Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H
Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H[superscript 2]S biochemistries, but its existence and stability in vivo remain controversial. We establish that HSNO is spontaneously formed in high concentration when NO and H[...
| Main Authors: | , , , , , , , , , |
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2018
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| Online Access: | http://hdl.handle.net/1721.1/116934 https://orcid.org/0000-0002-9239-7505 https://orcid.org/0000-0003-2568-3269 |
| _version_ | 1826195513542705152 |
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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 H[superscript 2]S biochemistries, but its existence and stability in vivo remain controversial. We establish that HSNO is spontaneously formed in high concentration when NO and H[subscript 2]S gases are mixed at room temperature in the presence of metallic surfaces. Our measurements reveal that HSNO is formed by the reaction H[superscript 2]S + N[subscript 2]O[subscript 3] → HSNO + HNO[subscript 2], where N[superscript 2]O[superscript 3] is a product of NO disproportionation. These studies also suggest that further reaction of HSNO with H[subscript 2]S 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 | 2024-09-23T10:13:56Z |
| format | Article |
| id | mit-1721.1/116934 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T10:13:56Z |
| publishDate | 2018 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1169342022-09-30T19:47:02Z Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H 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 H[superscript 2]S biochemistries, but its existence and stability in vivo remain controversial. We establish that HSNO is spontaneously formed in high concentration when NO and H[subscript 2]S gases are mixed at room temperature in the presence of metallic surfaces. Our measurements reveal that HSNO is formed by the reaction H[superscript 2]S + N[subscript 2]O[subscript 3] → HSNO + HNO[subscript 2], where N[superscript 2]O[superscript 3] is a product of NO disproportionation. These studies also suggest that further reaction of HSNO with H[subscript 2]S 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. 2018-07-12T15:21:48Z 2018-07-12T15:21:48Z 2016-08 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/116934 Nava, Matthew, et al. “Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H 2 S and Nitroso Chemistries.” Journal of the American Chemical Society, vol. 138, no. 36, Sept. 2016, pp. 11441–44. © 2016 American Chemical Society https://orcid.org/0000-0002-9239-7505 https://orcid.org/0000-0003-2568-3269 en_US 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 repository |
| 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 H |
| title | Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H |
| title_full | Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H |
| title_fullStr | Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H |
| title_full_unstemmed | Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H |
| title_short | Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H |
| title_sort | spontaneous and selective formation of hsno a crucial intermediate linking h |
| url | http://hdl.handle.net/1721.1/116934 https://orcid.org/0000-0002-9239-7505 https://orcid.org/0000-0003-2568-3269 |
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