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Since the first description of hydrogen sulfide (H 2 S) as a toxic gas in 1713 by Bernardino Ramazzini, most studies on H 2 S have concentrated on its toxicity. In 1989, Warenycia et al. demonstrated the existence of endogenous H 2 S in the brain, suggesting that H 2 S may have physiological roles. In 1996, we demonstrated that hydrogen sulfide (H 2 S) is a potential signaling molecule, which can be produced by cystathionine β-synthase (CBS) to modify neurotransmission in the brain. Subsequently, we showed that H 2 S relaxes vascular smooth muscle in synergy with nitric oxide (NO) and that cystathionine γ-lyase (CSE) is another producing enzyme. This study also opened up a new research area of a crosstalk between H 2 S and NO. The cytoprotective effect, anti-inflammatory activity, energy formation, and oxygen sensing by H 2 S have been subsequently demonstrated. Two additional pathways for the production of H 2 S with 3-mercaptopyruvate sulfurtransferase (3MST) from l- and d-cysteine have been identified. We also discovered that hydrogen polysulfides (H 2 S n , n ≥ 2) are potential signaling molecules produced by 3MST. H 2 S n regulate the activity of ion channels and enzymes, as well as even the growth of tumors. S -Sulfuration ( S -sulfhydration) proposed by Snyder is the main mechanism for H 2 S/H 2 S n underlying regulation of the activity of target proteins. This mini review focuses on the key findings on H 2 S/H 2 S n signaling during the first 25 years.

Hydrogen Sulfide (H2S) and Polysulfide (H2Sn) Signaling: The First 25 Years