Controlled release from modified amino acid hydrogels governed by molecular size or network dynamics.

Hydrogels can be prepared using the commercially available Fmoc-phenylalanine or Fmoc-tyrosine as the gelator. Gelation is triggered by careful adjustment of the pH of the solution using glucono-delta-lactone (GdL). Model dyes have been entrapped in the hydrogels, and the release of the dyes from the hydrogels has been monitored. The release ratios indicate that the systems are under Fickian diffusion control. A range of dyes with different radii of gyration diffuse from the Fmoc-phenylalanine hydrogels with similar diffusion coefficients, implying that the network is not specifically retaining even relatively large (5 nm) dyes. On the other hand, the larger dyes are restricted in their diffusion from Fmoc-tyrosine hydrogels. These results correlate with the rheological measurements for the hydrogels, where those formed from Fmoc-tyrosine were shown to have significantly higher storage moduli than those formed from Fmoc-phenylalanine. In addition, the frequency-dependent behavior of the hydrogels demonstrates that Fmoc-tyrosine shows the classic response of a strong gel with a storage modulus that is nearly independent of frequency. However, for Fmoc-phenylalanine, the frequency dependence of moduli is very strong and very similar to that displayed by a transient network, where the interconnections between junction zones in the network are highly flexible and able to withstand large deformations.