Highly Efficient Wavelength-Resolved Electrochemiluminescence of Carbon Nitride Films for Ultrasensitive Multiplex MicroRNA Detection

The development of electrochemiluminescence (ECL) emitters of different colors with high ECL efficiency (Φ_ECL) is appealing yet challenging for ultrasensitive multiplexed bioassays. Herein, we report the synthesis of highly efficient polymeric carbon nitride (CN) films with fine-tuned ECL emission from blue to green (410, 450, 470, and 525 nm) using the precursor crystallization method. More importantly, naked eye-observable and significantly enhanced ECL emission was achieved, and the cathodic Φ_ECL values were ca. 112, 394, 353, and 251 times those of the aqueous Ru(bpy)₃Cl₂/K₂S₂O₈ reference. Mechanism studies showed that the density of surface-trapped electrons, the associated nonradiative decay pathways, and electron-hole recombination kinetics were crucial factors for the high Φ_ECL of CN. Based on high Φ_ECL and different colors of ECL emission, the wavelength-resolved multiplexing ECL biosensor was constructed to simultaneously detect miRNA-21 and miRNA-141 with superior low detection limits of 0.13 fM and 25.17 aM, respectively. This work provides a facile method to synthesize wavelength-resolved ECL emitters based on metal-free CN polymers with high Φ_ECL for multiplexed bioassays.