Influence of nanopesticide surface chemistry on adsorption to plant cuticle and wax layer: The role of zeta potential and wetting

Nanopesticidal adsorption on plant surfaces is a critical determinant of their application efficacy, persistence, and ecological impact. In this study, we systematically investigate the impact of surface chemistry on the attachment of nanopesticides for seven different nanocarriers: ethyl lauroyl arginate (ELA, cationic), cocamidopropyl betaine (CAPB, zwitterionic), tween 80 (TW80, nonionic), β-cyclodextrin (βCD), sodium dodecyl sulfate (SDS, anionic), whey protein isolate (WPI), and poloxamer 407 (PXL, nonionic). Azadirachtin from neem seed extract was employed as a model pesticide active ingredient. The nanopesticides were characterized using dynamic light scattering, UV–visible spectroscopy, static contact angle (SCA, θ), and zeta (ζ) potential measurements. Pepper leaves (ζ = −11.6 mV) and candelilla wax (ζ = −2.6 mV) films were utilized to analyze the effect of nanocarrier chemical composition on nanopesticide adsorption. Fluorescence microscopy was utilized to quantify the adsorption of nanopesticides (with fluorophore tagging) on the substrates. It was found that the choice of nanocarrier significantly influenced the adsorption behavior. Nanopesticides with ELA corona, which was cationic with a zeta potential of ∼+19 mV and θ of ∼ 61°, exhibited the highest affinity towards the leaf cuticle and wax substrates, attributed to favorable electrostatic interactions forces. Conversely, nanopesticides with SDS (ζ = −48 mV; θ = 45°), WPI (ζ = −24 mV; θ = 54°), and PXL (ζ = −31 mV; θ = 64°) corona demonstrated the least adsorption. These findings indicate a weak correlation between the wetting behavior of nanopesticide suspensions and nanopesticide adsorption on plant and wax surfaces, as well as a strong correlation between nanopesticide zeta potential and nanopesticide adsorption. These findings heuristically recommend that aqueous cationic and zwitterionic nanocarriers for pesticides provide superior adsorption characteristics on pepper leaves and candelilla wax surfaces. Aqueous macromolecular carriers such as PXL and WPI have performed less effectively in adherence compared to shorter chain amphiphiles with similar zeta potential and wetting characteristics, indicating that the steric and osmotic chain effects of hydrophilic macromolecules hinder the adsorption relative to shorter chains.