Degradation Profiles of Poly(ethylene glycol) diacrylate (PEGDA)-based hydrogel nanoparticles.

Hydrogel nanoparticles (also known as nanogels) have been utilized for a wide range of applications including analytics, sensors, drug delivery, immune engineering, and biotechnology. While these types of nanoparticles can be characterized using standard colloidal characterization techniques, degradation profiles typically must be inferred from those of bulk gels with the same formulation, typically by applying swelling ratios and rheological measurements that tend to severely underestimate nanoparticle degradation rates. Herein, we present an analysis of the degradation via ester hydrolysis of poly(ethylene glycol) diacrylate (PEGDA)-based hydrogel nanoparticles in water, varied pH conditions, and redox environments. We perform this characterization using thermogravimetric analysis and mass spectrometry to analyze rates of degradation and products released, respectively, and compare results to those for equivalent bulk gel formulations. Our findings show that PEGDA-based nanoparticles display significant mass loss over time accompanied by negligible changes in hydrodynamic diameter, indicating a bulk mode of degradation. Nanoparticle mass loss occurs at a much higher rate than for bulk gels under comparable incubation conditions, confirming that bulk gel degradation serves as a poor surrogate for nanoparticle degradation. We further demonstrate that the incorporation of other diacrylate-based co-monomers drastically accelerates nanoparticle degradation rates. Through formulation considerations of co-monomer content and weight percent of PEGDA, we demonstrate the ability to tune the degradation rates of PEGDA-based nanoparticles on a range of hours to weeks. These findings highlight critical design considerations for enhancing the tunability and utility of PEGDA hydrogel nanoparticles and introduce a rigorous framework for the characterization of nanogel degradation.