Resonance Description of <i>S</i>-Nitrosothiols:  Insights into Reactivity

Timerghazin, Qadir K.; Peslherbe, Gilles H.; English, Ann M.

doi:10.1021/ol0711016

Cited by 40 publications

(59 citation statements)

References 24 publications

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“…On the other hand, the computed homolytic dissociation energy, typically 30 kcal mol −1 ,18 suggests that this bond is relatively weak. A balance between two different electronic effects has been suggested: 1) delocalization of the p‐type lone pair formally located on the sulfur atom into the π*(NO) orbital imparts a partial double‐bond character to the SN bond and explains the tendency for planarity of the CSNO group; and 2) the hyperconjugative interaction between the p‐type lone pair at oxygen and the σ*(SN) orbital contrarily weakens the SN bond 19. The contribution of an ionic resonance structure can be considered based on the corresponding NO stretching frequency.…”

Section: Methodsmentioning

confidence: 99%

The Structure and Conformation of (CH₃)₃CSNO

Cánneva

Erben

Romano

et al. 2015

Chemistry A European J

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The gas-phase molecular structure of (CH3 )3 CSNO was investigated by using electron diffraction, allowing the first experimental geometrical parameters for an S-nitrosothiol species to be elucidated. Depending on the orientation of the -SNO group, two conformers (anti and syn) are identified in the vapor of (CH3 )3 CSNO at room temperature, the syn conformer being less abundant. The conformational landscape is further scrutinized by using vibrational spectroscopy techniques, including gas-phase and matrix-isolation IR spectroscopy, resulting in a contribution of ca. 80:20 for the anti:syn abundance ratio, in good agreement with the computed value at the MP2(full)/cc-pVTZ level of approximation. The UV/Vis and resonance Raman spectra also show the occurrence of the conformational equilibrium in the liquid phase, with a moderate post-resonance Raman signature associated with the 350 nm electronic absorption.

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Section: Methodsmentioning

confidence: 99%

The Structure and Conformation of (CH₃)₃CSNO

Cánneva

Erben

Romano

et al. 2015

Chemistry A European J

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“…High-level ab initio calculations indicate that the RSNO wave function possesses significant multireference character [102,103] due to its zwitterionic RS + /NO − structure. Nucleophilic attack on the sulfur atom in the ion pair by a thiolate would yield HNO.…”

Section: Mechanisms Of H2s-based Signalingmentioning

confidence: 99%

H2S and its role in redox signaling

Kabil

Motl

Banerjee

2014

Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics

195

148

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Hydrogen sulfide (H2S) has emerged as an important gaseous signaling molecule that is produced endogenously by enzymes in the sulfur metabolic network. H2S exerts its effects on multiple physiological processes important under both normal and pathological conditions. These functions include neuromodulation, regulation of blood pressure and cardiac function, inflammation, cellular energetics and apoptosis. Despite the recognition of its biological importance and its beneficial effects, the mechanism of H2S action and the regulation of its tissue levels remain unclear in part owing to its chemical and physical properties that render handling and analysis challenging. Furthermore, the multitude of potential H2S effects has made it difficult to dissect its signaling mechanism and to identify specific targets. In this review, we focus on H2S metabolism and provide an overview of the recent literature that sheds some light on its mechanism of action in cellular redox signaling in health and disease. This article is part of a Special Issue entitled: Thiol-Based Redox Processes.

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“…The properties of HSNO investigated by high-level ab initio calculations indicate that the SNO group exists in mixed electronic states, with a predominant RS − /NO + resonance structure accounting for its overall reactivity (276, 277). Recent studies indicate that the electronic structure of S -nitrosothiol (RSNO) could be modulated by its specific interactions with residues in proteins (272).…”

Section: H2s As a Signaling Moleculementioning

confidence: 99%

Sulfur as a Signaling Nutrient Through Hydrogen Sulfide

Vitvitsky²,

2014

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Hydrogen sulfide (H2S) has emerged as an important signaling molecule with beneficial effects on various cellular processes affecting, for example, cardiovascular and neurological functions. The physiological importance of H2S is motivating efforts to develop strategies for modulating its levels. However, advancement in the field of H2S-based therapeutics is hampered by fundamental gaps in our knowledge of how H2S is regulated, its mechanism of action, and its molecular targets. This review provides an overview of sulfur metabolism; describes recent progress that has shed light on the mechanism of H2S as a signaling molecule; and examines nutritional regulation of sulfur metabolism, which pertains to health and disease.

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Resonance Description of S-Nitrosothiols: Insights into Reactivity

Cited by 40 publications

References 24 publications

The Structure and Conformation of (CH₃)₃CSNO

The Structure and Conformation of (CH₃)₃CSNO

H2S and its role in redox signaling

Sulfur as a Signaling Nutrient Through Hydrogen Sulfide

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Resonance Description of S-Nitrosothiols: Insights into Reactivity

Cited by 40 publications

References 24 publications

The Structure and Conformation of (CH3)3CSNO

The Structure and Conformation of (CH3)3CSNO

H2S and its role in redox signaling

Sulfur as a Signaling Nutrient Through Hydrogen Sulfide

Contact Info

Product

Resources

About

The Structure and Conformation of (CH₃)₃CSNO

The Structure and Conformation of (CH₃)₃CSNO