Natural-Synthetic Hybrid Nanostructures Formed Through the Interaction of Chitosan with Carboxylate-Ended PNIPAM: Structure and Curcumin Encapsulation.

Chitosan is widely used in drug delivery applications, due to its biocompatibility, bio-degradability, and low toxicity. Nevertheless, its properties can be enhanced through the physical or chemical modification of its amino and hydroxyl groups. This work explores the electrostatic complexation of two chitosan samples of differing lengths with two poly(-isopropylacrylamide) (PNIPAM) homopolymers of different molecular weight carrying a chargeable carboxyl end group. This interaction enables the electrostatic binding of PNIPAM side chains onto the chitosan backbone through the amino groups, and could be considered as an alternative grafting method. Dynamic and electrophoretic light scattering techniques were employed in order to study the solution/dispersion properties of the formed complexes as a function of the PNIPAM concentration, or, equivalently, the molar/charge ratio of the two components. The obtained results revealed that their mass, size, and charge mostly depend on the length of the two individual constituents, as well as their mixing ratio. Furthermore, their response to changes in their environment, namely temperature and ionic strength, was also examined, demonstrating the effect of either the thermoresponsiveness of PNIPAM or the electrostatic charge screening, respectively. Fluorescence spectroscopy, utilizing pyrene as a probe, provided information regarding the hydrophobicity of the formed complexes, while images from scanning transmission electron and atomic force microscopies further elucidated their morphology, which was found to be closely related to that of the corresponding chitosan molecule. Finally, their potential as drug delivery vehicles was also investigated, utilizing curcumin as a model drug at various loading concentrations.