Ready-to-use paraquat sensor using a graphene-screen printed electrode modified with a molecularly imprinted polymer coating on a platinum core

Abstract

We propose the fabrication of a novel ready-to-use electrochemical sensor based on a screen-printed graphene paste electrode (SPGrE) modified with platinum nanoparticles and coated with a molecularly imprinted polymer (PtNPs@MIP) for sensitive and cost-effective detection of paraquat (PQ) herbicide. Successive coating of the PtNPs surface with SiO₂ and vinyl end-groups formed the PtNPs@MIP. Next, we terminated the vinyl groups with a molecularly imprinted polymer (MIP) shell. MIP was attached to the PtNPs cores using PQ as the template, methacrylic acid (MAA) as the monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linker, and 2,2′-azobisisobutyronitrile (AIBN) as the initiator. Coating the SPGrE surface with PtNPs@MIP furnished the PQ sensor. We studied the electrochemical mechanism of PQ on the MIP sensor using cyclic voltammetry (CV) experiments. The PQ oxidation current signal appears at −1.08 V and −0.71 V vs. Ag/AgCl using 0.1 M potassium sulfate solution. Quantitative analysis was performed by anodic stripping voltammetry (ASV) using a deposition potential of −1.4 V for 60 s and linear sweep voltammetric stripping. The MIP sensor provides linearity from 0.05 to 1000 μM (r² = 0.999), with a lower detection limit of 0.02 μM (at −0.71 V). The compact imprinted sensor gave a highly sensitive and selective signal toward PQ. The ready-to-use MIP sensor can provide an alternative approach to the determination of paraquat residue on vegetables and fruits for food safety applications.