Amorphous Fe-Containing Phosphotungstates Featuring Efficient Peroxidase-like Activity at Neutral pH: Toward Portable Swabs for Pesticide Detection with Tandem Catalytic Amplification

Peroxidase-mimetic materials are intensively applied to establish multienzyme systems because of their attractive merits. However, almost all of the nanozymes explored exhibit catalytic capacity only under acidic conditions. The pH mismatch between peroxidase mimics in acidic environments and bioenzymes under neutral conditions significantly restricts the development of enzyme-nanozyme catalytic systems especially for biochemical sensing. To solve this problem, here amorphous Fe-containing phosphotungstates (Fe-PTs) featuring high peroxidase activity at neutral pH were explored to fabricate portable multienzyme biosensors for pesticide detection. The strong attraction of negatively charged Fe-PTs to positively charged substrates as well as the accelerated regeneration of Fe2+ by the Fe/W bimetallic redox couples was demonstrated to play important roles in endowing the material with peroxidase-like activity in physiological environments. Consequently, integrating the developed Fe-PTs with acetylcholinesterase and choline oxidase led to an enzyme- nanozyme tandem platform with good catalytic efficiency at neutral pH for organophosphorus pesticide response. Furthermore, they were immobilized onto common medical swabs to fabricate portable sensors for paraoxon detection conveniently based on smartphone sensing, showing excellent sensitivity, good anti-interference capacity, and low detection limit (0.28 ng/mL). Our contribution expands the horizon of acquiring peroxidase activity at neutral pH, and it will also open avenues to construct portable and effective biosensors for pesticides and other analytes.

Automated summary

Peroxidase-mimetic Fe-containing phosphotungstates (Fe-PTs) were explored as a portable multienzyme biosensor for pesticide detection under neutral pH conditions. The material exhibited peroxidase-like activity in physiological environments due to its strong attraction to positively charged substrates and accelerated regeneration of Fe2+ by the Fe/W bimetallic redox couples. Integration of Fe-PTs with acetylcholinesterase and choline oxidase resulted in an enzyme-nanozyme tandem platform with good catalytic efficiency at neutral pH for organophosphorus pesticide response. The immobilized sensors on medical swabs showed excellent sensitivity, good anti-interference capacity, and a low detection limit (0.28 ng/mL) for paraoxon detection using smartphone sensing.