PEG‐PLA copolymers with dumbbell‐ and Y‐shaped structures are prepared. They can self‐assemble from nanoparticles to micro‐sized fusiform micellar particles in aqueous solution. In particular the micelles formed by the (PLA)2‐PEG‐(PLA)2 particles show a better drug loading capacity and encapsulation efficiency than those formed by linear MPEG‐PLA. In vitro studies show that the particles formed by Y‐shaped copolymers show a particularly quick drug release. The copolymers have good biocompatibility with low cytotoxicity. These unique self‐assembled systems thus have many possible biomedical applications, such as a sustained delivery of high‐dosed water insoluble drugs, quick effective drugs for trauma, controlled delivery of the oral‐administration drugs, and so forth.
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