Programmed Interfacial Phase Separation for Spatiotemporal Fungicide Delivery via Tunable Micro/Nano Architectures

ABSTRACT

Translating dynamic liquid‐liquid phase separation into robust solid‐state architectures remains a challenge in materials engineering. Here, we report a composition‐driven interfacial assembly strategy that couples supramolecular coacervation with metal‐phenolic coordination to engineer tunable fungicide carriers. By modulating the mass ratio between tea polyphenols (TP) and non‐ionic surfactants, we generate fluid templates that are kinetically trapped via pH‐triggered iron complexation. This one‐pot protocol allows for the precise regulation of the micro‐to‐nano population ratio, effectively addressing the dimensional mismatch between soil retention and systemic uptake. The resulting architecture achieves a functional division: microcapsules function as stationary reservoirs for rhizosphere protection, while nanocapsules act as mobile vectors for systemic curative action. Furthermore, the metal‐phenolic shell exhibits pathogen‐responsive disassembly upon exposure to fungal virulence factors, including oxalic acid and cellulases secreted by Fusarium pathogens. Validated in a peanut root rot model, this system demonstrates improved spatiotemporal efficacy and reduced aquatic toxicity toward zebrafish compared to commercial formulations. Consequently, this work presents a versatile methodology for structuring dynamic liquid interfaces based on TP‐surfactant supramolecular interactions, offering a potent solution for precision agriculture through the controlled solidification of supramolecular assemblies.