Metal-pyrimidine nanocubes immobilized enzymes with pH-switchable multienzyme-like activity for broad-pH-responsive sensing assay for organophosphorus pesticides.

Peroxidase (POD)-like can only function in acidic environments and the pH mismatch restricts the application of enzyme-nanozyme cascade catalytic sensing platforms in the broad-pH-responsive assay for organophosphorus pesticides (OPs). Herein, the metal-pyrimidine nanocubes (MPNCs) with intrinsic pH-switchable POD-like and catalase (CAT)-like properties were synthesized via the coordination of pyrimidin-2-ol with Cu. Meanwhile, acetylcholinesterase (AChE) and choline oxidase (CHO) were simultaneously encapsulated in MPNCs to construct an enzyme-nanozyme cascade catalytic platform (AChE/CHO@MPNCs). AChE/CHO@MPNCs could catalyze the hydrolysis of acetylcholine to choline, which was subsequently converted to HO. The POD-like activity of MPNCs was dominant under acidic conditions, while the CAT-like activity prevailed under neutral and alkaline conditions, which could catalyze HO to •OH and O, respectively, then oxidizing dopamine (DA) to polydopamine quantum dots (PDA QDs) with different fluorescence characteristics. Consequently, OPs could be detected in a linear range from 0.05 to 1000 nM with a LOD of 0.015 nM in acidic environments and a linear range from 0.05 to 500 nM with a LOD of 0.023 nM in alkaline environments. Overall, our work expands the horizon of constructing enzyme@MOFs composites with high catalytic activity. Meanwhile, the intrinsic pH-switchable multienzyme-like property opens avenues to construct sensing platforms with broad-pH-responsive for OPs and other analytes detection.