Exonuclease-catalyzed recycling and annular four-footed DNA walking amplification-assisted “on-off-super on” signal transitions for photoelectrochemical biosensing of kanamycin

Photoelectrochemical (PEC) biosensors have exhibited a promising potential for assays of a large variety of analytes; however, how to realize their low background-based "super on" signal output is still a great challenge. Herein, we report a novel multiple nucleic acid amplification-assisted "on-off-super on" signal transition mechanism for the PEC biosensing of kanamycin antibiotics. The biosensing platform was constructed on a perylene-3,4,9,10-tetracarboxylic dianhydride-based photoelectrode, and its strong photocurrent could be well inhibited by an anchored ferrocene (Fc)-labeled hairpin DNA to produce a low background signal. Two target biorecognition-triggered exonuclease III-catalytic reactions were adopted to produce an annular four-footed DNA walker (AFW) and a methylene blue (MB)-labeled DNA strand. By using their synergistic effect to release Fc quenchers and simultaneously capture MB sensitizers, a "super on" signal output was realized. As a result, a very wide linear range from 10 fg mL