In situ generated PANI promoted flexible photoelectrochemical biosensor for ochratoxin A based on GOx-stuffed DNA hydrogel as enhancer

A flexible photoelectrochemical (PEC) biosensor is proposed for the sensitive detection of ochratoxin A (OTA) based on glucose oxidase (GOx)-encapsulated target-responsive hydrogel, using Fenton reaction-mediated in situ formation of polyaniline (PANI) as signal amplified strategy. The target-responsive DNA hydrogels with high loading capacity can carry a large amount of GOx, which not only avoids laborious labeling process but also enhances the analytical performance. Upon introduction of target molecules, the hydrogel can be opened, and multiple GOx was released, thus producing lots of H₂O₂ via catalytic reduction of glucose. As a component of the Fenton reagent, H₂O₂ can react with the Fe²⁺ on the graphene oxidase-PAMAM-Fe²⁺ (GO-PAMAM-Fe²⁺) to generate Fe³⁺ and ·OH. This in turn can oxidize aniline and generate polyaniline (PANI), resulting in the enhancement of the photocurrent signal of GO-MoS₂-CdS photoelectrode. The GO-PAMAM-Fe²⁺ as the neighborhood component of GO-MoS₂-CdS-based photoactive material not only can increase the loading amount of Fe²⁺, but also can inhibit the decrease of photocurrent of GO-MoS₂-CdS by direct modification of Fe²⁺ on the photoactive material. Moreover, the high loading capacity of DNA hydrogel can efficiently promote the performance of the PEC biosensor. The PEC biosensor exhibited satisfactory analytical performance for OTA with a linear range of 0.0001-0.1 ng/mL and a low detection limit of 0.05 pg/mL. It presents recommendable specificity, stability, and practical applications. Importantly, the PEC biosensor provides a new concept for construction of PEC biosensing platform.