3D printable multifunctional pH-responsive double-network hydrogels via TCNF reinforcement and Fe3+ crosslinking: mechanical, antibacterial, and computational analysis
摘要
Hydrogels, characterized by their integration of physical, chemical, and biological cues within a dynamic polymeric network, have emerged as versatile platforms for a wide range of biomedical applications. However, their inherently low mechanical strength has necessitated the development of advanced formulations. Among these, double-network (DN) hydrogels have garnered significant attention due to their enhanced mechanical robustness and toughness, attributed to the synergistic interaction between two interpenetrating polymer networks. In the present study, composite hydrogels comprising cellulose nanofibers (CNF) or TEMPO-oxidized CNF (TCNF) reinforced poly(acrylamide)/alginate (PAM/ALG) matrices were synthesized via in situ polymerization. The PAM/ALG/TCNF-Fe3+ DN hydrogel integrates covalent crosslinking—primarily through acrylamide chains crosslinked with N, N′-methylenebisacrylamide (MBA) and noncovalent ionic interactions between carboxylate groups and Fe3+ ions, forming a secondary network. The incorporation of CNF and Fe3+ ions facilitate the formation of printable anisotropic hydrogel architectures, which exhibit pH responsive swelling behavior (pH 4 composite shrinks pH 9 swells with swelling ratios as 8.8 and 14, respectively), and rheological performance. Notably, incorporation of Fe3+ ions loading facilitate the double composite network (DCN) formulation (PAM/ALG1.5/3TCNF-Fe3+) demonstrating a ~ 6–7 folds enhancement in tensile toughness (276 kPa) and strength (218 kPa), respectively and also exhibit pH responsive capabilities, swelling behavior, and shape recovery performance. Furthermore, Fe3+ loading contributed to improved energy dissipation (42 kJ/m3 energy dissipation at ~ 40% strain), shape recoverability (demonstrated upto10 successive loading–unloading cycles), electrical conductivity (0.062 S/m), and potent antimicrobial activity against S. aureus. Additionally, the experimentally measured mechanical performance of the anisotropic functional composite hydrogel structures showed good agreement with the predictions obtained from the finite element (FE) simulations. Moreover, the 3D printable engineered composite hydrogels exhibited intrinsic physical and mechanical properties and antibacterial potency, thereby expanding their applicability in advanced biomedical domains such as wearable bioelectronics, antibacterial wound dressing and load bearing biomedical applications.