Amperometric nanobiosensor for quantitative determination of glyphosate and glufosinate residues in corn samples

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.