Polysulfides (H2Sx) represent a class of reactive sulfur species (RSS) which includes
molecules such as H2S2, H2S3, H2S4, and H2S5, and whose presence and impact in biological systems,
when compared to other sulfur compounds, has only recently attracted the wider attention of
researchers. Studies in this field have revealed a facet-rich chemistry and biological activity associated
with such chemically simple, still unusual inorganic molecules. Despite their chemical simplicity,
these inorganic species, as reductants and oxidants, metal binders, surfactant-like “cork screws” for
membranes, components of perthiol signalling and reservoirs for inorganic hydrogen sulfide (H2S),
are at the centre of complicated formation and transformation pathways which affect numerous
cellular processes. Starting from their chemistry, the hidden presence and various roles of polysulfides
in biology may become more apparent, despite their lack of clear analytical fingerprints and often
murky biochemical footprints. Indeed, the biological chemistry of H2Sx follows many unexplored
paths and today, the relationship between H2S and its oxidized H2Sx species needs to be clarified as
a matter of “unmistaken identity”. Simultaneously, emerging species, such as HSSeSH and SenS8−n,
also need to be considered in earnest
