Abstract
Glutathione-based products, GSnX, of the reaction of hydrogen sulfide, H2S, S-nitroso glutathione, and GSNO, at varied stoichiometries have been analyzed by liquid chromatography high-resolution mass spectrometry (LC-HRMS) and chemical trapping experiments. A wide variety of glutathione-based species with catenated sulfur chains have been identified including sulfanes (GSSnG), sulfides (GSSnH), and sulfenic acids (GSnOH); sulfinic (GSnO2H) and sulfonic (GSnO3H) acids are also seen in reactions exposed to air. The presence of each species of GSnX within the original reaction mixtures was confirmed using Single Ion Chromatograms (SICs), to demonstrate the separation on the LC column, and given approximate quantification by the peak area of the SIC. Further, confirmation for different GSnX families was obtained by trapping with species-specific reagents. Several unique GSnX families have been characterized, including bridging mixed di- and tetra-valent polysulfanes and internal trithionitrates (GSNHSnH) with polysulfane branches. Competitive trapping experiments suggest that the polysulfane chains are formed via the intermediacy of sulfenic acid species, GSSnOH. In the presence of radical trap vinylcyclopropane (VCP) the relative distributions of polysulfane speciation are relatively unaffected, suggesting that radical coupling is not a dominant pathway. Therefore, we suggest polysulfane catenation occurs via reaction of sulfides with sulfenic acids.
Highlights
In the last decade, hydrogen sulfide (H2 S) has been identified as an important gasotransmitter [1], analogous to NO, CO, and other small molecules that act as signal transducers in mammalian physiology [2]
C-type nucleophilic traps like dimedone, 1of glutathione glutathione sulfenic acids can trapped by various traps like dimedone, of glutathione sulfenic acidsacids can be trapped bythat various traps like dimedone, 1- 1of sulfenic can bebetrapped bythe various traps like dimedone, In a recent report, we demonstrated sulfenyl and sulfinyl tautomeric forms, Scheme
We have previously shown that small oxoacids of sulfur, SOS, such as HSOH and HOSOH can be trapped during the aqueous oxidations of H2 S [21]
Summary
Hydrogen sulfide (H2 S) has been identified as an important gasotransmitter [1], analogous to NO, CO, and other small molecules that act as signal transducers in mammalian physiology [2]. There is speculation that vasorelaxation effects may be induced through some biotransformation of H2 S and NO resulting in polysulfide (RSSn H) [6,7], polysulfane (RSSn R) [8,9], and S-nitroso (RSNO) [10] species. All of these derivatives have been shown to be endogenously formed in cells, but their generation and activities are still much debated [11]. Akaike et al identified cysteinyl-tRNA synthetases that generate cysteine polysulfides (CysSSn H) which are integrated into proteins during
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