Dithioesters: simple, tunable, cysteine-selective H 2 S donors.

Autor: Cerda MM; Department of Chemistry and Biochemistry , Materials Science Institute , Institute of Molecular Biology , University of Oregon , Eugene , Oregon 97403 , USA . Email: pluth@uoregon.edu., Newton TD; Department of Chemistry and Biochemistry , Materials Science Institute , Institute of Molecular Biology , University of Oregon , Eugene , Oregon 97403 , USA . Email: pluth@uoregon.edu., Zhao Y; Department of Chemistry and Biochemistry , Materials Science Institute , Institute of Molecular Biology , University of Oregon , Eugene , Oregon 97403 , USA . Email: pluth@uoregon.edu., Collins BK; Department of Chemistry and Biochemistry , Materials Science Institute , Institute of Molecular Biology , University of Oregon , Eugene , Oregon 97403 , USA . Email: pluth@uoregon.edu., Hendon CH; Department of Chemistry and Biochemistry , Materials Science Institute , Institute of Molecular Biology , University of Oregon , Eugene , Oregon 97403 , USA . Email: pluth@uoregon.edu., Pluth MD; Department of Chemistry and Biochemistry , Materials Science Institute , Institute of Molecular Biology , University of Oregon , Eugene , Oregon 97403 , USA . Email: pluth@uoregon.edu.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2018 Nov 30; Vol. 10 (6), pp. 1773-1779. Date of Electronic Publication: 2018 Nov 30 (Print Publication: 2019).
DOI: 10.1039/c8sc04683b
Abstrakt: 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.
Databáze: MEDLINE
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