Asymmetric Block Extension of Star-Shaped [PEG-SH]4 - toward Poly(dehydroalanine)-Functionalized PEG Hydrogels for Catch and Release of Charged Guest Molecules.

With the incorporation of polyampholytic segments into soft matter, hydrogels can serve as a reservoir for a variety of charged molecules which can be caught and released upon changes in pH value. Asymmetric block extension of one arm for star-shaped poly(ethylene glycol) [PEG26 -SH]4 using short segments of polyampholytic poly(dehydroalanine) (PDha) is herein demonstrated while maintaining the functional thiol end groups for network formation. For subsequent hydrogel synthesis with up to 10 wt.% PDha a straightforward and biocompatible photoinitiated thiol-ene click reaction is exploited. The investigation of the swelling properties of the hydrogel revealed responsive behavior toward ionic strength and variations in pH value. Moreover, the reversible adsorption of the model dyes methylene blue (MB) and acid orange 7 (AO7) is investigated by UV-vis measurements and the procedure can be successfully transferred to the adsorption of the adhesion peptide RGDS resulting in an uptake of 1.5 wt% RGDS with regard to the dry weight of the hydrogel.