Modern tissue regeneration strategies rely on soft biocompatible materials with adequate mechanical properties to support the growing tissues. Polymer hydrogels have been shown to be available for this purpose, as their mechanical properties can be controllably tuned. In this work, we introduce interpenetrating polymer networks (IPN) hydrogels with improved elasticity due to a dual cross-linking mechanism in one of the networks. The proposed hydrogels contain entangled polymer networks of covalently cross-linked poly(ethylene glycol) methacrylate/diacrylate (PEGMA/PEGDA) and poly(vinyl alcohol) (PVA) with two types of physical cross-links-microcrystallites and tannic acid (TA). Rheological measurements demonstrate the synergistic enhancement of the elastic modulus of the single PEGMA/PEGDA network just upon the addition of PVA, since the entanglements between the two components are formed. Moreover, the mechanical properties of IPNs can be independently tuned by varying the PEGMA/PEGDA ratio and the concentration of PVA. Subsequent freezing-thawing and immersion in the TA solution of IPN hydrogels further increase the elasticity because of the formation of the microcrystallites and OH-bonds with TA in the PVA network, as evidenced by X-ray diffraction and ATR FTIR-spectroscopy, respectively. Structural analysis by cryogenic scanning electron microscopy and light microscopy reveals a microphase-separated morphology of the hydrogels. It promotes extensive contact between PVA macromolecules, but nevertheless enables the formation of a 3D network. Such structural arrangement results in the enhanced mechanical performance of the proposed hydrogels, highlighting their potential use for tissue engineering.

BCMaterials Basque Center for Materials Applications and Nanostructures UPV EHU Science Park 48940 Leioa Spain

Faculty of Chemistry Karaganda Buketov University Karaganda 100028 Kazakhstan

IKERBASQUE Basque Foundation for Science 48009 Bilbao Spain

Institute of Macromolecular Chemistry 16200 Prague Czech Republic

Physics Department Lomonosov Moscow State University Moscow 119991 Russia

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