Solute diffusion and partitioning in multi-arm poly(ethylene glycol) hydrogels

Controlling solute transport in hydrogels is critical for numerous chemical separation applications, tissue engineering, and drug delivery systems. In previous review work, we have pointed out that proposed theoretical models and associated experiments tend to oversimplify the influence of the hydrogel structure on solute transport by addressing only the effects of the polymer volume fraction and mesh size of the networks on solute transport. Here, we reexamine these models by experimenting with a library of multi-arm poly(ethylene glycol) (PEG) hydrogels with simultaneous variations in four independent structural parameters. Standardized, high-throughput fluorescence recovery after photobleaching (FRAP) experiments in hydrogels characterize size-dependent solute diffusion and partitioning in each hydrogel formulation. Solute diffusivity dependence on junction functionality shows an influence from network geometry that is not addressed by mesh size-based models, experimentally validating the use of the geometry-responsive mesh radius in solute diffusivity modeling. Furthermore, the Richbourg-Peppas swollen polymer network (SPN) model accurately predicts how three of the four structural parameters affect solute diffusivity in hydrogels. Comparison with the large pore effective medium (LPEM) model showed that the SPN model better predicts solute size and hydrogel structure effects on diffusivity. This study provides a framework for investigating solute transport in hydrogels that will continue to improve hydrogel design for tissue engineering and drug delivery.