Pure and Applied Chemistry

Abstract: This study presents a simple, sensitive, rapid, and low-cost amperometric method for direct and quantitative determination of glyphosate and glufosinate herbicides. Electrochemical synthesis and characterization of poly(2,5-dimethoxyaniline)-poly(4-styrenesulfonic acid) (PDMA-PSS) nanoparticles was achieved by cyclic voltammetry (CV) and scanning electron microscopy (SEM). The nanobiosensor was constructed by immobilizing the enzyme horseradish peroxidase (HRP) electrostatically onto the surface of a rotating gold disk electrode modified with PDMA-PSS nanoparticles. The biosensing principle was based on determination of the sensor response to glyphosate and glufosinate by amperometric methods. Hydrogen peroxide (H₂O₂) was used to measure activity of the enzyme before injection of the herbicides into the electrolyte solution. The enzyme electrode was stable for a long period of time and was used for over 60 measurements. Glyphosate and glufosinate analyses were realized on spiked corn samples within a concentration range of 2.0-78.0 μg L^-1, corroborating that the nanobiosensor is sensitive enough to detect herbicides in these matrices. Based on a 20-μL sample injection volume, the detection limits were 0.1 μg L^-1 (10^-10 M) for both glyphosate and glufosinate without sample clean-up or preconcentration.