A cup shape is a dynamic morphology of cells and organelles. With the aim of elucidating the formation of the biotic cup-shaped morphology, this study investigated cup-shaped vesicles consisting of an amphiphilic diblock copolymer from the aspect of synthetic polymer chemistry. Cup-shaped vesicles were obtained by the polymerization-induced self-assembly of poly(methacrylic acid)-block-poly(n-butyl methacrylate-random-methacrylic acid), PMAA-b-P(BMA-r-MAA), in an aqueous methanol solution using the photo nitroxide-mediated controlled/living radical polymerization technique. Field emission scanning electron microscopic observations demonstrated that the cup-shaped vesicles were suddenly formed during the late stage of the polymerization due to the extension of the hydrophobic P(BMA-r-MAA) block chain. During the early stage, the polymerization produced spherical vesicles rather than a cup shape. As the hydrophobic block chain was extended by the polymerization progress, the spherical vesicles reduced the size and were accompanied by the generation of small particles that were attached to the vesicles. The vesicles continued to reduce the size due to further extension of the hydrophobic chain; however, they suddenly grew into cup-shaped vesicles. This growth was accounted for by a change in the critical packing shape of the copolymer due to the hydrophobic chain extension. These findings are helpful for a better understanding of the biotic cup-shaped vesicle formation.
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