posted on 2022-01-13, 21:45authored byKaylin
G. Fosnacht, Matthew M. Cerda, Emma J. Mullen, Hannah C. Pigg, Michael D. Pluth
Persulfides
(RSSH) are important reactive sulfur species (RSS)
that are intertwined with the biological functions of hydrogen sulfide
(H2S). The direct study of persulfides is difficult, however,
due to their both nucleophilic and electrophilic character, which
leads to the generation of an equilibrium of different RSS. To investigate
the effects of persulfides directly, especially in biological systems,
persulfide donors are needed to generate persulfides in situ. Here, we report the synthesis of esterase-activated perthiocarbonate
persulfide donors and investigate the effects of structural modifications
on persulfide release. Although steric bulk of the ester did not significantly
alter persulfide release kinetics, increased steric bulk of the thiol
increased the persulfide release rate. In addition, we found that
the steric bulk and identity of the thiol significantly impact persulfide
persistence. Further mechanistic investigations into different competing
reaction pathways from perthiocarbonates revealed that multiple RSS
can be delivered (i.e., H2S, COS, or RSSH)
depending on the persulfide donor structure and activator identity.