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Dithioesters: simple, tunable, cysteine-selective H(2)S donors
Dithioesters have a rich history in polymer chemistry for RAFT polymerizations and are readily accessible through different synthetic methods. Here we demonstrate that the dithioester functional group is a tunable motif that releases H(2)S upon reaction with cysteine and that structural and electron...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2018
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6368244/ https://www.ncbi.nlm.nih.gov/pubmed/30842844 http://dx.doi.org/10.1039/c8sc04683b |
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author | Cerda, Matthew M. Newton, Turner D. Zhao, Yu Collins, Brylee K. Hendon, Christopher H. Pluth, Michael D. |
author_facet | Cerda, Matthew M. Newton, Turner D. Zhao, Yu Collins, Brylee K. Hendon, Christopher H. Pluth, Michael D. |
author_sort | Cerda, Matthew M. |
collection | PubMed |
description | Dithioesters have a rich history in polymer chemistry for RAFT polymerizations and are readily accessible through different synthetic methods. Here we demonstrate that the dithioester functional group is a tunable motif that releases H(2)S upon reaction with cysteine and that structural and electronic modifications enable the rate of cysteine-mediated H(2)S release to be modified. In addition, we use (bis)phenyl dithioester to carry out kinetic and mechanistic investigations, which demonstrate that the initial attack by cysteine is the rate-limiting step of the reaction. These insights are further supported by complementary DFT calculations. We anticipate that the results from these investigations will allow for the further development of dithioesters as important chemical motifs for studying H(2)S chemical biology. |
format | Online Article Text |
id | pubmed-6368244 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-63682442019-03-06 Dithioesters: simple, tunable, cysteine-selective H(2)S donors Cerda, Matthew M. Newton, Turner D. Zhao, Yu Collins, Brylee K. Hendon, Christopher H. Pluth, Michael D. Chem Sci Chemistry Dithioesters have a rich history in polymer chemistry for RAFT polymerizations and are readily accessible through different synthetic methods. Here we demonstrate that the dithioester functional group is a tunable motif that releases H(2)S upon reaction with cysteine and that structural and electronic modifications enable the rate of cysteine-mediated H(2)S release to be modified. In addition, we use (bis)phenyl dithioester to carry out kinetic and mechanistic investigations, which demonstrate that the initial attack by cysteine is the rate-limiting step of the reaction. These insights are further supported by complementary DFT calculations. We anticipate that the results from these investigations will allow for the further development of dithioesters as important chemical motifs for studying H(2)S chemical biology. Royal Society of Chemistry 2018-11-30 /pmc/articles/PMC6368244/ /pubmed/30842844 http://dx.doi.org/10.1039/c8sc04683b Text en This journal is © The Royal Society of Chemistry 2019 https://creativecommons.org/licenses/by-nc/3.0/This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0) |
spellingShingle | Chemistry Cerda, Matthew M. Newton, Turner D. Zhao, Yu Collins, Brylee K. Hendon, Christopher H. Pluth, Michael D. Dithioesters: simple, tunable, cysteine-selective H(2)S donors |
title | Dithioesters: simple, tunable, cysteine-selective H(2)S donors
|
title_full | Dithioesters: simple, tunable, cysteine-selective H(2)S donors
|
title_fullStr | Dithioesters: simple, tunable, cysteine-selective H(2)S donors
|
title_full_unstemmed | Dithioesters: simple, tunable, cysteine-selective H(2)S donors
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title_short | Dithioesters: simple, tunable, cysteine-selective H(2)S donors
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title_sort | dithioesters: simple, tunable, cysteine-selective h(2)s donors |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6368244/ https://www.ncbi.nlm.nih.gov/pubmed/30842844 http://dx.doi.org/10.1039/c8sc04683b |
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