A Hierarchical core-shell nanohybrid for dual-stimuli-responsive antifungal delivery against Botrytis cinerea

The persistent threat of phytopathogenic fungi necessitates precision-targeted and sustainable antifungal strategies beyond conventional agrochemicals. This study presents a hierarchically structured micro/nanosystem (CMC@Eu-ZIF@ZnO) engineered for precision antifungal delivery by leveraging the specific virulence mechanisms of Botrytis cinerea. The composite features a dual core-shell architecture: a ZnO microsphere core encapsulated within a ZIF-8 intermediate shell and an outer carboxymethyl cellulose (CMC) coating. This intelligent design integrates pH- and cellulase-triggered release pathways, exploiting fungal-induced and enzymatic secretion for on-demand cargo delivery. Synergistic action between Eu and ZnO nanoparticles enhances membrane disruption and oxidative stress, resulting in superior antifungal activity. The system achieved 91.5 % cumulative release under dual stimuli and 67.9 % rainfast retention, with negligible phytotoxicity in soybean germination assays and effective lesion control in tomato leaves. By overcoming instability, non-target leakage, and limited responsiveness of conventional fungicides, this study establishes a microenvironment-responsive hierarchical delivery platform. This work highlights the potential of integrating natural antifungals with hierarchical nanostructures for eco-friendly, precision crop protection.