Synthesis, characterization and evaluation of azobenzene nanogels for their antibacterial properties in adhesive dentistry.

The presence of cariogenic bacteria within the prepared tooth cavity at the adhesive resin-dentin interface is detrimental to the long-term stability and function of composite restorations. Here, we report the synthesis and incorporation of methacrylated azobenzene nanogels within bisphenol A-glycidyl methacrylate/hydroxyethyl methacrylate/ethanol (B/H/E) adhesive resins and evaluate their ability to reduce the bacterial invasion of cariogenic Streptococcus mutans biofilms while preserving the mechanical strength and structural integrity of the critical interfacial connection between the restoration and the tooth. The azobenzene nanogel, with a hydrodynamic radius of < 2 nm and a molecular weight of 12,000 Da, was polymerized within B/H/E adhesive formulations at concentrations of 0.5 wt.%, 1.5 wt.%, and 2.5 wt.%. While the double-bond conversion, cytocompatibility, water solubility, and sorption of the adhesive networks were comparable, azobenzene nanogel networks showed improved hydrophobicity with a ≥ 25° increase in water contact angle. The polymerized adhesive surfaces formulated with azobenzene nanogels showed a 66% reduction in bacterial biofilms relative to the control while maintaining the mechanical properties and micro-tensile bond strength of the adhesive networks. The increased hydrophobicity and antibacterial activity are promising indicators that azobenzene nanogel additives have the potential to increase the durability and longevity of adhesive resins.

Photoreactive nanogels as versatile polymer networks with tunable in situ drug release kinetics.

A simple, yet powerful approach to synthesize photoreactive nanogel networks <5 nm that can swell between ~3 and ~200 times their initial radius with control over the size and surface charge via a solution polymerization reaction protocol was demonstrated. Nanogels with hydrodynamic radii from 0.9 nm to 3.2 nm and surface charges from -6.4 mV to -16.5 mV with dramatically different abilities to swell were synthesized by altering the solvent ratio before synthesis. Additionally, the control over the release kinetics of a small molecule over a period of 30 days was demonstrated by the methacrylate functionalization of the nanogels post-synthesis and the subsequent photo-aggregation of the nanogels. Thepotential to control the release of small molecule drugs via the concentration of photoreactive groups and the photo-induced aggregation of the nanogels offers the unique ability to tailor the in situ release kinetics of the delivery network.