Naturally Derived Maleic Chitosan/Thiolated Sodium Hyaluronate Hydrogels as Potential 3D Printing Tissue Engineering Materials

3D printing is an attractive method to accurately construct artificial organs or alternative materials with complicated structures and functional performance. Naturally derived hydrogels have emerged as promising materials for the preparation of biomimetic 3D organization or scaffolds by 3D printing due to their good biocompatibility, high water content, and fascinating 3D network. However, the poor printing properties and weak structural stability of naturally derived hydrogels limit their applications. In this study, photopolymerizable hydrogels are designed based on maleic chitosan (MCS) and thiolated sodium hyaluronate (SHHA). The Michael addition between MCS and SHHA improves the viscosity of the mixed solution. Moreover, it benefits the 3D printing process, followed by photopolymerization (acrylate-thiol step-chain polymerization and acrylate–acrylate chain polymerization) to form a stable covalent network rapidly. The rheological property, swelling behaviors, microstructure, and in vitro degradation are tuned by adjusting the molar ratio of the thiol group and acrylate group. In addition, MCS/SHHA hydrogel scaffolds with good accuracy and enhanced structural stability are prepared using extrusion-based 3D printing and photopolymerization technology. The hydrogels display excellent cytocompatibility and can support adherence of L929 cells, which can be used as prospective materials for tissue engineering applications.