Spontaneous Formation and Fusion of Raspberry Vesicle Self-Assembled from Star Block Terpolymers in Aqueous Solution.

The spontaneous formation and fusion of raspberry vesicles was studied using the dissipative particle dynamics (DPD) method. The vesicles were formed through the self-assembly of amphiphilic EOF star terpolymers in selective solvent. E and F blocks are solvophobic and the O block is solvophilic. The shortest F block plays a major role in the formation of raspberry vesicles. Distinct vesicle formation mechanisms were observed at different polymer concentrations. At higher concentrations, vesicles form via the bending and closure of an oblate F-bump-E bilayer. At lower concentrations, the formation pathway contains: the initial formation of a vesicle with a core, the combination of such vesicles into cylindrical micelles, and the bending of the cylindrical micelles to form a hollow vesicle. In addition, raspberry vesicle fusion is regulated by F bumps through the continuous coalescence of them from apposed vesicle membranes. The contact area bends, followed by the formation of a fusion pore and a tilted inner layer. As the pore sealed, the hemifusion structure appears, which further restructures to form a vesicle. Our results provide guidance on understanding the dynamic processes of complex vesicles and biological membrane fusion.