Fabrication and Caffeine Release from Fe3O4/P(MAA-co-NVP) Magnetic Microspheres with Controllable Core–Shell Architecture

A novel route was proposed to design and construct a magnetic composite microsphere consisting of Fe(3)O(4) nanoparticles chemically-covalently encapsulated with pH-smart poly(methacrylic acid-co-N-vinyl pyrrolidone) (P(MAA-co-NVP)) cross-linked co-polymers by a surface-initiated radical dispersion polymerization route. The multistep surface treatment was employed to improve the dispersity and surface-chemical reactivity of Fe(3)O(4) nanoparticles, involving introduction of active -NH(2) groups, coupling of 1,1-methylene bis-(4-isocyanato-cyclohexane) and immobilization of 2,2'-azobis[2-methyl-N-(2-hydroxyethyl) propionamide]. The structure and morphological characterization was carried out by FT-IR, TEM, SEM and XRD. The chemically covalent interactions were investigated by FT-IR, TEM, TGA and DSC. The neat Fe(3)O(4) nanoparticles took on an aggregated spherical shape with an average diameter of about 12 nm, while Fe(3)O(4)/P(MAA-co-NVP) magnetic microspheres assumed controllable and monodispersed spheres with a mean dimension of ca. 0.8 μm. The microspheres exhibited superparamagnetic properties. The in vitro caffeine release behavior under varying pH environment was investigated to evaluate the potential of Fe(3)O(4)/P(MAA-co-NVP) magnetic microspheres as a magnetic drug targeting carrier. The results indicated that the microspheres have a faster drug-release rate at pH 7.4 than at pH 1.4, corresponding to their pH swelling. The kinetic modeling demonstrated that the drug release is controlled by a balance between co-polymer chain relaxation and Fickian diffusion process, and the proposed carrier is suitable for a magnetic targeting drug-delivery system.