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Effects of sulfane sulfur content in benzyl polysulfides on thiol-triggered H2S release and cell proliferation.

ABSTRACT: Investigations into hydrogen sulfide (H2S) signaling pathways have demonstrated both the generation and importance of persulfides, which are reactive sulfur species that contain both reduced and oxidized sulfur. These observations have led researchers to suggest that oxidized sulfur species, including sulfane sulfur (S0), are responsible for many of the physiological phenomena initially attributed to H2S. A common method of introducing S0 to biological systems is the administration of organic polysulfides, such as diallyl trisulfide (DATS). However, prior reports have demonstrated that commercially-available DATS often contains a mixture of polysulfides, and furthermore a lack of structure-activity relationships for organic polysulfides has limited our overall understanding of different polysulfides and their function in biological systems. Advancing our interests in the chemical biology of reactive sulfur species including H2S and S0, we report here our investigations into the rates and quantities of H2S release from a series of synthetic, pure benzyl polysulfides, ranging from monosulfide to tetrasulfide. We demonstrate that H2S is only released from the trisulfide and tetrasulfide, and that this release requires thiol-mediated reduction in the presence of cysteine or reduced glutathione. Additionally, we demonstrate the different effects of trisulfides and tetrasulfides on cell proliferation in murine epithelial bEnd.3 cells.

SUBMITTER: Bolton SG

PROVIDER: S-EPMC6347403 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature

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Effects of sulfane sulfur content in benzyl polysulfides on thiol-triggered H2S release and cell proliferation.

Bolton Sarah G SG Cerda Matthew M MM Gilbert Annie K AK Pluth Michael D MD

Free radical biology & medicine 20181221

Investigations into hydrogen sulfide (H2S) signaling pathways have demonstrated both the generation and importance of persulfides, which are reactive sulfur species that contain both reduced and oxidized sulfur. These observations have led researchers to suggest that oxidized sulfur species, including sulfane sulfur (S0), are responsible for many of the physiological phenomena initially attributed to H2S. A common method of introducing S0 to biological ...[more]

PMID: 30579781

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Project description:Nitrite-to-NO transformation is of prime importance due to its relevance in mammalian physiology. Although such a one-electron reductive transformation at various redox-active metal sites (e.g., Cu and Fe) has been illustrated previously, the reaction at the [ZnII] site in the presence of a sacrificial reductant like thiol has been reported to be sluggish and poorly understood. Reactivity of [(Bn3Tren)ZnII-ONO](ClO4) (1), a nitrite-bound model of the tripodal active site of carbonic anhydrase (CA), toward various organic probes, such as 4-tert-butylbenzylthiol (tBuBnSH), 2,4-di-tert-butylphenol (2,4-DTBP), and 1-fluoro-2,4-dinitrobenzene (F-DNB), reveals that the ONO-moiety in the [ZnII]-nitrite coordination motif of complex 1 acts as a mild electrophile. tBuBnSH reacts mildly with nitrite at a [ZnII] site to provide S-nitrosothiol tBuBnSNO prior to the release of NO in 10% yield, whereas the phenolic substrate 2,4-DTBP does not yield the analogous O-nitrite compound (ArONO). The presence of sulfane sulfur (S0) species such as elemental sulfur (S8) and organic polysulfides (tBuBnSnBntBu) during the reaction of tBuBnSH and [ZnII]-nitrite (1) assists the nitrite-to-NO conversion to provide NO yields of 65% (for S8) and 76% (for tBuBnSnBntBu). High-resolution mass spectrometry (HRMS) analyses on the reaction of [ZnII]-nitrite (1), tBuBnSH, and S8 depict the formation of zinc(II)-persulfide species [(Bn3Tren)ZnII-Sn-BntBu]+ (where n = 2, 3, 4, 5, and 6). Trapping of the persulfide species (tBuBnSS-) with 1-fluoro-2,4-dinitrobenzene (F-DNB) confirms its intermediacy. The significantly higher nucleophilicity of persulfide species (relative to thiol/thiolate) is proposed to facilitate the reaction with the mildly electrophilic [ZnII]-nitrite (1) complex. Complementary analyses, including multinuclear NMR, electrospray ionization-MS, UV-vis, and trapping of reactive S-species, provide mechanistic insights into the sulfane sulfur-assisted reactions between thiol and nitrite at the tripodal [ZnII]-site. These findings suggest the critical influential roles of various reactive sulfur species, such as sulfane sulfur and persulfides, in the nitrite-to-NO conversion.

Dataset Information

Effects of sulfane sulfur content in benzyl polysulfides on thiol-triggered H2S release and cell proliferation.

Publications

Effects of sulfane sulfur content in benzyl polysulfides on thiol-triggered H<sub>2</sub>S release and cell proliferation.

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