Synthesis of poly(N-vinyl pyrrolidone) (PVP) nanogels by gamma irradiation using different saturation atmospheres

Abstract

Nanogels are internally crosslinked particles of nanometric size used in various fields e.g. as such as carriers in drug delivery systems. They can be produced using ionizing radiation in dilute aqueous solutions. This method is carried out in a pure polymer-solvent system, avoiding the addition of any additives such as monomers, surfactants, catalysts and crosslinking agents and no further purification step is necessary. Poly(N-vinyl pyrrolidone) (PVP K-90) nanogels were prepared by gamma irradiation in an aqueous solution. The samples were prepared in triplicate in multipurpose cobalt-60 gamma irradiator using 1, 10, 25 and 100 mM PVP solutions. Samples were irradiated in argon and nitrous oxide conditions with doses from 1 kGy up to 25 kGy with 10 kGy/h dose rate. The mean particle size (Rh) was determined by Dynamic Light Scattering (DLS) and radius of gyration (Rg) and weight-average molecular weight (Mw) by Static Light Scattering (SLS). These samples were morphologically characterized using Atomic Force Microscopy (AFM) and Transmission Electron Microscopy (TEM). Samples prepared with 100 mM PVP K-90 solution formed macroscopic gels, in the samples obtained with 25 mM PVP K-90 solution there was a prevalence of intermolecular crosslinking. On the other hand, in the samples generated with 10 mM PVP K-90 solution, there was a predominance of intramolecular crosslinking demonstrated in the tendency to: decrease in the radius of gyration (Rg), in the constancy of the weight-average molecular weight (Mw), in the increase in polymer coil density (ρcoil), in the Rg/Rh ratio (shape factor) around 1.0 indicating homogenous, internally cross-linked spheres, in the high relief spherical structures observed in the AFM images and in the spherical particles with high contrast observed in the TEM images. The saturation of the samples with nitrous oxide doubled formation of hydroxyl radicals, favoring the generation of polymeric radicals. Higher average number of radicals in each macromolecule contributed to the higher number of intramolecular crosslinks.