Bioinspired Co‐Assembly Enables Multiscale Architected Hydrogels for 3D Printing With Integrated Antibacterial and Bioactive Functions

ABSTRACT Bioinspired materials have emerged as a versatile platform for engineering functional systems that mimic the structural and biological complexity of natural tissues. However, translating molecular self‐assembly into mechanically robust and structurally defined constructs suitable for fabrication remains a major challenge. Here, we report a multicomponent hydrogel based on the co‐assembly of cell‐adhesive peptide, Fluorenylmethoxycarbonyl‐Lysine‐fluorenylmethoxycarbonyl‐Arginine‐Glycine‐Aspartic Acid (Fmoc‐K(Fmoc)‐RGD), and an antibacterial fluorinated peptide, Fmoc‐pentafluorophenylalanine (Fmoc‐F 5 ‐Phe), within an alginate (Alg)‐cellulose nanofibril (CNF) matrix. The resulting hierarchical networks that couple bioactivity with enhanced mechanical performance, exhibiting pronounced shear‐thinning behavior and rapid post‐extrusion recovery, enabling extrusion‐based three dimentional (3D) printing of constructs with high filament fidelity and shape retention. Rheological and structural analyses further demonstrate that peptide‐driven supramolecular organization links nanoscale fibrillar architecture to macroscopic mechanical properties, providing tunable reinforcement of the composite network. Biological analysis demonstrates high cytocompatibility alongside concentration‐dependent antibacterial activity against Escherichia coli ( E. coli) , highlighting the integration of multiple functionalities within a single material system. This work establishes multicomponent supramolecular co‐assembly as a versatile strategy to bridge molecular design with macroscale fabrication, offering a framework for the development of multifunctional biohybrid materials for advanced biofabrication applications.