Harnessing Chemical and Light Energy for Controlled Mechanical Deformation in Rigid Polymersomes

The molecular transduction of biochemical or light inputs into mechanical responses, which underlies a wide range of essential biological functions, remains highly challenging to achieve in synthetic assemblies with programmable precision. Here, we report rigid polymersomes with stimuli-cleavable polycarbonate bilayers that undergo programmable shape transformations, including unidirectional elongation, invagination, and disassembly, in response to chemical or light triggers. These dynamic morphological and microstructural changes are monitored in situ by confocal microscopy combined with fluorescence probe analysis. Mechanistically, localized dissipation of chemical energy establishes reactive gradients across the polymersome membrane. Upon triggered cleavage of hydrophobic blocks into smaller fragments, these gradients promote transmembrane asymmetry, permeability enhancement, and curvature modulation, thereby dictating the transformation pathway. The resulting behaviors are governed by the interplay among radial diffusion of chemical fuel (H 2 O 2 ), its consumption through cleavage reactions, and the generation of surface area and curvature asymmetry across the bilayer membrane. In parallel, light input enables precise spatiotemporal control of deformation at the single-polymersome level, including directional invagination reminiscent of cellular endocytosis. By integrating light-triggered deformation with multivalent molecular recognition, we further establish a strategy for targeted nanoparticle internalization through programmable artificial endocytosis. This work provides a general framework for converting chemical and light energy into molecular cleavage events and further into real-time microscale mechanical motion, offering a versatile platform for responsive soft matter engineering and biomimetic functions.