Temperature-Sensitive Water-Soluble Hybrid Organic/Inorganic Nanoparticles Formed through Complexation of Cu2+ Ions with Poly(sodium acrylate)-g-poly(N-isopropylacrylamide) Comb-Type Copolymers in Aqueous Solution

Abstract

The preparation of temperature-sensitive water-soluble hybrid organic/inorganic nanoparticles, exploiting the complexation of Cu2+ ions with PANa-g-PNIPAMx comb-type copolymers, is presented. These copolymers consist of a Cu2+-complexing poly(sodium acrylate) backbone, PANa, and thermosensitive poly(N-isopropylacrylamide), PNIPAM, side chains. UV-vis spectrophotometry verified that the polymer/Cu2+ complexation follows a charge neutralization process, while turbidimetry revealed that the complexes formed can indeed be stabilized in water, provided that copolymers with a sufficiently high PNIPAM content (x approximately 80 mol % in monomer units) are used. Dilute solution viscometry and dynamic light scattering indicated that the hydrodynamic dimensions of the hybrid polymer/Cu2+ nanoparticles decrease substantially upon heating, reflecting the lower critical solution temperature behavior of the PNIPAM side chains. However, when the net negative charge of the hybrid polymer/Cu2+ nanoparticles decreases, interparticle aggregation and, eventually, phase separation may take place. In semidilute aqueous solution, the complexation of the polymer backbone with Cu2+ ions effectively controls the thermothickening properties of the thermosensitive comb-type PANa-g-PNIPAM copolymers. Finally, the temperature-induced formation of a compartmentalized hydrophilic-hydrophobic nanocontainer, where the hydrophilic and the hydrophobic compartments can be loaded with Cu2+ ions and hydrophobic substances, respectively, was evidenced through pyrene fluorescence probing.