Highly Selective Electrochemiluminescence Chemosensor for Sulfide Enabled by Hierarchical Reactivity

Hydrogen sulfide (H₂S) is a well-known toxic gas with the odor of rotten eggs. Several reaction-based electrochemiluminescence (ECL) chemosensors for H₂S have been developed; however, no homogeneous ECL probe with high selectivity toward H₂S in aqueous media has been reported. Herein, we report an iridium(III) complex-based ECL chemodosimetric probe employing two 7-nitrobenz-2-oxa-1,3-diazol-4-yl (NBD) groups known as a photo-induced electron transfer quencher and a reaction site for the selective detection of H₂S; the detection mechanism involves H₂S being clearly distinguished from biothiols based on the different cleavage rates of the two NBD groups and extremely weak ECL interferences caused by reaction by-products. The probe was rationally designed to improve selectivity toward H₂S within the ECL analysis platform by enabling the removal of nonspecific background signals observed via fluorescence analysis. This analytical system exhibited remarkable selectivity toward H₂S, a rapid reaction rate, and high sensitivity (LOD = 57 nM) compared to conventional fluorescence methods. Furthermore, the probe could successfully quantify H₂S in tap water samples and commercial ammonium sulfide solutions, which demonstrates the effectiveness of this probe in field monitoring.