Abstract
Tools to enable spatiotemporally controlled upregulation of supersulfides, which are highly reactive, unstable sulfur species, are needed to study the pathophysiological roles of post-translational protein modification with catenated sulfur atoms. Here, we set out to design N,N-diethylaminocoumarin (DEAC)-based visible-light-responsive N-acetylcysteine persulfide donors (NAC-SS-DEAC), and serendipitously found that upon visible light irradiation, they donate a sulfane sulfur (S(0)) atom to nucleophiles, including thiols and cyanate. Light-assisted tautomerization of the disulfide moiety of NAC-SS-DEAC to transiently afford unstable thiosulfoxide plays a key role in the S(0) donation. We show that this reaction can be utilized to achieve visible-light-inducible manipulation of supersulfide levels in living cells.