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Extraordinary self-healing efficiency is rarely observed in mechanically strong hydrogels, which often limits the applications of hydrogels in biomedical engineering. We have presented an approach to utilize a special type of graphene oxide-based crosslinker (GOBC) for the simultaneous improvement of toughness and self-healing properties of conventional hydrogels. The GOBC has been prepared from graphene oxide (GO) by surface oxidation and further introduction of vinyl groups. It has been designed in such a way that the crosslinker is able to form both covalent bonds and noncovalent interactions with the polymer chains of hydrogels. To demonstrate the efficacy of GOBC, it was incorporated in a conventional polyacrylamide (PAM) and polyacrylic acid (PAA) hydrogel matrix, and the mechanical and self-healing properties of the prepared hydrogels were investigated. In PAM-GOBC hydrogels, it has been observed that the mechanical properties such as tensile strength, Young's modulus, and toughness are significantly improved by the incorporation of GOBC without compromising the self-healing efficiency. The PAM-GOBC hydrogel with a modulus of about 0.446 MPa exhibited about 70% stress healing efficiency after 40 h. Whereas, under the same conditions a PAM hydrogel with commonly used crosslinker N , N '-methylene-bis(acrylamide) of approximately the same modulus demonstrated no self-healing at all. Similar improvement of self-healing properties and toughness in PAA-GOBC hydrogel has also been observed which demonstrated the universality of the crosslinker. This crosslinker-based approach to improve the self-healing properties is expected to offer the possibility of the application of commonly used hydrogels in many different sectors, particularly in developing artificial tissues., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The mechanical performances of hydrogels are greatly influenced by the functionality of cross-linkers and their covalent and non-covalent interactions with the polymer chains. Conventional chemical cross-linkers fail to meet the demand of large toughness and high extensibility for their immediate applications as artificial tissues like ligaments, blood vessels, and cardiac muscles in human or animal bodies. Herein, we synthesized a new graphene oxide-based two-dimensional (2D) cross-linker (GOBC) and exploited the functionality of the cross-linker for the enhancement of toughness and stretchability of a poly(acrylic acid) (PAA) hydrogel. The 2D nanosheets of GO were modified in such a way that they could provide multifunctional sites for both physical and chemical bonding with the polymer chains. Carboxylic acid groups at the surfaces of the GO sheets were coupled with the acrylate functional groups for covalent cross-linking, while the other oxygen-containing functional groups are responsible for physical cross-linking with polymers. The GOBC had been successfully incorporated into the PAA hydrogel and the mechanical properties of the GOBC cross-linked PAA hydrogel (PAA-GOBC) were investigated at various compositions of cross-linker. Seven times enhancement in both toughness and elongation at break has been achieved without compromising on the modulus for the as-synthesized PAA-GOBC compared to the conventional N , N '-methylenebis(acrylamide) (MBA) cross-linked PAA hydrogel. This facile and efficient way of GO modification is expected to lead the development of a high-performance nanocomposite for cutting-edge applications in biomedical engineering., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A combination of strong load-bearing capacity and high swelling degree is desired in hydrogels for many applications including drug delivery, tissue engineering, and biomedical engineering. However, a compromising relationship exists between these two most important characteristics of hydrogels. Improving both of these important properties simultaneously in a single hydrogel material is still beyond the satisfactory limit. Herein, we report a novel approach to address this problem by introducing a silica-based bi-functional 3D crosslinker. Our bi-functional silica nanoparticles (BF-Si NPs) possess amine groups that are able to offer pseudo-crosslinking effects induced by inter-cohesive bonding, and acrylate groups that can form conventional covalent crosslinking in the same hydrogel. We fabricated polyacrylic acid (PAc-Si) and polyacrylamide (PAm-Si) hydrogels using our BF-Si NPs via free radical polymerization to demonstrate this concept. Incorporation of the BF-Si crosslinkers into the hydrogels has resulted in a large enhancement in the mechanical properties compared to conventional hydrogel crosslinked with N , N '-methylene bisacrylamide (MBA). For instance, tensile strength and the toughness increased by more than 6 times and 10 times, respectively, upon replacing MBA with BF-Si in polyacrylamide hydrogel. Moreover, the hydrogels crosslinked with BF-Si exhibited a remarkably elevated level of swelling capacity in the aqueous medium. Our facile yet smart strategy of employing the 3D bi-functional crosslinker for combining high swelling degree and strong mechanical properties in the same hydrogels can be extended to the fabrication of many similar acrylate or vinyl polymer hydrogels., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)