Photoluminescence and Electrochemiluminescence Dual-Signaling Sensors for Selective Detection of Cysteine Based on Iridium(III) Complexes

Cysteine (Cys) is important in biosynthesis, detoxification, and metabolism. The selective detection of Cys over structurally similar homocysteine (Hcy) or glutathione (GSH) remains an immense challenge. Although there are many methods for detecting Cys, photoluminescence (PL) and electrochemiluminescence (ECL) techniques are well-suited for clinical diagnostics and analytical technology because of their high sensitivities. Herein, we report PL and ECL dual-channel sensors using cyclometalated iridium­(III) complexes for the discrimination of Cys from Hcy and GSH. The sensors react with cysteine preferentially because of kinetic differences in intramolecular conjugate addition/cyclization, enabling phosphorescence enhancement and ECL decrease in the blue-shifted region. Sensor 1 shows ratiometric PL turn-on and ECL turn-off for Cys. In addition, unique ECL-enhancing behavior of sensor 1 toward GSH enables discrimination between Cys and GSH. Sensor 1 was successfully applied to the detection of Cys in human serum by the ECL method. We demonstrate the first case of a Cys-selective PL and ECL dual-channel chemodosimetric sensor based on cyclometalated iridium­(III) complexes and expect that the rational design of efficient PL and ECL dual-channel sensors will be useful in diagnostic technology.