Light-driven reconfiguration of catanionic self-assembly enables bidirectional modulation of drug-release kinetics

Light-responsive control over supramolecular self-assembly provides a route to dynamically regulate nanoscale transport processes. Here we demonstrate that photoisomerization of a membrane-bound chalcone amphiphile enables light-driven reprogramming of catanionic self-assembly, producing composition-dependent morphological transitions that directly govern drug-release kinetics. Mixtures of a 2-hydroxychalcone-derived cationic amphiphile (C₆NCh) with the biocompatible anionic surfactant sodium N-lauroyl sarcosinate spontaneously form stable unilamellar vesicles (hydrodynamic diameter ≈ 130-200 nm) across a broad concentration range on the anion-rich side of the phase diagram. Upon near-UV irradiation, chalcone photoisomerization and tautomerization induce marked reconfiguration of the self-assembled structures, leading either to vesicle-to-micelle transitions or to membrane reorganization with faceted vesicle morphologies, depending on composition. These light-driven structural pathways generate distinct nanoscale transport regimes, enabling bidirectional modulation of paclitaxel release kinetics. Accelerated release is observed when irradiation promotes formation of highly dynamic micellar aggregates, whereas membrane ordering and domain formation correlate with reduced permeability and slower release. Under selected conditions, zero-order release behavior is achieved, with irradiation increasing the release rate by approximately 50%. These results identify chalcone-based catanionic assemblies as a useful model system in which external stimuli reprogram self-assembly and thereby tune molecular transport, offering a conceptual basis for the design of adaptive self-assembled nanocarriers.