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-block-poly(N-isopropylacrylamide) block copolymers (PS-b-PNIPAM-SH and PS-b-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-b-PNIPAM brushes on silica particles were prepared by thiol-disulfide exchange reaction between PS-b-PNIPAM-SH and SiO2-SS-Py. Surface micelles on silica particles were prepared by coassembly of PS-b-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.

Macromolecular brushes with thermo-sensitive poly(N-isopropylacrylamide) (PNIPAM) backbones and pendant poly(γ-benzyl-L-glutamate) (PBLG) side chains were synthesized by reversible addition-fragmentation chain transfer (RAFT) and ring-opening polymerization (ROP). Copolymers of NIPAM and N-acryloxysuccinimide (NAS) were synthesized by RAFT polymerization. Boc-protected amino groups were introduced to the backbone chains by substituting the NAS groups with N-Boc-ethylenediamine, and after removal of the Boc groups amine groups were produced on the backbones. PBLG side chains were synthesized by ROP. Size exclusion chromatograph, 1 H NMR and 13 C NMR results all indicated successful synthesis of well-defined brush macromolecules. The self-assembly of the macromolecules in aqueous solutions was investigated in this research. Depending on the backbone and side chain lengths, the brush macromolecules self-assemble into spherical micelles, worm-like structures and vesicles. Temperature exerted a significant effect on the morphology of the structures. At a temperature above lower critical temperature (LCST) of PNIPAM backbone, the selfassembled structures aggregated together. The functionalization of PBLG side chains with 1-pyrenebutyric acid was also performed. The fluorescence properties and morphology of the functionalized brush macromolecules were investigated in this research.