Effect of active carbonyl-carboxyl ratio on dynamic Schiff base crosslinking and its modulation of high-performance oxidized starch-chitosan hydrogel by hot extrusion 3D printing

The quest to develop 3D starch-based printing hydrogels for the controlled release of active substances with excellent mechanical and printing properties has gained significant attention. This work introduced a facile method based on crosslinking via Schiff base reaction for preparing bicomponent hydrogels. The method involved the utilization of customizable oxidized starch (OS) and chitosan (CS), enabling superior printing performance through the precise control of various active carbonyl-carboxyl ratios (ACR, 2:1, 1:1, and 2:3, respectively) of OS. OS-CS hydrogel (OSC) with an ACR level of 2:1 (OS-2-y%CS) underwent rearrangement during printing environment, fostering increased Schiff base reaction with a higher crosslinking degree and robust high structural recovery (>95 %). However, with decreasing ACR levels (from 2:1 to 2:3), the printing performance and mechanical strength of printed OSC (POSC) declined due to lower Schiff base bonds and increased phase separation. Compared with printed OS, POS-2-2%CS exhibited a remarkable 1250.52 % increase in tensile strength and a substantial 2424.71 % boost in compressive strength, enhanced shape fidelity and notable self-healing properties. Moreover, POS-2-2%CS exhibited stable diffusive drug release, showing potential application in the pH-responsive release of active substances. Overall, controlling the active carbonyl-carboxyl ratios provided an efficient and manageable approach for preparing high-performance 3D-printed hydrogels.