Natural polymer hydrogels are one of the best biomaterials for soft tissue repair because of their excellent biocompatibility, biodegradability and low immune rejection. However, they lack mechanical strength matching that of natural tissue and desired functionality (e.g., self-healing and 3D-printability). To solve these problems, we developed a host–guest supramolecule (HGSM) with three arms covalently crosslinked with a natural polymer to construct a novel hydrogel with non-covalent bonds integrated into a covalently crosslinked network. This unique structure enabled the hydrogel to exhibit improved mechanical properties and show both self-healing and 3D printing capabilities. The three-armed HGSM was first prepared via efficient non-covalent host–guest inclusion interactions between isocyanatoethyl acrylate-modified β-cyclodextrin (β-CD-AOI₂) and acryloylated tetra-ethylene glycol-modified adamantane (A-TEG-Ad). Subsequently, a host–guest supramolecular hydrogel (HGGelMA) was obtained through copolymerization between the arms of the HGSM and gelatin methacryloyl (GelMA) to form a covalently crosslinked network. The HGGelMA was robust, fatigue resistant, reproducible and rapidly self-healing. In the HGGelMA, the covalent crosslinking maintained its overall shape, whereas the weak reversible non-covalent host–guest interactions reinforced its mechanical properties and enabled it to rapidly self-heal upon fracturing. The reversible non-covalent interactions could be re-established upon breaking, so as to heal the hydrogel and dissipate energy to prevent catastrophic fracture propagation. Furthermore, the precursors of the HGGelMA were sufficiently viscous and could be rapidly photocrosslinked to produce a robust scaffold with an exquisite internal structure through 3D printing. The 3D-printed HGGelMA hydrogel scaffold was biocompatible, promoted cell adhesion and proliferation, and supported tissue in-growth. Our strategy of integrating a non-covalently linked HGSM into a covalently linked hydrogel network represents a new approach to the development of natural polymers into biocompatible hydrogels with improved strength as well as desired self-healing and 3D-printability.

While hydrogels enable a variety of applications in wearable sensors and electronic skins, they are susceptible to fatigue fracture during cyclic deformations owing to their inefficient fatigue resistance. Herein, acrylated β-cyclodextrin with bile acid is self-assembled into a polymerizable pseudorotaxane via precise host-guest recognition, which is photopolymerized with acrylamide to obtain conductive polymerizable rotaxane hydrogels (PR-Gel). The topological networks of PR-Gel enable all desirable properties in this system due to the large conformational freedom of the mobile junctions, including the excellent stretchability along with superior fatigue resistance. PR-Gel based strain sensor can sensitively detect and distinguish large body motions and subtle muscle movements. The three-dimensional printing fabricated sensors of PR-Gel exhibit high resolution and altitude complexity, and real-time human electrocardiogram signals are detected with high repeating stability. PR-Gel can self-heal in air, and has highly repeatable adhesion to human skin, demonstrating its great potential in wearable sensors.

Nanosized celluloses are attractive building blocks to generate hierarchically advanced materials and have been gradually explored in emulsion applications. Here we report a high internal phase emulsion (HIPE) prepared by using supramolecular cellulose nanocrystals (CNCs) as Pickering stabilisers via one-step emulsification, and interconnected macroporous hybrid hydrogels were produced by utilizing this HIPE as a template. A quadruple hydrogen bonding moiety 2-ureido-4[1H]-pyrimidone (UPy) was firstly grafted onto the surface of cellulose nanocrystals through simple free radical polymerization. The polymer grafting was confirmed by elemental analysis and thermogravimetry. The UPy modified CNCs (CNC-UPy) exhibited superior emulsion stabilising ability compared to the pristine CNCs, and the oil-in-water emulsions with an internal phase volume ratio of 80% showed good long-term stability. The properties of resulting macroporous polyHIPE hydrogels, such as swelling behaviours, porous structures and mechanical strength, were investigated on the dependence of CNC-UPy concentrations. In addition, the macroporous hybrid hydrogel exhibits excellent cytocompatibility and cell adhesion as demonstrated by mouse bone mesenchymal stem cell (mBMSC) culture. With these promising properties, the developed hydrogels demonstrate great potential as active biological scaffolds for tissue engineering.