Chemical trapping and characterization of small oxoacids of sulfur (SOS) generated in aqueous oxidations of H2S

Redox Biol. 2018 Apr:14:485-491. doi: 10.1016/j.redox.2017.10.012. Epub 2017 Oct 16.

Abstract

Small oxoacids of sulfur (SOS) are elusive molecules like sulfenic acid, HSOH, and sulfinic acid, HS(O)OH, generated during the oxidation of hydrogen sulfide, H2S, in aqueous solution. Unlike their alkyl homologs, there is a little data on their generation and speciation during H2S oxidation. These SOS may exhibit both nucleophilic and electrophilic reactivity, which we attribute to interconversion between S(II) and S(IV) tautomers. We find that SOS may be trapped in situ by derivatization with nucleophilic and electrophilic trapping agents and then characterized by high resolution LC MS. In this report, we compare SOS formation from H2S oxidation by a variety of biologically relevant oxidants. These SOS appear relatively long lived in aqueous solution, and thus may be involved in the observed physiological effects of H2S.

Keywords: And bromobimane; Dimedone; Hydrogen sulfide; Sulfenic acid; Sulfinic acid.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Biomimetics / methods
  • Chromatography, Liquid / methods
  • Globins / chemistry
  • Heme / chemistry
  • Hydrogen Sulfide / chemistry*
  • Keto Acids / chemical synthesis
  • Keto Acids / chemistry*
  • Mass Spectrometry / methods
  • Oxidation-Reduction
  • Sulfenic Acids / chemical synthesis
  • Sulfenic Acids / chemistry
  • Sulfinic Acids / chemical synthesis
  • Sulfinic Acids / chemistry
  • Sulfur Compounds / chemical synthesis
  • Sulfur Compounds / chemistry*
  • Vitamin B 12 / chemistry
  • Water / chemistry*

Substances

  • Keto Acids
  • Sulfenic Acids
  • Sulfinic Acids
  • Sulfur Compounds
  • Water
  • Heme
  • Globins
  • Vitamin B 12
  • Hydrogen Sulfide