Radiolytic synthesis of gold nanoparticles in HEMA-based hydrogels: Potentialities for imaging nanocomposites

This article reports on the radiolytic synthesis of nanocomposites containing gold nanoparticles (AuNPs) within two types of hydrogels based on 2-hydroxyethyl methacrylate (HEMA): (i) plain networks with various contents in ethylene glycol dimethacrylate (EGDMA), as a cross-linker and (ii) stimuli-responsive (SR) networks prepared from these monomers copolymerized with [2-(methacryloyloxy)ethyl]trimethylammonium chloride (MADQUAT) to confer pH-switchable swelling. Hydrogels were prepared by photopolymerization with well-defined composition and a high degree of monomer conversion using two experimental procedures, as xerogels or in aqueous solution. Besides MADQUAT, acrylic acid (AA) or N-isopropylacrylamide have been tested as copolymers, yielding pHor temperature-sensitive hydrogels, respectively. Isothermal swelling in water was affected by monomer composition. Electron beam (EB) irradiation at doses up to 100 kGy of poly(HEMA) xerogels and water-swollen networks prepared with 0.5 wt% of EGDMA had a moderate impact on swelling characteristics and thermomechanical properties of the plain materials, whereas small amounts of extractables were formed. Poly(HEMA)-based nanocomposites containing AuNPs were successfully obtained by EB irradiation of samples swollen by aqueous solutions of Au(III). The effects of dose and cross-linking density on the formation of AuNPs were monitored by UV-visible spectroscopy. Irradiation at well-defined temperatures of the Au(III)-loaded SR hydrogels induced the formation of nanoparticles with size-dependent features, whereas the efficiency of Au(III) reduction at 10 kGy was not significantly affected by the network structure. EB-induced reduction of Au(III) in poly(HEMA) hydrogels using a lead mask to generate well-defined patterns yielded coloured and long-lasting images in the zones where the nanocomposite was formed.