Biological control of S-nitrosothiol reactivity: potential role of sigma-hole interactions
Literature Information
Niloufar Hendinejad, Qadir K. Timerghazin
S-Nitrosothiols (RSNOs) are ubiquitous biomolecules whose chemistry is tightly controlled in vivo, although the specific molecular mechanisms behind this biological control remain unknown. In this work, we demonstrate, using high-level ab initio and DFT calculations, the ability of RSNOs to participate in intermolecular interactions with electron pair donors/Lewis bases (LBs) via a σ-hole, a region of positive electrostatic potential on the molecular surface at the extension of the N–S bond. Importantly, σ-hole binding is able to modulate the properties of RSNOs by changing the balance between two chemically opposite (antagonistic) resonance components, R–S+N–O− (D) and R–S−/NO+ (I), which are, in addition to the main resonance structure R–S–NO, necessary to describe the unusual electronic structure of RSNOs. σ-Hole binding at the sulfur atom of RSNO promotes the resonance structure D and reduces the resonance structure I, thereby stabilizing the weak N–S bond and making the sulfur atom more electrophilic. On the other hand, increasing the D-character of RSNO by other means (e.g. via N- or O-coordination of a Lewis acid) in turn enhances the σ-hole bonding. Our calculations suggest that in the protein environment a combination of σ-hole bonding of a negatively charged amino acid sidechain at the sulfur atom and N- or O-coordination of a positively charged amino acid sidechain is expected to have a profound effect on the RSNO electronic structure and reactivity.
Related Literature
How controlled and versatile is N-carboxy anhydride (NCA) polymerization at 0 °C? Effect of temperature on homo-, block- and graft (co)polymerization
Gijs J. M. Habraken, Maloes Peeters, Carin H. J. T. Dietz, Cor E. Koning
DOI: 10.1039/B9PY00337A
Process intensification of ozonolysis reactions using dedicated microstructured reactors
Dominique M. Roberge, Paul Hanselmann, Petteri Elsner
DOI: 10.1039/D1RE00264C
Green and sustainable synthesis of poly(δ-valerolactone) with a TBD catalyzed ring-opening polymerization reaction
Kai Cheng, Shiyao Lu, Kai Wang, Guangsheng Luo
DOI: 10.1039/D1RE00434D
Microwave desorption mechanism and microwave effect based on SO2 chemical dissociation and mass transfer of basic aluminium sulfate desulfurization rich liquid
Zijing Zhang, Junna Wang, Yu Feng, Weiwei Zhang, Shuangji Zuo, Jianmin Guo
DOI: 10.1039/D1RE00109D
Polymer micelles decorated by gadolinium complexes as MRI blood contrast agents: design, synthesis and properties
Mathurin Grogna, Rudi Cloots, André Luxen, Christine Jérôme, Catherine Passirani, Nolwenn Lautram, Jean-F. Desreux, Christophe Detrembleur
DOI: 10.1039/C0PY00117A
Electricity-induced micro-flow C–H/N–H alkyne annulation: a greener approach to access heteroaromatic compounds
Bhanwar Kumar Malviya, Genji Sukumar
DOI: 10.1039/D1RE00260K
Characterization of single-phase flow hydrodynamics in a Berty reactor using computational fluid dynamics (CFD)
Khunnawat Ountaksinkul, Sirada Sripinun, Surapon Bubphacharoen, Amnart Jantharasuk, Piyasan Praserthdam
DOI: 10.1039/D1RE00390A
Large-scale and clean preparation of low-defect few-layered graphene from commercial graphite via hydroxyl radical exfoliation in an acidic medium
Wenqiao Du, Zaiqian Yu, Xin Wang, Jingdong Wu, Long Zhang
DOI: 10.1039/D1RE00289A
You might also like
What precautions should be taken when handling lithium chloride hydrate (1:1:1) (CAS: 16712-20-2)?
When handling lithium chloride hydrate (1:1:1) (CAS: 16712-20-2), it is importan...
Is 4-(4H-1,2,4-Triazol-4-yl)piperidine (CAS: 690261-92-8) safe?
4-(4H-1,2,4-Triazol-4-yl)piperidine is generally considered safe for use in phar...
How should waste containing 1,3-Thiazole-2-carboxamide (CAS: 16733-85-0) be handled?
Waste containing 1,3-Thiazole-2-carboxamide (CAS: 16733-85-0) should be collecte...
What regulatory guidelines apply to 5-(Difluoromethyl)-2-fluorobenzonitrile (CAS: 934175-58-3)?
5-(Difluoromethyl)-2-fluorobenzonitrile (CAS: 934175-58-3) is subject to regulat...
How is Methyl 3-acetamido-2-thiophenecarboxylate (CAS: 22288-79-5) typically synthesized?
Methyl 3-acetamido-2-thiophenecarboxylate can be synthesized by the reaction of ...
What is 4-Isoquinolinecarbonitrile (CAS: 34846-65-6)?
4-Isoquinolinecarbonitrile is a chemical compound with the CAS number 34846-65-6...
How should Methyl 1H-1,2,3-triazole-4-carboxylate (CAS: 877309-59-6) be stored?
Store Methyl 1H-1,2,3-triazole-4-carboxylate (CAS: 877309-59-6) in a cool, dry p...
What regulatory guidelines apply to 6-Bromo[1,3]thiazolo[5,4-b]pyridin-2-amine (CAS: 1160791-13-8)?
6-Bromo[1,3]thiazolo[5,4-b]pyridin-2-amine (CAS: 1160791-13-8) is subject to the...
Is (2S,3S)-2-Ammonio-3-(3,4-dihydroxyphenyl)-3-hydroxypropanoate (CAS: 23651-95-8) safe?
(2S,3S)-2-Ammonio-3-(3,4-dihydroxyphenyl)-3-hydroxypropanoate (CAS: 23651-95-8) ...
What are the physical and chemical properties of 7-bromo-3-methyl-3,4-dihydroquinazolin-4-one (CAS: 1293987-84-4)?
7-Bromo-3-methyl-3,4-dihydroquinazolin-4-one is a solid with a crystalline form....
Source Journal
Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










![Ethyl 4-[8-chloro(5,5,6,6,7-~2~H_5_)-5,6-dihydro-11H-benzo[5,6]cyclohepta[1,2-b]pyridin-11-ylidene]-1-piperidinecarboxylate structure Ethyl 4-[8-chloro(5,5,6,6,7-~2~H_5_)-5,6-dihydro-11H-benzo[5,6]cyclohepta[1,2-b]pyridin-11-ylidene]-1-piperidinecarboxylate structure](https://static.chemtradehub.com/structs/102/1020719-57-6-37e2.webp)
![(1R,5R)-3-{[(2-Methyl-2-propanyl)oxy]carbonyl}-3-azabicyclo[3.1.0]hexane-1-carboxylic acid structure (1R,5R)-3-{[(2-Methyl-2-propanyl)oxy]carbonyl}-3-azabicyclo[3.1.0]hexane-1-carboxylic acid structure](https://static.chemtradehub.com/structs/116/1165450-63-4-bfe1.webp)
![Benzeneacetic acid, 2-bromo-α-[[(1,1-dimethylethoxy)carbonyl]amino]-, (αS)- structure Benzeneacetic acid, 2-bromo-α-[[(1,1-dimethylethoxy)carbonyl]amino]-, (αS)- structure](https://static.chemtradehub.com/structs/122/1228547-87-2-f296.webp)
![6-(Benzyloxy)-8-(2-bromoacetyl)-2H-benzo[b][1,4]oxazin-3(4H)-one structure 6-(Benzyloxy)-8-(2-bromoacetyl)-2H-benzo[b][1,4]oxazin-3(4H)-one structure](https://static.chemtradehub.com/structs/926/926319-53-1-2287.webp)
![(R)-N-[(S)-1-[2-(Diphenylphosphino)phenyl]ethyl]-2-methylpropane-2-sulfinamide structure (R)-N-[(S)-1-[2-(Diphenylphosphino)phenyl]ethyl]-2-methylpropane-2-sulfinamide structure](https://static.chemtradehub.com/structs/159/1595319-98-4-33e7.webp)