Tunable Hairy and Crew-Cut Supermicelles from Poly(N-Octyl Glycine)-Based Diblock Copolymer via a Hierarchical Assembly Strategy

Fabrication of hierarchical superstructures by utilizing bioinspired polymeric materials shows great potential that has attracted considerable attention. A new hierarchical assembly approach has been developed to fabricate supramolecular structures in a one-pot preparation from crystallizable polypeptoids-based block copolymers. Herein, both hairy and crew-cut supermicelles are reported by systematically tuning the temperature and solvent from a series of poly(ethylene glycol)(112)-block-poly(N-octylglycine)(n) (PEG(112)-b-PNOG(n)) with different degrees of polymerization of PNOG. The incorporation of a third polar component poly(N-allylglycine)-graft-COOH (PNAG-g-COOH) into the amphiphilic diblock copolymers can promote the formation of crew-cut supermicelles owing to enhanced intermolecular interactions. It is demonstrated that both surface energy and crystallization energy are of great importance for the preparation of different types of supermicelles.