Diffusion and Concentration of Molecular Probes in Thermoresponsive Poly(N-isopropylacrylamide) Hydrogels:  Effect of the Volume Phase Transition

Poly(N-isopropylacrylamide), NIPA, thermoresponsive hydrogels with well-defined concentrations of an electroactive probe, 1,1'-ferrocenedimethanol, Fc(MeOH)2, were prepared. The discontinuous reversible volume phase transition of such gels occurs at 32 +/- 1 degrees C and results in a release of approximately 93% of the solution from the polymeric network. Transport of Fc(MeOH)2 in both swollen and collapsed gels was studied using steady-state voltammetry and chronoamperometry at platinum microelectrodes. The diffusion coefficient of Fc(MeOH)2 in collapsed gels was approximately 2 orders of magnitude smaller than that in swollen gels. UV/vis spectroscopic studies showed that for 3.0% NIPA gel, the concentration of Fc(MeOH)2 in the collapsed phase was approximately 6 times higher than that in released solution and 4.5 times higher than in the original swollen gel.