Computational Study of H2S Release in Reactions of Diallyl Polysulfides with Thiols

You Ru Cai, Ching-Han Hu

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Hydrogen sulfide (H2S) is a gasotransmitter molecule recognized for its role in cell signaling. Garlic-derived polysulfides including diallyl disulfide (DADS) and diallyl trisulfide (DATS) have been shown to release H2S. We investigated the mechanism of the reaction of DADS and DATS with biological thiols, including cysteine (Cys) and glutathione (GSH), using density functional theory. We propose that Cys and GSH react with DADS and DATS in their anionic forms. Thiol anions are much more likely to attack the sulfur atoms of DADS and DATS than the α-carbon of allyl groups. We found that nucleophilic attack of thiol anions on the peripheral sulfur of DATS is kinetically and thermodynamically more favorable than that on the central sulfur atom, resulting in the formation of allyl perthiol anion (ASS-). In the presence of Cys or GSH, H2S is released by proton-shuffle from the thiol to ASS-, followed by another nucleophilic attack by thiol anion on ASSH. Our computed potential energy surfaces revealed that GSH and Cys are capable of releasing H2S from DATS and that DADS is a much poorer H2S donor than DATS.

Original languageEnglish
Pages (from-to)6359-6366
Number of pages8
JournalJournal of Physical Chemistry B
Volume121
Issue number26
DOIs
Publication statusPublished - 2017 Jul 6

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polysulfides
Polysulfides
disulfides
Sulfhydryl Compounds
thiols
cysteine
Negative ions
Sulfur
attack
anions
Anions
Cysteine
sulfur
Cell signaling
Atoms
Potential energy surfaces
Hydrogen sulfide
glutathione
hydrogen sulfide
Gasotransmitters

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

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title = "Computational Study of H2S Release in Reactions of Diallyl Polysulfides with Thiols",
abstract = "Hydrogen sulfide (H2S) is a gasotransmitter molecule recognized for its role in cell signaling. Garlic-derived polysulfides including diallyl disulfide (DADS) and diallyl trisulfide (DATS) have been shown to release H2S. We investigated the mechanism of the reaction of DADS and DATS with biological thiols, including cysteine (Cys) and glutathione (GSH), using density functional theory. We propose that Cys and GSH react with DADS and DATS in their anionic forms. Thiol anions are much more likely to attack the sulfur atoms of DADS and DATS than the α-carbon of allyl groups. We found that nucleophilic attack of thiol anions on the peripheral sulfur of DATS is kinetically and thermodynamically more favorable than that on the central sulfur atom, resulting in the formation of allyl perthiol anion (ASS-). In the presence of Cys or GSH, H2S is released by proton-shuffle from the thiol to ASS-, followed by another nucleophilic attack by thiol anion on ASSH. Our computed potential energy surfaces revealed that GSH and Cys are capable of releasing H2S from DATS and that DADS is a much poorer H2S donor than DATS.",
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Computational Study of H2S Release in Reactions of Diallyl Polysulfides with Thiols. / Cai, You Ru; Hu, Ching-Han.

In: Journal of Physical Chemistry B, Vol. 121, No. 26, 06.07.2017, p. 6359-6366.

Research output: Contribution to journalArticle

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AU - Hu, Ching-Han

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