Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries
Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H₂S biochemistries, but its existence and stability in vivo remain controversial. We establish that HSNO is spontaneously formed in high concentration when NO and H₂S gases are mi...
| Principais autores: | , , , , , , , , , |
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| Outros Autores: | |
| Formato: | Artigo |
| Publicado em: |
American Chemical Society (ACS)
2018
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| Acesso em linha: | http://hdl.handle.net/1721.1/113278 https://orcid.org/0000-0002-9239-7505 https://orcid.org/0000-0003-2568-3269 |
| _version_ | 1826214424772345856 |
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| author | Martin-Drumel, Marie-Aline Lopez, Christopher A. Crabtree, Kyle N. Nguyen, Thanh L. Thorwirth, Sven Stanton, John F. McCarthy, Michael C. Nava, Matthew Jordan Womack, Caroline C. Cummins, Christopher C |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Martin-Drumel, Marie-Aline Lopez, Christopher A. Crabtree, Kyle N. Nguyen, Thanh L. Thorwirth, Sven Stanton, John F. McCarthy, Michael C. Nava, Matthew Jordan Womack, Caroline C. Cummins, Christopher C |
| author_sort | Martin-Drumel, Marie-Aline |
| collection | MIT |
| description | Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H₂S biochemistries, but its existence and stability in vivo remain controversial. We establish that HSNO is spontaneously formed in high concentration when NO and H₂S gases are mixed at room temperature in the presence of metallic surfaces. Our measurements reveal that HSNO is formed by the reaction H₂S + N₂O₃ → HSNO + HNO₂, where N₂O₃ is a product of NO disproportionation. These studies also suggest that further reaction of HSNO with H₂S may form HNO and HSSH. The length of the S-N bond has been derived to high precision and is found to be unusually long: 1.84 Å, the longest S-N bond reported to date for an R-SNO compound. The present structural and, particularly, reactivity investigations of this elusive molecule provide a firm foundation to better understand its potential physiological chemistry and propensity to undergo S-N bond cleavage in vivo. |
| first_indexed | 2024-09-23T16:04:48Z |
| format | Article |
| id | mit-1721.1/113278 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T16:04:48Z |
| publishDate | 2018 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1132782022-09-29T18:08:15Z Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries Martin-Drumel, Marie-Aline Lopez, Christopher A. Crabtree, Kyle N. Nguyen, Thanh L. Thorwirth, Sven Stanton, John F. McCarthy, Michael C. Nava, Matthew Jordan Womack, Caroline C. Cummins, Christopher C Massachusetts Institute of Technology. Department of Chemistry Nava, Matthew Jordan Womack, Caroline C. Cummins, Christopher C Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H₂S biochemistries, but its existence and stability in vivo remain controversial. We establish that HSNO is spontaneously formed in high concentration when NO and H₂S gases are mixed at room temperature in the presence of metallic surfaces. Our measurements reveal that HSNO is formed by the reaction H₂S + N₂O₃ → HSNO + HNO₂, where N₂O₃ is a product of NO disproportionation. These studies also suggest that further reaction of HSNO with H₂S may form HNO and HSSH. The length of the S-N bond has been derived to high precision and is found to be unusually long: 1.84 Å, the longest S-N bond reported to date for an R-SNO compound. The present structural and, particularly, reactivity investigations of this elusive molecule provide a firm foundation to better understand its potential physiological chemistry and propensity to undergo S-N bond cleavage in vivo. United States. National Aeronautics and Space Administration (Grant NNX13AE59G) 2018-01-23T16:47:47Z 2018-01-23T16:47:47Z 2016-09 2016-06 2018-01-18T18:51:26Z Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/113278 Nava, Matthew, et al. “Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries.” Journal of the American Chemical Society 138, 36 (August 2016): 11441–11444 © 2016 American Chemical Society https://orcid.org/0000-0002-9239-7505 https://orcid.org/0000-0003-2568-3269 http://dx.doi.org/10.1021/JACS.6B05886 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) Other univ. web domain |
| spellingShingle | Martin-Drumel, Marie-Aline Lopez, Christopher A. Crabtree, Kyle N. Nguyen, Thanh L. Thorwirth, Sven Stanton, John F. McCarthy, Michael C. Nava, Matthew Jordan Womack, Caroline C. Cummins, Christopher C Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries |
| title | Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries |
| title_full | Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries |
| title_fullStr | Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries |
| title_full_unstemmed | Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries |
| title_short | Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries |
| title_sort | spontaneous and selective formation of hsno a crucial intermediate linking h₂s and nitroso chemistries |
| url | http://hdl.handle.net/1721.1/113278 https://orcid.org/0000-0002-9239-7505 https://orcid.org/0000-0003-2568-3269 |
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