Metabolism of hydrogen sulfide (H2S) and Production of Reactive Sulfur Species (RSS) by superoxide dismutase

Kenneth Olson, Yan Gao, Faihaan Arif, Kanika Arora, Shivali Patel, Eric R. DeLeon, Thomas R. Sutton, Martin Feelisch, Miriam M. Cortese-Krott, Karl D. Straub

Research output: Contribution to journalArticle

39 Citations (Scopus)

Abstract

Reactive sulfur species (RSS) such as H2S, HS, H2Sn, (n = 2–7) and HS2 •- are chemically similar to H2O and the reactive oxygen species (ROS) HO, H2O2, O2 •- and act on common biological effectors. RSS were present in evolution long before ROS, and because both are metabolized by catalase it has been suggested that “antioxidant” enzymes originally evolved to regulate RSS and may continue to do so today. Here we examined RSS metabolism by Cu/Zn superoxide dismutase (SOD) using amperometric electrodes for dissolved H2S, a polysulfide-specific fluorescent probe (SSP4), and mass spectrometry to identify specific polysulfides (H2S2-H2S5). H2S was concentration- and oxygen-dependently oxidized by 1 μM SOD to polysulfides (mainly H2S2, and to a lesser extent H2S3 and H2S5) with an EC50 of approximately 380 μM H2S. H2S concentrations > 750 μM inhibited SOD oxidation (IC50 = 1.25 mM) with complete inhibition when H2S > 1.75 mM. Polysulfides were not metabolized by SOD. SOD oxidation preferred dissolved H2S over hydrosulfide anion (HS-), whereas HS- inhibited polysulfide production. In hypoxia, other possible electron donors such as nitrate, nitrite, sulfite, sulfate, thiosulfate and metabisulfite were ineffective. Manganese SOD also catalyzed H2S oxidation to form polysulfides, but did not metabolize polysulfides indicating common attributes of these SODs. These experiments suggest that, unlike the well-known SOD-mediated dismutation of two O2 •- to form H2O2 and O2 SOD catalyzes a reaction using H2S and O2 to form persulfide. These can then combine in various ways to form polysulfides and sulfur oxides. It is also possible that H2S (or polysulfides) interact/react with SOD cysteines to affect catalytic activity or to directly contribute to sulfide metabolism. Our studies suggest that H2S metabolism by SOD may have been an ancient mechanism to detoxify sulfide or to regulate RSS and along with catalase may continue to do so in contemporary organisms.

Original languageEnglish (US)
Pages (from-to)74-85
Number of pages12
JournalRedox Biology
Volume15
DOIs
StatePublished - May 1 2018

Fingerprint

Hydrogen Sulfide
Hydrogen production
Sulfur
Metabolism
Superoxide Dismutase
Sulfides
Oxidation
Catalase
Sulfur Oxides
Reactive Oxygen Species
polysulfide
Thiosulfates
Sulfites
Nitrites
Fluorescent Dyes
Nitrates
Inhibitory Concentration 50
Sulfates
Anions
Mass spectrometry

Keywords

  • Antioxidants
  • Hydrogen peroxide
  • Oxidants
  • Reactive oxygen species
  • Reactive Species Interactome
  • Redox
  • Superoxide

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry

Cite this

Metabolism of hydrogen sulfide (H2S) and Production of Reactive Sulfur Species (RSS) by superoxide dismutase. / Olson, Kenneth; Gao, Yan; Arif, Faihaan; Arora, Kanika; Patel, Shivali; DeLeon, Eric R.; Sutton, Thomas R.; Feelisch, Martin; Cortese-Krott, Miriam M.; Straub, Karl D.

In: Redox Biology, Vol. 15, 01.05.2018, p. 74-85.

Research output: Contribution to journalArticle

Olson, K, Gao, Y, Arif, F, Arora, K, Patel, S, DeLeon, ER, Sutton, TR, Feelisch, M, Cortese-Krott, MM & Straub, KD 2018, 'Metabolism of hydrogen sulfide (H2S) and Production of Reactive Sulfur Species (RSS) by superoxide dismutase', Redox Biology, vol. 15, pp. 74-85. https://doi.org/10.1016/j.redox.2017.11.009
Olson, Kenneth ; Gao, Yan ; Arif, Faihaan ; Arora, Kanika ; Patel, Shivali ; DeLeon, Eric R. ; Sutton, Thomas R. ; Feelisch, Martin ; Cortese-Krott, Miriam M. ; Straub, Karl D. / Metabolism of hydrogen sulfide (H2S) and Production of Reactive Sulfur Species (RSS) by superoxide dismutase. In: Redox Biology. 2018 ; Vol. 15. pp. 74-85.
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