Immobilization-free photoelectrochemical aptasensor for environmental pollutants: Design, fabrication and mechanism

Atrazine (ATZ) is one of the most widely used and highly toxic triazine herbicides in the world. Photoelectrochemical (PEC) method is an attractive and sensitive alternate for ATZ. However, for conventional PEC sensors, recognition elements usually need to immobilize on electrode surface, where a complex procedure is unavoidable and the reproducibility of sensors fabrication is usually poor. Therefore, we herein proposed a new and feasible strategy for developing a signal-on immobilization-free PEC aptasensor to ATZ. Aptamer for ATZ is combined with graphene to obtain APT-GN complex, serving as the recognition element in solution. TiO2 nanotubes (NTs) electrode deposited with Au nanoparticles (NPs) is used as the substrate electrode. After further self-assembled with 1-Mercaptooctane (MCT), the photo-generated carriers transfer between the resultant electrode and the electrolyte will be blocked, leading to a signal-off of the photocurrent. But when sensing ATZ, aptamers on APT-GN will be grasped by ATZ, leaving free graphene to assemble onto MCT/Au NPs/TiO2 NTs, which will largely turn on the photocurrent response of the substrate electrode due to the efficient carrier transport efficiency of graphene. Meanwhile, simultaneous addition of deoxyribonuclease I (DNase I) can bring about further cycling amplification of the signal enhancement. The as-designed PEC aptasensor exhibits a linear range from 50.0 fM to 0.3 nM with detection limit of 12.0 fM for ATZ. Since the reaction of recognition elements and targets ATZ occurs in homogeneous solution rather than on the photoelectrode surface, this PEC aptasensor exhibits advantages of high stability, anti-interference ability, reproducibility, and wide pH and ion strength feasibility range. A promising immobilization-free aptasensing platform has thus been provided not only for ATZ but also for other kinds of environmental pollutants.