Piezotronic Effect-Assisted Photoelectrochemical Exosomal MicroRNA Monitoring Based on an Electron Donor Self-Supplying Strategy

Exosomal microRNAs (miRNAs) as newly emerging reliable and noninvasive biomarkers have demonstrated a significant function in early cancer diagnosis. Photoelectrochemical (PEC) biosensing has attracted unprecedented attention in exosomal miRNA monitoring due to its inherent advantages of both electrochemical and optical techniques; however, the severe charge carrier recombination greatly restricts the PEC assay performance. Herein, a high-sensitive PEC strategy assisted by the piezoelectric effect is designed based on Bi₂WO₆/Cu₂S heterojunctions and implemented for the monitoring of exosomal miRNAs. The introduction of the piezoelectric effect enables promoted electron-hole transfer and separation, thereby improving the analytical sensitivity. In addition, a target reprogramming metal-organic framework-capped CaO₂ (MOF@CaO₂) hybrids is prepared, in which MOF@CaO₂ being responsive to exosomal miRNAs induces exposure of the capped CaO₂ to H₂O and then triggers self-supplying of H₂O₂, which effectively suppresses the electron-hole recombination, giving rise to an amplified photocurrent and a decrease in the cost of the reaction. Benefiting from the coupled sensitization strategy, the as-fabricated PEC strategy exhibits high sensitivity, specificity, low cost, and ease of use for real-time analysis of exosomal miRNAs within the effectiveness linear range of 0.1 fM-1 μM. The present work demonstrates promising external field coupling-enhanced PEC bioassay and offers innovative thoughts for applying this strategy in other fields.