Issue 10, 2021

Hierarchical self-assembly of miktoarm star copolymers with pathway complexity

Abstract

The hierarchical self-assembly of molecular building blocks provides promising opportunities toward the exploration of functional soft materials with structural programmability. Here, we report the hierarchical self-assembly behaviors of amphiphilic miktoarm star copolymers with pathway complexity. In our experiments, supramolecular miktoarm star copolymers with a cluster core of [α-SiW12O40]4− and four polystyrene-block-poly(ethylene glycol) cations (PSn-b+-PEGm, n = 17, 26, 39, 57, 81; m = 45, SEW-1–5) are used as a model of amphiphilic miktoarm stars. When dispersed in the selective THF/methanol and toluene/methanol mixture solvents, the miktoarm stars of SEW-2–5 self-assemble to form bundled fibers, sheet-like assemblies, and hollow spheres. These complex structures are packed by reverse cylindrical or spherical micelles having [α-SiW12O40]4−/PEG45 cores and PSn coronas, wherein the micelle building blocks are originally formed by SEW-2–5 in the nonselective solvents THF and toluene. These hierarchically self-assembled structures do not resemble micelle-like nano-objects formed by amphiphilic copolymers in selective solvents. The mechanism behind such unconventional aggregates is presumably due to intra- and inter-micelle van der Waals attractions occurring under poor solvent conditions for the PSn coronas. The difference is that SEW-3–5 self-assemble into normal vesicles with a PSn core and a [α-SiW12O40]4−/PEG45 corona in the chloroform/methanol mixture solvent. The reverse cylinders, rices, and spheres originally fabricated from SEW-3–5 in chloroform experience molecular reorganization for such normal vesicles in the present selective solvents. Moreover, SEW-1 forms normal lamellae in all the methanol based mixture solvents. The results presented herein not only enable us to reconsider the self-assembly behaviors of amphiphilic miktoarm stars in solution, but also provide opportunities for constructing advanced functional materials with high-level structural hierarchy.

Graphical abstract: Hierarchical self-assembly of miktoarm star copolymers with pathway complexity

Supplementary files

Article information

Article type
Paper
Submitted
17 Aug 2020
Accepted
07 Dec 2020
First published
09 Dec 2020

Polym. Chem., 2021,12, 1476-1486

Hierarchical self-assembly of miktoarm star copolymers with pathway complexity

J. Xiao, Q. He, M. Yang, H. Li, X. Qiu, B. Wang, B. Zhang and W. Bu, Polym. Chem., 2021, 12, 1476 DOI: 10.1039/D0PY01170C

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