Bioinspired Approach to Silica Nanoparticle Synthesis Using Amine-Containing Block Copoly(vinyl ethers): Realizing Controlled Anisotropy

Core-shell polymer-silica hybrid nanoparticles smaller than 50 nm in diameter were formed in the presence of micelles of poly(2-aminoethyl vinyl ether-block-isobutyl vinyl ether) (poly(AEVE_m-b-IBVE_n)) through the hydrolysis and polycondensation of alkoxysilane in aqueous solution at a mild pH and temperature. The size of the nanoparticles as well as the number and size of the core parts were effectively controlled by varying the molecular weight of the copolymers. The polymers could be removed by calcination to give hollow silica nanoparticles with Brunauer-Emmett-Teller surface areas of more than 500 m² g^-1. Among these, silica nanoparticles formed with poly(AEVE₁₁₅-b-IBVE₄₀) displayed an anisotropy of single openings in the shell. The use of an alternative copolymer, poly(AEVE-b-2-naphthoxyethyl vinyl ether) (poly(AEVE₁₁₃-b-βNpOVE₄₀)), yielded core-shell nanoparticles with less pronounced anisotropy. These results showed that the degree of anisotropy could be controlled by the rigidity of micelles; the micelle of poly(AEVE₁₁₅-b-IBVE₄₀) was more deformable during silica deposition than that of poly(AEVE₁₁₃-b-βNpOVE₄₀) in which aromatic interactions were possible. This bioinspired, environmentally friendly approach will enable large-scale production of anisotropic silica nanomaterials, opening up applications in the field of nanomedicine, optical materials, and self-assembly.