On-Site Detection of Neonicotinoid Pesticides Using Functionalized Gold Nanoparticles and Halogen Bonding

Neonicotinoid (NN) pesticides have emerged globally as one of the most widely used agricultural tools for protecting crops from pest damage and boosting food production. Unfortunately, some NN compounds, such as extensively employed imidacloprid-based pesticides, have also been identified as likely endangering critical pollinating insects like honey bees. To this end, NN pesticides pose a potential threat to world food supplies. As more countries restrict or prohibit the use of NN pesticides, tools are needed to effectively and quickly identify the presence of NN compounds like imidacloprid on site (e.g., in storage areas on farms or pesticide distribution warehouses). This study represents a proof-of-concept where the colloidal properties of specifically modified gold nanoparticles (Au-NPs) able to engage in the rare intermolecular interaction of halogen bonding (XB) can result in the detection of certain NN compounds. Density functional theory and diffusion-ordered NMR spectroscopy (DOSY NMR) are used to explore the fundamental XB interactions between strong XB-donor structures and NN compounds, with the latter found to possess multiple XB-acceptor binding sites. A fundamental understanding of these XB interactions allows for the functionalization of alkanethiolate-stabilized Au-NPs, known as monolayer-protected gold clusters (MPCs), with XB-donor capability (f-MPCs). In the presence of certain NN compounds such as imidacloprid, the f-MPCs subsequently exhibit visual XB-induced aggregation that is also measured with absorption (UV-vis) spectroscopy and verified with transmission electron microscopy (TEM) imaging. The demonstrated f-MPC-aggregation detection scheme has a number of favorable attributes, including quickly reporting the presence of the NN target, requiring only micrograms of suspect material, and being highly selective for imidacloprid, the most prevalent and most important NN insecticide compound. Requiring no instrumentation, the presented methodology can be envisioned as a simple screening test in which dipping a cotton swab of an unknown powder from a surface in a f-MPC solution causes f-MPCs to aggregate and yield a preliminary indication of imidacloprid presence.