Preparation of 'click' hydrogels from polyaspartamide derivatives

Abstract

Lately, copper-assisted azide-alkyne cycloaddition (CuAAC) has become a very interesting tool for synthesizing biocompatible polymer-based materials such as hydrogels or microgels, which can be used as biomaterials for tissue engineering and drug delivery. Novel poly(2-hydroxyethyl aspartamide)s (PHEAs) functionalized with pendent acetylene or azide groups were prepared from polysuccinimide, which is the thermal polycondensation product of aspartic acid, through successful ring-opening reactions using propargylamine, 1-azido-2-aminoethane and ethanolamine. The composition of the prepared copolymers was analyzed using 1H NMR spectroscopy. Clickable PHEA derivatives were crosslinked by mixing together in water with a catalyst system of Cu(I) and N, N, N′, N′, N″-pentamethyldiethylenetriamine, a type of Huisgen's 1,3-dipolar azide-alkyne cycloaddition. The reaction of the polymers resulted in a chemoselective coupling between alkynyl and azido functional groups with multiple formation of triazole crosslinks to give hydrogels. The triazole linkages in the hydrogels are highly stable and may also play a role in swelling behavior. PHEA-based hydrogels were also obtained by the crosslinking of azide- or alkyne-modified PHEA with a small-molecule crosslinker. The hydrogels prepared using these two methods were characterized by their degree of swelling and the morphology of the hydrogels was confirmed using scanning electron microscopy. The approach we describe here presents a promising alternative to common chemical hydrogel preparation techniques, and these hydrogels seem to possess structures having potential for a variety of industrial and biomedical applications. © 2012 Society of Chemical Industry.