Morphological Evolution of Self-Assembled Structures Induced by the Molecular Architecture of Supra-Amphiphiles
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文摘
A series of telechelic supramolecular amphiphiles [POSS–Azo8@(β-CD–PDMAEMA)1→8] was accomplished by orthogonally coupling the multiarm host polymer β-cyclodextrin–poly(dimethylaminoethyl methacrylate) (β-CD–PDMAEMA) with an octatelechelic guest molecule azobenzene modified-polyhedral oligomeric silsesquioxanes (POSS–Azo8) under different host–guest ratios. These telechelic supramolecular amphiphiles possess a rigid core and flexible corona. Increasing the multiarm host polymer coupled onto the rigid POSS core made the molecular architecture tend to be symmetrical and spherical. POSS–Azo8@[β-CD–PDMAEMA]1→8 could self-assemble into diverse morphologies evolving from spherical micelles, wormlike micelles, and branched aggregates to bowl-shaped vesicles. Distinct from the traditional linear amphiphilic polymers, we discovered that the self-assembly of POSS–Azo8@[β-CD–PDMAEMA]1→8 was dominantly regulated by their molecular architectures instead of hydrophilicity, which has also been verified using computer simulation results.