Self-Circulation Oxygen-Hydrogen Peroxide-Oxygen System for Ultrasensitive Cathode Photoelectrochemical Bioassay...

In this work, a self-circulation oxygen-hydrogen peroxide-oxygen (O₂-H₂O₂-O₂) system with photogenerated electrons as fuel and highly active hemin monomers as operators was engineered for ultrasensitive cathode photoelectrochemical bioassay of microRNA-141 (miRNA-141) using a stacked sealed paper device. During the circulation, the photogenerated electrons from BiVO₄/Cu₂O photosensitive structures assembled on a reduced graphene oxide paper electrode first reduced the electron acceptors (dissolved O₂) to H₂O₂, which was then catalytically decomposed by hemin monomers to generate O₂ again. The regenerated O₂ continued to be reduced, which made O₂ and H₂O₂ stuck in the infinite loop of O₂-H₂O₂-O₂ accompanied by the fast consumption of photogenerated electrons, generating an amplified photocurrent signal. When a target existed, a duplex-specific nuclease-induced target recycling reaction with dual trigger DNA probes as the output was performed to initiate the assembly of bridge-like DNA nanostructures, which endowed the self-circulation system with dual destruction functions as follows. (i) Reduced fuel supply: the assembled DNA bridges acting as a negatively charged barrier prevented the photogenerated electrons from participating in the O₂ reduction to H₂O₂. (ii) Incapacitation of operators: DNA bridging induced the dimerization of hemin monomers linked on the DNA hairpins to catalytically inactive hemin dimers, leading to the abortive regeneration of O₂. These destruction functions resulted in the circulation interruption and a remarkably decreased photocurrent signal. Thus, the developed cathode photoelectrochemical biosensing platform achieved ultrasensitive miRNA-141 detection with a linear range of 0.25 fM to 1 nM and a detection limit of 83 aM, and it also exhibited high accuracy, selectivity, and practicability.