In situ formation of nanocomposite double-network hydrogels with shear-thinning and self-healing properties

Nanocomposite double-network hydrogels (ncDN hydrogels) are recently introduced to address the limitations of traditional DN hydrogels, such as the lack of diversity in the network structure and the restricted functionalities. However, two challenges remain, including the time-consuming preparation and the lack of shear-thinning and self-healing properties. Here, our approach to developing versatile ncDN hydrogels is through the use of multiple interfacial crosslinking chemistries (i.e., noncovalent interactions of electrostatic interaction and hydrogen bonds as well as dynamic covalent interactions of imine bonds and boronate ester bonds) and surface functionalized nanomaterials (i.e. phenylboronic acid modified reduced graphene oxide (PBA-rGO)). PBA-rGO was used as a multivalent gelator to further crosslink the two polymer chains (i.e. triethylene glycol-grafted chitosan (TEG-CS) and polydextran aldehyde (PDA)) in DN hydrogels, forming the TEG-CS/PDA/PBA-rGO ncDN hydrogels in seconds. The microstructures (i.e. pore size) and properties (i.e. rheological, mechanical, and swelling properties) of the ncDN hydrogels can be simply modulated by changing the amount of PBA-rGO. The dynamic bonds in the polymeric network provided the shear-thinning and self-healing properties to the ncDN hydrogels, allowing the hydrogels to be injected and molded into varied shapes as well as self-repair the damaged structure. Besides, the designed TEG-CS/PDA/PBA-rGO ncDN hydrogels were cytocompatible and also exhibited antibacterial activity. Taken together, we hereby provide a nanomaterial approach to fabricate a new class of ncDN hydrogels with tailorable networks and favorite properties for specific applications.