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. 2022 Nov:57:102486.
doi: 10.1016/j.redox.2022.102486. Epub 2022 Sep 25.

The antioxidant and oxidant properties of hydropersulfides (RSSH) and polysulfide species

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The antioxidant and oxidant properties of hydropersulfides (RSSH) and polysulfide species

Christopher H Switzer et al. Redox Biol. 2022 Nov.

Abstract

It has become apparent that hydrogen sulfide (H2S), hydropersulfides (RSSH) and other polysulfide species are all intimately linked biochemically. Indeed, at least some of the biological activity attributed to hydrogen sulfide (H2S) may actually be due to its conversion to RSSH and derived polysulfur species (and vice-versa). The unique chemistry associated with the hydropersulfide functional group (-SSH) predicts that it possesses possible protective properties that can help a cell contend with oxidative and/or electrophilic stress. However, since RSSH and polysulfides possess chemical properties akin to disulfides (RSSR), they can also be sources of oxidative/electrophilic stress/signaling as well. Herein are discussed the unique chemistry, possible biochemistry and the physiological implications of RSSH (and polysulfides), especially as it pertains to their putative cellular protection properties against a variety of stresses and/or as possible stressors/signaling agents themselves.

Keywords: Hydrogen sulfide; Hydropersulfides; Polysulfides; S-nitrosothiol.

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Conflict of interest statement

Declaration of competing interest The authors declare no conflicts of interest.

Figures

Fig. 1
Fig. 1
A) Alpha effect associated with increased nucleophilicity of RSSH/RSS over RSH/RS. B) Delocalization of unpaired electron of RSS· responsible for increased stability over RS·.
Fig. 2
Fig. 2
Chemical reactivities of thiols (RSH), disulfides (RSSR) and hydropersulfides (RSSH).
Fig. 3
Fig. 3
Possible mechanisms of RSH protection via conversion to RSSH. (Note: RSSH can be PSSH in these mechanisms).
Fig. 4
Fig. 4
Pathways of inorganic polysulfide generation from sulfide oxidation.
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