Electrochemical Sensing of Neonicotinoids Using Laser-Induced Graphene

Neonicotinoids are the fastest-growing insecticide accounting for over 25% of the global pesticide market and are capable of controlling a range of pests that damage croplands, home yards/gardens, and golf course greens. However, widespread use has led to nontarget organism decline in pollinators, insects, and birds, while chronic, sublethal effects on humans are still largely unknown. Therefore, there is a need to understand how prevalent neonicotinoids are in the environment as there are currently no commercially available field-deployable sensors capable of measuring neonicotinoid concentrations in surface waters. Herein, we report the first example of a laser-induced graphene (LIG) platform that utilizes electrochemical sensing for neonicotinoid detection. These graphene-based sensors are created through a scalable direct-write laser fabrication process that converts polyimide into LIG, which eliminates the need for chemical synthesis of graphene, ink formulation, masks, stencils, pattern rolls, and postprint annealing commonly associated with other printed graphene sensors. The LIG electrodes were capable of monitoring four major neonicotinoids (CLO, IMD, TMX, and DNT) with low detection limits (CLO, 823 nM; IMD, 384 nM; TMX, 338 nM; and DNT, 682 nM) and a rapid response time (∼10 s) using square-wave voltammetry without chemical/biological functionalization. Interference testing exhibited negligible responses from widely used pesticides including the broad-leaf insecticides parathion, paraoxon, and fipronil, as well as systemic herbicides glyphosate (roundup), atrazine, dicamba, and 2,4-dichlorophenoxyacetic acid. These scalable, graphene-based sensors have the potential for wide-scale mapping of neonicotinoids in watersheds and potential use in numerous electrochemical sensor devices.