In-Situ Generation of Hydrogen Polysulfides (H 2 S n ) with Thioglucose, Glucose Oxidase, and Chloroperoxidase.

Hydrogen polysulfides (H 2 S n ) have emerged as critical physiological mediators that are closely associated with hydrogen sulfide (H 2 S) signaling. H 2 S n exhibit greater nucleophilicity than H 2 S while also having electrophilic characteristics, enabling unique activities such as protein S-persulfidation. Despite their physiological importance, mechanisms and reactivities of H 2 S n remain inadequately explored due to their inherent instability in aqueous environments. Consequently, there is a need to develop biocompatible methods for controlled H 2 S n generation to elucidate their behaviors in biological contexts. Herein, we present a dual enzyme system (containing glucose oxidase (GOx) and chloroperoxidase (CPO)) with thioglucose as the substrate to facilitate the controlled release of H 2 S n . Fluorescence measurements with SSP4 and the trapping studies allowed us to confirm the production of H 2 S n . Such a method may be useful in elucidating the reactivity of hydrogen polysulfides in biological systems as well as provide a potential delivery of H 2 S n to target sites for biological applications.