Effect of hydrophilic block end groups and block junction on block copolymer self-assembly in solution
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Recent research suggests that the end groups of polymers can affect their self-assembly. However, the effect of end groups on the self-assembly of block copolymers in solution remains unclear, and thus far, only micelle–vesicle transformations have been achieved via end-group modification. Herein, we report that hydrophilic block end groups and the junction between two blocks can affect the solution self-assembly of block copolymers, leading to the formation of different morphologies, including vesicles, cubosomes, and hexosomes. Poly(ethylene glycol)-b-polystyrene (PEG-b-PS) with hydroxyl, methoxy, azido, or amino groups at the PEG chain ends was synthesized and self-assembled in solution via the cosolvent method. As a result, the morphology of the block copolymers transformed from vesicles to hexosomes upon increasing the end-group hydrophobicity.