Water, solute and protein diffusion in physiologically responsive hydrogels of poly(methacrylic acid-g-ethylene glycol)

Grafted poly(methacrylic acid-g-ethylene glycol) [P(MAA-g-EG)]copolymers were synthesized and their pH sensitivity was investigated. P(MAA-g-EG) membranes showed pH sensitivity due to complex formation and dissociation. Uncomplexed equilibrium swelling ratios were 40 to 90 times higher than those of the complexed states and varied according to copolymer composition and poly(ethylene glycol) (PEG) graft length. Mesh sizes in the two states were determined. Swelling under oscillatory pH conditions revealed the dynamic sensitivity of P(MAA-g-EG) membranes as well as the diffusional mechanisms causing network expansion and collapse. Network collapse (complexation) occurred more rapidly than network expansion (decomplexation). A Boltzmann superposition model was used to analyse this behaviour. Mechanical testing was used to evaluate the strength of P(MAA-g-EG) membranes and to elucidate the mesh size under various conditions. Solute diffusion coefficients were higher in uncomplexed than in complexed P(MAA-g-EG) membranes and decreased as solute size increased. Lower diffusion coefficients were observed with membranes or hydrogels containing longer PEG grafts, since in the uncomplexed state the PEG grafts dangled into the polymer mesh space. Membrane permeability was responsive to changing pH conditions, and separation of solutes was achieved.