Physical Properties and Various Reactions of Thionitrites and Related Substances

Ōae, Shigeru; Shinhama, Kōichi; Fujimori, Keiya; Kim, Yong Hae

doi:10.1246/bcsj.53.775

Cited by 59 publications

(45 citation statements)

References 19 publications

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“…The addition of tBuSNO 2 to aqueous buffer solutions (pH 7.4) caused hydrolysis with a half-life of about 20 s, as followed spectrometrically at 276 nm (44). In contrast, the addition of 500 M tBuSNO 2 to a solution containing 2 mM GSH resulted in immediate decomposition (Ͻ1 s) with stoichiometric formation of NO 2 Ϫ and oxidation of GSH, consistent with a recent report by Artz et As a third possible mechanism, S-nitrosation by ONOOH could be mediated via direct nucleophilic attack of the thiolate anion on the nitrogen atom in ONOOH, with elimination of HOO Ϫ (which is protonated to H 2 O 2 ) (Reaction 5).…”

mentioning

confidence: 99%

Formation of S-Nitrosothiols via Direct Nucleophilic Nitrosation of Thiols by Peroxynitrite with Elimination of Hydrogen Peroxide

Vliet¹,

Hoen²,

Wong³

et al. 1998

Journal of Biological Chemistry

140

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Peroxynitrite (ONOO ؊ ), a potent oxidant formed by reaction of nitric oxide (NO ⅐ ) with superoxide anion, can activate guanylyl cyclase and is able to induce vasodilation or inhibit platelet aggregation and leukocyte adhesion, via thiol-dependent formation of NO ⅐ . Reaction of ONOO ؊ with thiols is thought to proceed through formation of a S-nitrothiol (thionitrate; RSNO 2 ) intermediate and yields low levels of S-nitrosothiols (thionitrites; RSNO), both of which are theoretical sources of NO (2, 3). An important component of NO ⅐ biochemistry involves the formation of thionitrite esters with cysteine or cysteine-residues (Snitrosothiols; RSNO), and low molecular weight S-nitrosothiols or S-nitrosothiol adducts in proteins such as albumin or hemoglobin are known to be generated in vivo (4 -7). Formation of S-nitrosothiols may provide a buffering system regulating the bioavailability of NO ⅐ and/or serve to increase its range of action, since S-nitrosothiols are more stable and can release NO ⅐ by site-specific regulatory mechanisms, via reactions with transition metal ions or other reducing systems such as thioredoxin or superoxide anion (7-10). Furthermore, S-nitrosation and transnitrosation reactions with protein cysteine residues may regulate the activity of many enzymes and represent an important signaling mechanism (11-13). Despite the growing interest in the role of S-nitrosothiols in the biological actions of NO ⅐ , there is still uncertainty regarding the mechanism of S-nitrosation in vivo, which most likely does not involve direct reaction of NO ⅐ with thiols but requires electrophilic activation to a nitrosyl cation (NO ϩ )-like intermediate. Metabolites formed during NO ⅐ (auto)oxidation, such as dinitrogen trioxide (N 2 O 3 ), are likely candidates in this respect (14 -17). Alternatively, NO ⅐ can be activated to intermediates with NO ϩ character via interaction with ferric heme proteins (18) or via formation of dinitrosyl-iron complexes (19), in both cases leading to more efficient S-nitrosation. Finally, thiols are important physiological targets for peroxynitrite (ONOO Ϫ ) 2 (20), a potent oxidant formed during simultaneous generation of NO ⅐ and superoxide anion (O 2 . ) (4, 21), and formation of S-nitrosothiols has been detected after reaction of ONOO Ϫ with thiols (22,23). This chemistry has been linked to an increasing number of findings that ONOO -is capable of activating guanylyl cyclase (23-25) and can induce vasodilation, inhibition of platelet aggregation, or leukocyte adhesion and activation (26 -29), actions involving (re)generation of NO ⅐ via reaction with * This study was supported by National Institutes of Health Grant HL57452 (to C. E. C.), the Cystic Fibrosis Foundation, the American Lung Association of California, and a Fellowship from the Parker B. Francis Foundation (to A. v. d. V.). The costs of publication of this article were defrayed in part by the payment of page charges. This article must therefore be hereby marked "advertisement" in accordance with 18 U.S.C. Sectio...

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mentioning

confidence: 99%

Formation of S-Nitrosothiols via Direct Nucleophilic Nitrosation of Thiols by Peroxynitrite with Elimination of Hydrogen Peroxide

Vliet¹,

Hoen²,

Wong³

et al. 1998

Journal of Biological Chemistry

140

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“…We do not expect that the inclusion of more dynamic and/or static correlation energy will drastically change the conclusions drawn here. Since one type of RSNO 2 (R = t-Butyl) can be readily synthesized 26 and known to produce the NO radical probably via RSONO, it may still be worthwhile searching for rearrangement pathways with smaller activation energies. Figure 2.…”

Section: Resultsmentioning

confidence: 99%

The Rearrangement Reaction of CH₃SNO₂to CH₃SONO Studied by a Density Functional Theory Method

2004

Bulletin of the Korean Chemical Society

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Several critical geometries associated with the rearrangement of CH 3 SNO 2 to CH 3 SONO are calculated with the density functional theory (DFT) method and compared with those of the ab initio molecular orbital methods. There are two probable pathways for this rearrangement, one involving the transition state of an oxygen migration and the other through the homolytic decomposition to radicals. The reaction barrier via the transition state is about 60 kcal/mol and the decomposition energy into radicals about 35 kcal/mol, suggesting that the reaction pathway via the homolytic cleavage to radical species is energetically favorable. Since even the homolytic cleavage requires large energies, the rearrangement reaction is unlikely without the aid of catalysts.

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“…Reactions of BmtSNO (8) which decompose rapidly at room temperature [14]. The reaction of 11 with triphenylphosphine gave S-nitrosothiol 8, providing an alternative synthetic approach to 8.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of highly reactive organosulfur compounds

Okazaki

Goto

2002

Heteroatom Chemistry

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Physical Properties and Various Reactions of Thionitrites and Related Substances

Cited by 59 publications

References 19 publications

Formation of S-Nitrosothiols via Direct Nucleophilic Nitrosation of Thiols by Peroxynitrite with Elimination of Hydrogen Peroxide

Formation of S-Nitrosothiols via Direct Nucleophilic Nitrosation of Thiols by Peroxynitrite with Elimination of Hydrogen Peroxide

The Rearrangement Reaction of CH₃SNO₂to CH₃SONO Studied by a Density Functional Theory Method

Synthesis of highly reactive organosulfur compounds

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Physical Properties and Various Reactions of Thionitrites and Related Substances

Cited by 59 publications

References 19 publications

Formation of S-Nitrosothiols via Direct Nucleophilic Nitrosation of Thiols by Peroxynitrite with Elimination of Hydrogen Peroxide

Formation of S-Nitrosothiols via Direct Nucleophilic Nitrosation of Thiols by Peroxynitrite with Elimination of Hydrogen Peroxide

The Rearrangement Reaction of CH3SNO2to CH3SONO Studied by a Density Functional Theory Method

Synthesis of highly reactive organosulfur compounds

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The Rearrangement Reaction of CH₃SNO₂to CH₃SONO Studied by a Density Functional Theory Method