Bioinspired Interfacial Hitchhiking: 3D Hierarchical Nanopesticide Aggregates via Heterointerface-Confined Coassembly for Spatiotemporal Foliar Deposition and Translocation In Vivo

Efficient foliar delivery of agrochemicals requires precise spatiotemporal control over both foliar deposition and translocation in vivo. Drawing inspiration from natural systems, such as biomolecular recognition and vesicular transport across cellular membranes, the work proposes a heterointerface-confined coassembly (HICA) strategy that leverages emulsion interfaces to construct programmable three-dimensional (3D) hierarchical nanopesticide aggregates, thereby substantially enhancing the bioavailability and efficacy of active ingredients (AIs). At the molecular level, π-π stacking between a lipophilic herbicide (oxyfluorfen, Oxy) and amphiphilic alginate derivatives functionalized with azobenzene (Azo) and polydopamine (PDA) drives the formation of two-dimensional (2D) interfacial nanoparticle films, which template the growth of 3D flexible nanopesticide systems. These structurally ordered emulsions exhibit dual environmental responsiveness: NIR (808 nm) triggered photothermal morphing for adaptive foliar adhesion, while ultraviolet (UV) (365 nm) regulated Azo isomerization to enable spatiotemporally controlled Oxy release. Through a multiscale characterization integrating density functional theory (DFT), molecular dynamics (MD) simulations, ultraviolet-visible (UV-vis) spectroscopy, isothermal titration calorimetry (ITC), and confocal laser scanning microscopy (CLSM), the work confirms programmable supramolecular assembly and efficient translocation in vivo via both cuticular and vascular pathways. The resulting formulations demonstrated the desired impact resistance on superhydrophobic surfaces and achieved 100% weed mortality through a contact-translocation mode of action. By bridging supramolecular design, interfacial engineering, and functional emulsions, this work establishes a sustainable platform for intelligent agrochemical delivery with tailored environmental adaptability, offering a versatile route toward precision crop protection.