Asymmetric Incorporation of Silver Nanoparticles in Polymeric Assemblies by Coassembly of Tadpole-Like Nanoparticles and Amphiphilic Block Copolymers

A general approach to asymmetrically localize nanoparticles (NPs) in larger polymeric nanostructures is demonstrated by coassembly of tadpole-like silver NPs (AgNPs) and amphiphilic block copolymers (BCPs). The tadpole-like AgNPs are prepared by template synthesis using a tailor-made A(BC)₂₀ star polymer, namely poly(ethylene glycol)[poly(acrylic acid)-block-polystyrene]₂₀ [PEG(PAA-b-PS)₂₀], as template resulting in AgNPs decorated with twenty short PS chains and one long PEG chain, named Ag@PEG(PS)₂₀. The asymmetric distribution of these AgNPs in various polymeric nanostructures, e.g., spherical micelles, cylindrical micelles, vesicles, and sponge phase, is achieved via coassembly of the as-prepared Ag@PEG(PS)₂₀ and PEG-b-PS in solution driven by the anisotropic nature of the Ag@PEG(PS)₂₀. This report not only provides a new strategy for the fabrication of tadpole-like NPs but also offers opportunity for off-center distributing NPs in hybrid assemblies, which may find applications in, e.g., sensing, catalysis, and diagnostics.