Ultrasensitive Paper-Based Photoelectrochemical Biosensor for Acetamiprid Detection Enabled by Spin-State Manipulation and Polarity-Switching.

Efficient carrier separation is vitally crucial to improving the detection sensitivity of photoelectrochemical (PEC) biosensors. Here, we developed a facile strategy to efficiently regulate the carrier separation efficiency of the photoactive matrix BiOI and In2S3 signal label functionalized paper chip by manipulation of electrons spin-state and rational design of electron transport pathways. The spin-dependent electronic structures of BiOI and In2S3 were regulated via enhanced electron-spin parallel alignment induced by an external magnetic field, markedly retarding carrier recombination and extending their lifetime. Simultaneously, with the progress of the target-induced catalytic hairpin assembly process, the transfer path of photogenerated carriers was changed, leading to a switch in photocurrent polarity from cathode to anode. This reversed electron transport pathway not only boosted the separation ability of photogenerated electrons but also eliminated false-positive and false-negative signals, thereby further improving the detection sensitivity. As a proof of concept, the well-designed magnetic field-stimulated paper-based PEC biosensor showed highly selectivity and sensitivity for acetamiprid assay with a wide linear range of 1 fM to 20 nM and an ultralow detection limit of 0.73 fM. This work develops a universal strategy for improving the sensitivity of biosensors and exhibits enormous potential in the fields of bioanalysis and clinical diagnosis.