Giant Polymer Vesicles with a Latticelike Membrane

Hierarchical self-assembly offers great possibilities to mimic biological systems with finely arranged complex structures. Herein, we demonstrate the preparation and formation mechanism of an unusual giant polymer vesicle with a latticelike membrane (GVLM). This GVLM is formed by fusion-induced particle assembly (FIPA) of small vesicles that are self-assembled from poly­(ethylene oxide)-block-poly­[(2-(tetrahydro­furanyloxy)­ethyl methacrylate)-stat-(6-(3,3-diphenyl­naphthopyranyl­oxy)­hexyl methacrylate)] [PEO₄₃-b-P­(TMA₂₂-stat-NMA₄)]. Flexible TMA units with high chain mobility and relatively rigid NMA units with intrinsic π–π stacking form the hydrophobic block. These units act as “antifusion” and “profusion” components, respectively. The latticelike membrane of the final GVLM consists of hundreds of small polymer vesicles that are interconnected via multiple interactions. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) studies show that the diameter of the GVLMs is 800–1000 nm. Overall, we provide a new insight into the judicious preparation of hierarchical nanostructures via chemical synthesis and FIPA.