Ultrathin graphdiyne nanosheets confining Cu quantum dots as robust electrocatalyst for biosensing featuring remarkably enhanced activity and stability

Abstract

There is an urgent need for developing electrochemical biosensor based on the acetylcholinesterase (AChE) inhibition to real-time analysis of organophosphorus pesticides (OPs), but it is suffered from the sluggish electrode kinetics and high oxidation potential toward signal species. Herein, a nanocomposite of ultrafine Cu quantum dots (QD) uniformly loaded on three-dimensional ultrathin graphdiyne (GDY) nanosheets (denoted as Cu@GDY) was synthesized via a one-step strategy, which showing high-density of active sites with persistent stability. Then an AChE biosensor based on Cu@GDY was fabricated to detect OPs, and the results revealed that the Cu@GDY nanocomposite can significantly amplifies electrochemical signal and reduces the oxidation potential for OPs. The strong interaction between active site of Cu@GDY and thiocholine signal species caused rapid analyte aggregation and decreased the reaction activation energy of thiocholine electro-oxidation. Benefiting from the excellent catalytic activity of Cu@GDY nanocomposite and reasonable regulation of enzyme inhibition kinetics, the biosensor achieved rapid and sensitive detection of OPs with a detection limit of 1 μg L−1 for paraoxon. Furthermore, the biosensor demonstrated great reproducibility, good stability and high recovery rate for OPs detection in real samples. Cu@GDY based sensor also displayed high catalytic activities and good selectivity to the non-enzymatic detection of glucose in alkaline medium. Cu@GDY offers a versatile and promising platform for sensors and biosensors featuring remarkably enhanced activity and stability, and can be applied to many other fields as desirable electrocatalyst.