Bio-inspired nanoreactor based on a miniemulsion system to create organic-inorganic hybrid nanoparticles and nanofilms

We developed a novel route to control both mineralization and polymerization inside a nanoreactor based on a miniemulsion system to create organic-inorganic hybrid nanomaterials with diverse structures and morphologies. Nanodroplets of calcium nitrate (Ca(NO3)(2))/monomer and nanodroplets of sodium carbonate (Na2CO3) were separately prepared and suspended in the oil phase. They were mixed through the fusion and fission process triggered by ultrasonication to precipitate a biomineral only inside the nanodroplets. In the presence of monomer, 2-hydroxyethyl methacrylate (HEMA), we could obtain unique structures of nano-sized CaCO3 particles, which were crystalline with spherical or rod-like shapes or amorphous. By subsequent polymerization, we could encapsulate nano-CaCO3 inside the polymeric nanoparticles at a desired stage of crystal growth. The preincubation period for CaCO3 nucleation and growth and the polymerization rate were important factors to manipulate the structures and polymorphs of nano-CaCO3 inside the hybrid nanoparticles, owing to inhibition of crystal growth and transformation by polymerization of HEMA. Also, the growth of rod-like CaCO3 inside the nanoparticles led to formation of spheroidal hybrid nanoparticles. By using hybrid nanoparticles as building blocks, we could produce nanofilms containing nano-CaCO3 with a variety of sizes and structures. Crystal transformation of amorphous CaCO3 was induced inside the nanofilm by increasing the temperature to above the T-g of PHEMA.