Potentiometric MIP-Modified Screen-Printed Cell for Phenoxy Herbicides Detection

In this study, a molecularly imprinted polymer (MIP)-based screen-printed cell is developed for detecting phenoxy herbicides using 2-methyl-4-chlorophenoxyacetic acid (MCPA) as the template. MCPA is a phenoxy herbicide widely used since 1945 to control broadleaf weeds via growth regulation, primarily in pasture and cereal crops. The potentiometric cell consists of a silver/silver chloride pseudo-reference electrode and a graphite working electrode coated with a MIP film. The polymeric layer is thermally formed after drop-coating of a pre-polymeric mixture composed of the reagents at the following molar ratio: 1 MCPA: 15 MAA (methacrylic acid): 7 EGDMA (ethylene glycol dimethacrylate). After template removal, the recognition cavities function as the ionophore of a classical ion selective electrode (ISE) membrane. The detected ion is the deprotonated MCPA specie, negatively charged, so the measurements were performed in phosphate buffer at pH 5.5. A linear decrease of the potential with MCPA concentration, ranging from 4 × 10^-8 to 1 × 10^-6 mol L^-1, was obtained. The detection limit and the limit of quantification were, respectively, 10 nmol L^-1 and 40 nmol L^-1. A Nernstian slope of about -59 mV/dec was achieved. The method has precision and LOD required for MCPA determination in contaminated environmental samples.