Ultrasensitive and Visual Electrochemiluminescence Ratiometry Based on a Constant Resistor-Integrated Bipolar Electrode for MicroRNA Detection

In this work, a new electrochemiluminescence (ECL) platform was constructed for detecting the prostate cancer marker microRNA-141 (miRNA-141) on a constant resistor-integrated closed bipolar electrode (BPE). It consisted of two reservoirs and a constant resistor, and both ends were connected to the anode of the driving electrode and the cathode of BPE. The cathode of BPE was modified with boron nitride quantum dots (BNQDs), and the anode reservoir was the [Ru(bpy)₃](PF₆)₂/TPrA system. After introducing a certain amount of hairpin DNA 3 (H3) and ferrocene-labeled single-stranded DNA (Fc-ssDNA) on the surface of the BNQDs, the ECL emission signal of the BNQDs was difficult to be observed by the naked eye, while [Ru(bpy)₃](PF₆)₂ emitted a strong and visible ECL signal. In the presence of the target, bipedal DNA assembled by catalytic hairpin assembly (CHA) took away the Fc-ssDNA and the ECL intensity of the BNQDs was enlarged, and as the concentration of miRNA-141 increased to the cutoff value, yellow-green light was visible by the naked eye. Meanwhile, the red emission signal of [Ru(bpy)₃](PF₆)₂/TPrA became weakened. Thus, an ultrasensitive "color switch" ECL biosensor for detection of miRNA-141 was constructed and endowed with a wide linear range from 10^-17 to 10^-7 M and a detection limit of 10^-17 M (S/N = 3). This study provides the potential for investigating portable devices in the detection of low-concentration nucleic acids.