Surfactant vesicles containing monomers in the interior of the bilayer were used to template hollow polymer nanocapsules. This study investigated the formation of surfactant/monomer assemblies by two loading methods, concurrent loading and diffusion loading. The assembly process and the resulting aggregates were investigated with dynamic light scattering, small angle neutron scattering, and small-angle X-ray scattering. Acrylic monomers formed vesicles with a mixture of cationic and anionic surfactants in a broad range of surfactant ratios. Regions with predominant formation of vesicles were broader for compositions containing acrylic monomers compared with blank surfactants. This observation supports the stabilization of the vesicular structure by acrylic monomers. Diffusion loading produced monomer-loaded vesicles unless vesicles were composed from surfactants at the ratios close to the boundary of a vesicular phase region on a phase diagram. Both concurrent-loaded and diffusion-loaded surfactant/monomer vesicles produced hollow polymer nanocapsules upon the polymerization of monomers in the bilayer followed by removal of surfactant scaffolds.

Nanoreactors were created by entrapping homogeneous catalysts in hollow nanocapsules with 200 nm diameter and semipermeable nanometer-thin shells. The capsules were produced by the polymerization of hydrophobic monomers in the hydrophobic interior of the bilayers of self-assembled surfactant vesicles. Controlled nanopores in the shells of nanocapsules ensured long-term retention of the catalysts coupled with the rapid flow of substrates and products in and out of nanocapsules. The study evaluated the effect of encapsulation on the catalytic activity and stability of five different catalysts. Comparison of kinetics of five diverse reactions performed in five different solvents revealed the same reaction rates for free and encapsulated catalysts. Identical reaction kinetics confirmed that placement of catalysts in the homogeneous interior of polymer nanocapsules did not compromise catalytic efficiency. Encapsulated organometallic catalysts showed no loss of metal ions from nanocapsules suggesting stabilization of the complexes was provided by nanocapsules. Controlled permeability of the shells of nanocapsules enabled size-selective catalytic reactions.

Nanorattles made of hollow polymer nanocapsules with entrapped silver nanoparticles were synthesized in one step by using lipid vesicles as templates. Free radical photoinitiator facilitated both polymerization within the bilayer and formation of metal nanoparticles in the aqueous core.

Yolk–shell nanostructures, or nanorattles, are created by growing metal nanoparticles exclusively inside hollow porous polymer nanocapsules. Metal ions enter the nanocapsules through size-selective nanopores. Synthesis of metal nanoparticles is initiated by an agent entrapped in nanocapsules. Tannic acid, β-cyclodextrin, and polyether dendrimer were used as sacrificial molecules for initiation and growth of gold nanoparticles. If needed, initiator molecules can be fragmented by acid hydrolysis and removed from nanocapsules. Variations in reaction conditions yield encapsulated nanoparticles with different size and shape. Further functionalization of nanorattles forms encapsulated core–shell nanoparticles.

Yolk-shell nanoreactors with metal nanoparticle core and ultrathin porous polymer shells are effective catalysts for heterogeneous reactions. Polymer shells provide size-selectivity and improved reusability of catalyst. Nanocapsules with single-nanometer porous shells are prepared by vesicle-templated directed assembly. Metal nanoparticles are formed either by selective initiation in pre-fabricated nanocapsules or simultaneously with the creation of a crosslinked polymer shell. In this study, we investigated the oxidation of benzyl alcohol and benzaldehyde catalyzed by gold nanoparticles and hydrogenation of cyclohexene catalyzed by platinum nanoparticles. Comparison of newly created nanoreactors with commercially available nanoparticles revealed superior reusability and size selectivity in nanoreactors while showing no negative effect on reaction kinetics.

Nanoprobes for surface-enhanced Raman scattering (SERS) were prepared by creating nanorattles, or yolk-shell structures, containing gold or silver nanoparticles entrapped in porous hollow polymer nanocapsules. Controlled permeability of the shells of nanocapsules, achieved by controlling the pore size and/or shell surface functionalization, resulted in size- and charge-selective SERS analyses. For example, a trace amount of phenanthroline, a model analyte, was detected in human blood plasma without preprocessing of plasma samples. Comparison with commercially available nanoparticles showed superior performance of the newly prepared nanorattle structures.

Novel water-soluble amphiphilic copolymers have been synthesized by free radical copolymerization of 2-hydroxyethylacrylate with vinyl butyl ether. In water these copolymers exhibit lower critical solution temperature, which depends on the content of hydrophobic vinyl butyl ether units. The interaction between these copolymers and poly(acrylic acid) or poly(methacrylic acid) in aqueous solutions results in formation of interpolymer complexes stabilized by hydrogen bonds and hydrophobic interactions. An increase in hydrophobicity of the copolymers leads to the enhancement of their complex formation ability with respect to poly(acrylic acid) and poly(methacrylic acid). Poly-(methacrylic acid) forms stronger complexes with the copolymers when compared with poly(acrylic acid). The complexes exhibit dual sensitivity to pH-and temperature and this property may be easily adjusted regulating the strength of interaction. V V C 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 195-204, 2006

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