Hybrid Materials of Block Copolymers and Magnetic Nanoparticles

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Zhou, Zhihan
Hybrid material , magnetic nano particle , block copolymer , self-assembly , emulsion sphere
In this PhD thesis, the preparation of several types of hybrid materials of block copolymer and magnetic nanoparticles is described. The diversified morphologies of nanoaggregates formed by dispersing poly(glyceryl methacrylate)-block-poly(2-cinnamoyloxyethyl methacrylate)-block-poly(tert-butyl acrylate) tri-block copolymers in block selective solvents will be reported first. The volume occupied by the core block in these nanoaggregates can be swollen by solvent, and the core block can be sculpted. The cores can act potentially as the template to grow magnetic nanoparticles. Thus, a potential method for preparing hybrid magnetic materials of block copolymers and magnetic nanoparticles with different morphologies is developed. A one-pot method to synthesize cobalt nanoparticles covered by a polymer shell is then reported. This is achieved by thermally decomposing dicobalt octacarbonyl in the presence of polymeric multi-dentate ligand poly(ethylene glycol)-block-poly(acrylic acid). Using a similar method, cobalt nanoparticles covered by poly(2-cinnamoyloxyethyl methacryate)-block-poly(acrylic acid) ligand are synthesized. The cobalt nanoparticles fuse into chains for their magnetic dipole-dipole interaction. The chains are then coated with poly(tert-butyl acrylate)-block-poly(2-cinnamoyloxyethyl methacrylate). The coated Co chains are further locked by photo-crosslinking the poly(2-cinnamoyloxyethyl methacrylate) segments. The as-prepared cobalt nano wires have interesting magnetic response and may be used to build complicated magnetic nano devices. Another hybrid magnetic material is prepared via an oil-in-water emulsion method. The oil phase of the emulsion sphere consists of r-Fe2O3 magnetic nanoparticles covered with the poly(2-cinnamoyloxyethyl methacryate)-block-poly(acrylic acid) ligand and a poly(2-cinnamoyloxyethyl methacryate) homopolymer. It was dispersed in water using a mixture of poly(2-cinnamoyloxyethyl methacrylate)-block-poly(succinoylglyceryl methacrylate) and poly(2-cinnamoyloxyethyl methacrylate)-block-poly(glyceryl methacrylate) as the surfactants. The evaporation of the organic solvent left behind solid particles in water. The polymer chains on the surface of the obtained spheres allow the immobilization of biomolecules. Factors affecting the emulsion process are studied systematically. The emulsion spheres are characterized using TEM, AFM, TGA and etc. The emulsion sphere have potential application is immunoassay. The protein binding capacity of the spheres is determined.
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