Herein, a novel photocurrent polarity switchable photoelectrochemical (PEC) biosensor was fabricated based on the formation of a heterojunction between CuO nanocubes and two-dimensional crystalline covalent organic frameworks (COFs) by cyano-substituted buta-1,3-diene linkage for the detection of silver ion (Ag+), exhibiting an excellent anti-interference capability toward redox substances. Different from most of the COFs that were crystallized by condensation of two components, the proposed PTP-COF was generated by two competitive reversible reactions between the three components 4,4′,4″,4′′′-(pyrene-1,3,6,8-tetrayl)tetrabenzaldehyde (PTBD), 2,2′-(1,4-phenylene)-diacetonitrile (PDT) and acetaldehyde, which not only increased the conjugated π system of framework to accelerate the charge transfer efficiency, but also had strong acid and alkali resistance and bioavailability. Impressively, by combining with Mg2+ DNAzyme triggered DNA walker amplification strategy, the designed PEC biosensor exhibited excellent detection performance for Ag+ range from 100 fM to 1 μM with a limit of detection as low as 35 fM. This work puts forward a new idea for eliminating negative background signals for sensing and expands the application of COFs in the PEC system.
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