Fluorescent Supracolloidal Chains of Patchy Micelles of Diblock Copolymers Functionalized with Fluorophores.

By selective attachment of fluorescent dyes to the core-forming block, we produced patchy micelles of diblock copolymers with fluorophores localized in the micellar cores. From these patchy micelles functionalized with dyes, fluorescent supracolloidal chains in a few micrometers were polymerized by combining the patches in neighboring micelles, indicating that selective modification of the core-forming block delivered the functionality into the supracolloidal chain without altering the polymerization of patchy micelles. Thus, with the same polymerization condition, we were able to produce red-, green-, and blue-emitting supracolloidal chains by varying the fluorescent dyes attached to the core-forming block. In addition, we directly visualized individual supracolloidal chains by fluorescence confocal microscopy as well as by transmission electron microscopy.

Supracolloidal chains of patchy micelles of diblock copolymers with in situ synthesized nanoparticles.

Supracolloidal chains of diblock copolymer micelles were functionalized with gold and silver nanoparticles (NPs). Both NPs were independently synthesized in situ in the core of spherical micelles which were then converted to patchy micelles. With these patchy micelles as colloidal monomers, supracolloidal chains were polymerized by combining the patches of neighboring micelles. Since all micelles contained NPs, NPs were incorporated in every repeat unit of chains. In addition, a single gold NP was synthesized in the micellar core in contrast to several silver NPs so that we differentiated the chains with Au NPs from those with Ag NPs by the number of NPs in the repeat unit as well as by plasmonic bands in UV-Vis spectra.

Fabrication of size-controlled nanoring arrays by selective incorporation of ionic liquids in diblock copolymer micellar cores.

We report the synthesis of arrayed nanorings with tunable physical dimensions from thin films of polystyrene-block-poly(4-vinylpyridine) (PS-P4VP) micelles. For accurate control of the inner and outer diameters of the nanorings, we added imidazolium-based ionic liquids (ILs) into the micellar solution, which were eventually incorporated into the micellar cores. We observed the structural changes of the micellar cores coated on a substrate due to the presence of ILs. The spin-coated micellar cores were treated with an acidic precursor solution and generated toroid nanostructures, of which size depended on the amount of IL loaded into the micelles. We then treated the transformed micellar films with oxygen plasma to produce arrays of various metal and oxide nanorings on a substrate. The spacings and diameters of nanorings were governed by the molecular weight of the PS-P4VP and the amount of IL used. We also demonstrated that arrayed Pt nanorings enabled the fabrication of reduced graphene oxide anti-nanoring arrays via a catalytic tailoring process.