSA can decompose to give a urea residue and a reactive radical sulfur leaving group. This decomposition was confirmed in an earlier study from our laboratory (30,31).…”

Section: Acid Retardationsupporting

confidence: 85%

Oxidation of a Dimethylthiourea Metabolite by Iodine and Acidified Iodate: N,N‘-Dimethylaminoiminomethanesulfinic Acid ()

Otoikhian

Simoyi

Petersen

2005

Chem. Res. Toxicol.

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The two major metabolites after S-oxygenation of dimethylthiourea (dimethylaminoiminomethane sulfinic acid, DMAIMSA, and dimethylaminoiminomethane sulfonic acid, DMAIMSOA) were synthesized and tested for their reactivities in the presence of mild oxidants, aqueous iodine and acidic iodate. The stoichiometry of the iodate-DMAIMSA reaction is 2IO3- + 3NHCH3(=NCH3)CSO2H + 3H2O --> 3SO4(2-) + 2I- + 3CO(NHCH3)2 + 6H+ (A). The reaction commences with immediate formation of aqueous iodine, which is produced from the reaction between the iodide product of stoichiometry (A) and reactant iodate. The instant accumulation of aqueous iodine is due to the very slow reaction of iodine with both DMAIMSA and DMAIMSOA. In excess iodate over that required for stoichiometry (A), the stoichiometry of the reaction is 4IO3- + 5NHCH3(=NCH3)CSO2H + 3H2O --> 5SO4(2-) + 2I2 + 5CO(NHCH3)2 + 6H+ (B). Even though excess DMAIMSA solutions do not afford iodine, the initial rapid formation of iodine is still observed, which reaches a peak and then decays to conform to stoichiometry (A). The maximum transient iodine concentrations obtained are directly proportional to the acid concentrations because acid catalyzes formation of iodine and retards reactions that consume iodine. The zwitterionic forms of DMAIMSA and DMAIMSOA are very stable in acid, and DMAIMSOA, especially, is very inert and unreactive in low pH environments. The predominant pathway for the oxidation of DMAIMSOA is through an initial hydrolysis reaction to yield bisulfite and dimethylurea, while the oxidation of DMAIMSA proceeds through DMAIMSOA as well as through an early heterolytic cleavage of the C-S bond to produce a highly reducing sulfoxylate species, SO2(2-), which is later rapidly oxidized to sulfate. In aerobic conditions, the sulfoxylate species reacts with molecular oxygen to produce superoxide anion radical, which in turn will form hydrogen peroxide and hydroxyl radicals which will bring with them inadvertent genotoxicity.

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Section: Acid Retardationsupporting

confidence: 85%

Oxidation of a Dimethylthiourea Metabolite by Iodine and Acidified Iodate: N,N‘-Dimethylaminoiminomethanesulfinic Acid ()

Otoikhian

Simoyi

Petersen

2005

Chem. Res. Toxicol.

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“…Decomposition of sodium hydroxymethanesulfinate in acid media has been studied. 118,119 This process is autocatalytic, being accelerated by active sulfur. The catalytic effect of S a is attributable to its influence on the decomposition of sodium dithionite, which is one of the main intermediate compounds formed upon decomposition of HMS.…”

Section: The Kinetics and Mechanisms Of Reactions Involving Sulfur-co...mentioning

confidence: 99%

“…119,130 It was found that in the HMS decomposition under aerobic conditions, the appearance of dithionite is preceded by an induction period, which is missing when the experiment is carried out under an inert atmosphere. 119 Study of decomposition of HMS in the presence of superoxide dismutase, catalase and sodium formate showed that active forms of oxygen (superoxide, peroxide, hydroxyl radicals) have little influence on the rate of dithionite formation. Sulfite additives exert a much more pronounced influence under both anaerobic and aerobic conditions.…”

Section: The Kinetics and Mechanisms Of Reactions Involving Sulfur-co...mentioning

confidence: 99%

Recent trends in the chemistry of sulfur-containing reducing agents

Макаров¹

2001

Russ. Chem. Rev.

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“…383 The kinetics of the oxidation of (R 2 N) 2 CS (R H or Me) by OH shows 384 that the primary product, (R 2 N) 2 CS , reacts with the thiourea to give a dimeric species which then decays to formamidine disul¢de. 384 Aerobic decomposition of HOCH 2 SO 2 À in slightly acidic aqueous solution (important in cloud chemistry) produces 385 392,393 and chloride-ion catalysis is seen at pH 9^10. A 17-step mechanism has been formulated 394 for the BrO 3 À ^I2 and BrO 3 À ^IÀ reactions.…”

Section: Other Non-metal Redox Reactionsmentioning

confidence: 99%

26 Mechanisms of reactions in solution

Winterton

2000

Annu. Rep. Prog. Chem., Sect. A

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Reactive Oxygen Species in the Aerobic Decomposition of Sodium Hydroxymethanesulfinate

Cited by 28 publications

References 12 publications

Oxidation of a Dimethylthiourea Metabolite by Iodine and Acidified Iodate: N,N‘-Dimethylaminoiminomethanesulfinic Acid ()

Oxidation of a Dimethylthiourea Metabolite by Iodine and Acidified Iodate: N,N‘-Dimethylaminoiminomethanesulfinic Acid ()

Recent trends in the chemistry of sulfur-containing reducing agents

26 Mechanisms of reactions in solution

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