Patchy Micelles Based on Coassembly of Block Copolymer Chains and Block Copolymer Brushes on Silica Particles

Patchy particles are a type of colloidal particles with one or more well-defined patches on the surfaces. The patchy particles with multiple compositions and functionalities have found wide applications from the fundamental studies to practical uses. In this research patchy micelles with thiol groups in the patches were prepared based on coassembly of free block copolymer chains and block copolymer brushes on silica particles. Thiol-terminated and cyanoisopropyl-capped polystyrene-<i>block</i>-poly­(<i>N</i>-isopropylacrylamide) block copolymers (PS-<i>b</i>-PNIPAM-SH and PS-<i>b</i>-PNIPAM-CIP) were synthesized by reversible addition–fragmentation chain transfer polymerization and chemical modifications. Pyridyl disulfide-functionalized silica particles (SiO₂-SS-Py) were prepared by four-step surface chemical reactions. PS-<i>b</i>-PNIPAM brushes on silica particles were prepared by thiol–disulfide exchange reaction between PS-<i>b</i>-PNIPAM-SH and SiO₂-SS-Py. Surface micelles on silica particles were prepared by coassembly of PS-<i>b</i>-PNIPAM-CIP and block copolymer brushes. Upon cleavage of the surface micelles from silica particles, patchy micelles with thiol groups in the patches were obtained. Dynamic light scattering, transmission electron microscopy, and zeta-potential measurements demonstrate the preparation of patchy micelles. Gold nanoparticles can be anchored onto the patchy micelles through S–Au bonds, and asymmetric hybrid structures are formed. The thiol groups can be oxidized to disulfides, which results in directional assembly of the patchy micelles. The self-assembly behavior of the patchy micelles was studied experimentally and by computer simulation