Highly sensitive photoelectrochemical detection of bleomycin based on Au/WS2 nanorod array as signal matrix and Ag/ZnMOF nanozyme as multifunctional amplifier

Abstract

An ultrasensitive photoelectrochemical (PEC) biosensor was constructed based on gold nanoparticles (Au NPs)/tungsten sulfide nanorod array (WS₂ NA) photoelectrode as the PEC matrix and silver nanoparticles/flake-like zinc metal-organic framework (Ag/ZnMOF) nanozyme with the peroxidase mimetic enzyme property for sensitive detection of bleomycin (BLM). In particular, Au/WS₂ and Ag/ZnMOF were linked by thiolate DNA₁ and DNA₂ strand, respectively, and the Au/WS₂-Ag/ZnMOF probe was prepared via hybridization reaction between the two DNAs. The introduction of Ag/ZnMOF in the probe offers two functions: i) the steric hindrance effect can effectively impede electron transport and reduce the photocurrent; ii) Ag/ZnMOF nanozyme can also be used as mimic peroxidase to effectively catalyze 3,3-diaminobenzidine (DAB) to produce the relevant precipitation, which will further reduce photocurrent and eliminate false positive signals. When BLM exists, BLM with Fe²⁺ as irreversible cofactor can specifically recognize and cleave of the 5'-GC-3' active site of DNA₂, resulting in reduced precipitation deposited on the electrode and recovery of PEC signal. The highly sensitive PEC biosensor exhibits a the linear strategy from 0.5 nM to 500 nM with a detection limit down to 0.18 nM. Further, the unique strategy was conducted in biological samples for BLM detection with satisfactory consequence, offering available and efficient pathway for disease diagnosis.

Keywords: Ag/ZnMOF nanozyme; Bleomycin; Photoelectrochemical; WS(2) nanorod array.