In water, amphiphilic block copolymers (BCPs) can self-assemble into various micelle structures depicting curved liquid/liquid interface. Crystallization, which is incommensurate with this curved space, often leads to defect accumulation and renders the structures leaky, undermining their potential biomedical applications. Herein we report using an emulsion-solution crystallization method to control the crystallization of an amphiphilic BCP, poly (L-lactide acid)-b-poly (ethylene glycol) (PLLA-b-PEG), at curved liquid/liquid interface.
The resultant BCP crystalsomes (BCCs) structurally mimic the classical polymersomes and liposomes yet mechanically are more robust thanks to the single crystal-like crystalline PLLA shell. In blood circulation and biodistribution experiments, fluorophore-loaded BCCs show a 24 h circulation half-life and an 8% particle retention in the blood even at 96 h post injection. We further demonstrate that this good performance can be attributed to controlled polymer crystallization and the unique BCC nanostructure.
Over the past few decades, many elegant delivery systems emerged to mimic biological structures such as lipid membranes and virus capsid1,2,3. For example, red blood cells (RBCs)-mimicking particles were reported to resemble natural RBCs’ size, shape, and deformability4,5,6. Self-assembled liposomes that mimic envelope viral structures were developed as tumor-targeting gene delivery carriers7,8. Like lipids, synthetic amphiphilic block copolymers (BCPs) can also self-assemble into similar vesicle structures (defined as polymersomes to emphasize its synthetic polymer origin) in water9,10. Because of the high molecular weight and chain entanglement of the hydrophobic blocks, polymer vesicles are mechanically more stable than liposomes10. Yet polymersomes’ membranes are flexible, and their morphologies/shapes may change over time, particularly under a high shear field. While shape transformation of polymersomes is of great physical and biological interest, in vivo applications call for robust and mechanically stable carrier structures.
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