Supermacroporous hydrogels, possessing sponge-like structure and permeability, have drawn significant attention for their bioengineering and biomedical applications. However, their mechanical weakness due to their low-density structure is one of their biggest limitations. This work reports a multi-step cryogelation technique, which does not require special equipment, for preparing tough supermacroporous hydrogels on the basis of the double-network (DN) strategy. The produced supermacroporous DN gels possess interconnected pores with pore sizes of 50-230 µm. They also show a compressive modulus of up to ~100 kPa, which is 2-to 4-times higher than that of the corresponding supermacroporous singlenetwork (SN) gels, and compressive strength of up to 1 MPa at 80% compression. The supermacroporous DN cryogels are also stretchable with a work of extension of up to 38 kJ m -3 , which is 1 to 2 orders larger than that of the SN cryogels. The high stiffness and stretchability distinguish them from other types of cryogels. Supermacroporous triple-network (TN) gels and DN gels composed of different polymer combinations are also prepared. The technique presented herein is suitable for preparing supermacroporous DN gels from various polymers; hence, it is promising in meeting bioengineering and biomedical demands.
We present an investigation of the preparation of highly porous hydrogels based on biodegradable synthetic poly(α-amino acid) as potential tissue engineering scaffolds. Covalently cross-linked gels with permanent pores were formed under cryogenic conditions by free-radical copolymerization of poly[N(5)-(2-hydroxyethyl)-L-glutamine-stat-N(5)-(2-methacryloyl-oxy-ethyl)-L-glutamine] (PHEG-MA) with 2-hydrohyethyl methacrylate (HEMA) and, optionally, N-propargyl acrylamide (PrAAm) as minor comonomers. The morphology of the cryogels showed interconnected polyhedral or laminar pores. The volume content of communicating water-filled pores was >90%. The storage moduli of the swollen cryogels were in the range of 1-6 kPa, even when the water content was >95%. The enzymatic degradation of a cryogel corresponded to the decrease in its storage modulus during incubation with papain, a model enzyme with specificity analogous to wound-healing enzymes. It was shown that cryogels with incorporated alkyne groups can easily be modified with short synthetic peptides using azide-alkyne cycloaddition "click" chemistry, thus providing porous hydrogel scaffolds with biomimetic features.
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