In Situ Supramolecular Polymerization of Micellar Nanoobjects Induced by Polymerization

Supramolecular polymerization offers a fascinating opportunity to develop dynamic soft materials by associating monomeric building blocks via noncovalent interactions. We report that polymerization can spontaneously drive the supramolecular polymerization of nanoscale micellar objects. We constructed the patchy micelles via two-step polymerization-induced self-assembly. A horizontal association between the patches results in a 1D supermicellar chain in situ by minimizing the enthalpic penalty of exposing the growing chains to solvent Its length grows with increasing degree of polymerization, confirming that the supramolecular polymerization was triggered and controlled by polymerization. Our results highlight the observation that (1) the entire self-assembly process of forming, compartmentalizing, and associating the micelles can be driven by polymerization in a concerted manner and that (2) polymerization-induced self-assembly now can use compartmentalized nanoobjects as substrates beyond block copolymer chains. Polymerization-induced supramolecular polymerization could be useful for the autonomous preparation of hierarchical nanostructures.

Automated summary

Supramolecular polymerization, which involves the association of monomeric building blocks through non-covalent interactions, can spontaneously drive the polymerization of nanoscale micellar objects. By constructing patchy micelles through polymerization-induced self-assembly, we observed the formation of 1D supermicellar chains, with the length growing as the degree of polymerization increases. This study demonstrates the feasibility of using polymerization-induced supramolecular polymerization for the autonomous preparation of hierarchical nanostructures.