Hydrogels are a popular class of biomaterial that are used in a number of commercial applications (e.g.; contact lenses, drug delivery, and prophylactics). Alginate-based tough hydrogel systems, interpenetrated with acrylamide, reportedly form both ionic and covalent cross-links, giving rise to their remarkable mechanical properties. In this work, we explore the nature, onset and extent of such hybrid bonding interactions between the complementary networks in a model double-network alginate-acrylamide system, using a host of characterisation techniques (e.g.; FTIR, Raman, UV-vis, and fluorescence spectroscopies), in a time-resolved manner. Further, due to the similarity of bonding effects across many such complementary, interpenetrating hydrogel networks, the broad bonding interactions and mechanisms observed during gelation in this model system, are thought to be commonly replicated across alginate-based and broader double-network hydrogels, where both physical and chemical bonding effects are present. Analytical techniques followed real-time bond formation, environmental changes and re-organisational processes that occurred. Experiments broadly identified two phases of reaction; phase I where covalent interaction and physical entanglements predominate, and; phase II where ionic cross-linking effects are dominant. Contrary to past reports, ionic cross-linking occurred more favourably via mannuronate blocks of the alginate chain, initially. Evolution of such bonding interactions was also correlated with the developing tensile and compressive properties. These structure-property findings provide mechanistic insights and future synthetic intervention routes to manipulate the chemo-physico-mechanical properties of dynamically-forming tough hydrogel structures according to need (i.e.; durability, biocompatibility, adhesion, etc.), allowing expansion to a broader range of more physically and/or environmentally demanding biomaterials applications.
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