Polymerization-like multilevel hierarchical self-assembly of polymer vesicles into macroscopic superstructures with controlled complexity.
We demonstrate a high-leveled hierarchical self-assembly process into fractal structures. Two hyperbranched multiarm copolymers are first coassembled into binary isotropic vesicles in the primary self-assembly. Then, these primary vesicles are in situ endowed with anisotropic hydrophobic "binding sites" through a pH-induced lateral microphase separation, undergoing an isotropic-anisotropic transition. Subsequently, the anisotropic vesicles further assemble together through the specific self-recognition between the binding sites into linear, branched, cyclization, and network-like vesicle chains. Furthermore, the obtained vesicle chains can transform into linear, branched, ring-like, and network tubes through successive vesicle fusion. Such a hierarchical process is pH-triggered and well-controlled by adjusting the vesicle compositions and is coined as "polymerization-like" self-assembly due to the striking analogy between the vesicle association model and polymerization process.
Jin
Haibao
H
School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, PR China.
Zhou
Yongfeng
Y
Huang
Wei
W
Yan
Deyue
D