HNO Is Produced by the Reaction of NO with Thiols
Azanone (nitroxyl, HNO) is a highly reactive compound whose biological role is still a matter of debate. One possible route for its formation is NO reduction by biological reductants. These reactions have been historically discarded due to the negative redox potential for the NO,H+/HNO couple. Howev...
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2017
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v139_n41_p14483_Suarez http://hdl.handle.net/20.500.12110/paper_00027863_v139_n41_p14483_Suarez |
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paper:paper_00027863_v139_n41_p14483_Suarez2023-06-08T14:22:54Z HNO Is Produced by the Reaction of NO with Thiols Aromatic compounds Free radicals Manganese Molecules Ab initio method Anaerobic conditions Aromatic alcohols Aromatic thiol Mechanistic analysis Mn porphyrins Potential sources Redox potentials Redox reactions alpha tocopherol ascorbic acid azanone hydroquinone manganese nitric oxide nitroxyl thiol derivative tyrosine unclassified drug ab initio calculation Article chemical reaction controlled study density functional theory dimerization nuclear magnetic resonance spectroscopy nucleophilicity oxidation reduction potential proton transport rate constant tautomer Azanone (nitroxyl, HNO) is a highly reactive compound whose biological role is still a matter of debate. One possible route for its formation is NO reduction by biological reductants. These reactions have been historically discarded due to the negative redox potential for the NO,H+/HNO couple. However, the NO to HNO conversion mediated by vitamins C, E, and aromatic alcohols has been recently shown to be feasible from a chemical standpoint. Based on these precedents, we decided to study the reaction of NO with thiols as potential sources of HNO. Using two complementary approaches, trapping by a Mn porphyrin and an HNO electrochemical sensor, we found that under anaerobic conditions aliphatic and aromatic thiols (as well as selenols) are able to convert NO to HNO, albeit at different rates. Further mechanistic analysis using ab initio methods shows that the reaction between NO and the thiol produces a free radical adduct RSNOH•, which reacts with a second NO molecule to produce HNO and a nitrosothiol. The nitrosothiol intermediate reacts further with RSH to produce a second molecule of HNO and RSSR, as previously reported. © 2017 American Chemical Society. 2017 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v139_n41_p14483_Suarez http://hdl.handle.net/20.500.12110/paper_00027863_v139_n41_p14483_Suarez |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Aromatic compounds Free radicals Manganese Molecules Ab initio method Anaerobic conditions Aromatic alcohols Aromatic thiol Mechanistic analysis Mn porphyrins Potential sources Redox potentials Redox reactions alpha tocopherol ascorbic acid azanone hydroquinone manganese nitric oxide nitroxyl thiol derivative tyrosine unclassified drug ab initio calculation Article chemical reaction controlled study density functional theory dimerization nuclear magnetic resonance spectroscopy nucleophilicity oxidation reduction potential proton transport rate constant tautomer |
| spellingShingle |
Aromatic compounds Free radicals Manganese Molecules Ab initio method Anaerobic conditions Aromatic alcohols Aromatic thiol Mechanistic analysis Mn porphyrins Potential sources Redox potentials Redox reactions alpha tocopherol ascorbic acid azanone hydroquinone manganese nitric oxide nitroxyl thiol derivative tyrosine unclassified drug ab initio calculation Article chemical reaction controlled study density functional theory dimerization nuclear magnetic resonance spectroscopy nucleophilicity oxidation reduction potential proton transport rate constant tautomer HNO Is Produced by the Reaction of NO with Thiols |
| topic_facet |
Aromatic compounds Free radicals Manganese Molecules Ab initio method Anaerobic conditions Aromatic alcohols Aromatic thiol Mechanistic analysis Mn porphyrins Potential sources Redox potentials Redox reactions alpha tocopherol ascorbic acid azanone hydroquinone manganese nitric oxide nitroxyl thiol derivative tyrosine unclassified drug ab initio calculation Article chemical reaction controlled study density functional theory dimerization nuclear magnetic resonance spectroscopy nucleophilicity oxidation reduction potential proton transport rate constant tautomer |
| description |
Azanone (nitroxyl, HNO) is a highly reactive compound whose biological role is still a matter of debate. One possible route for its formation is NO reduction by biological reductants. These reactions have been historically discarded due to the negative redox potential for the NO,H+/HNO couple. However, the NO to HNO conversion mediated by vitamins C, E, and aromatic alcohols has been recently shown to be feasible from a chemical standpoint. Based on these precedents, we decided to study the reaction of NO with thiols as potential sources of HNO. Using two complementary approaches, trapping by a Mn porphyrin and an HNO electrochemical sensor, we found that under anaerobic conditions aliphatic and aromatic thiols (as well as selenols) are able to convert NO to HNO, albeit at different rates. Further mechanistic analysis using ab initio methods shows that the reaction between NO and the thiol produces a free radical adduct RSNOH•, which reacts with a second NO molecule to produce HNO and a nitrosothiol. The nitrosothiol intermediate reacts further with RSH to produce a second molecule of HNO and RSSR, as previously reported. © 2017 American Chemical Society. |
| title |
HNO Is Produced by the Reaction of NO with Thiols |
| title_short |
HNO Is Produced by the Reaction of NO with Thiols |
| title_full |
HNO Is Produced by the Reaction of NO with Thiols |
| title_fullStr |
HNO Is Produced by the Reaction of NO with Thiols |
| title_full_unstemmed |
HNO Is Produced by the Reaction of NO with Thiols |
| title_sort |
hno is produced by the reaction of no with thiols |
| publishDate |
2017 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v139_n41_p14483_Suarez http://hdl.handle.net/20.500.12110/paper_00027863_v139_n41_p14483_Suarez |
| _version_ |
1768544435653574656 |