3D Printable Hydrogel Based on TEMPO-Oxidized Cellulose Nanofibrils and Fmoc-FF for Enhanced Biological Performance and Cell Adhesion

作者：Dhanya Raveendran, Feras Dalloul, J. Benedikt Mietner, Enguerrand Barba, Shouzheng Chen, Daria Zaytseva‐Zotova, Benedikt Sochor, Sarathlal Koyiloth Vayalil, Peter Müller‐Buschbaum, Hanna Tiainen, Stephan V. Roth, Julien R. G. Navarro · 发表于：ACS Applied Nano Materials · 年份：2025 · DOI：10.1021/acsanm.5c03356 · 被引用次数：4 · 研究领域：Supramolecular Self-Assembly in Materials、Electrospun Nanofibers in Biomedical Applications、Hydrogels: synthesis, properties, applications

High Resolution Image Download MS PowerPoint Slide Herein, we report a 3D printable ink made of a peptide-polysaccharide hybrid hydrogel composed of fluorenylmethyloxycarbonyl-diphenylalanine (Fmoc-FF) peptide and TEMPO-oxidized cellulose nanofibrils (ToCNF), synthesized using a pH-dependent sol–gel transition method. The ToCNF suspension is synthesized through the mechanical breakdown of a cellulose pulp using a microfluidizer, followed by its oxidation mediated with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). The properties of the hybrid inks are compared in the presence (ToCNF/Fmoc-FF-Ca 2+ ) and absence (ToCNF/Fmoc-FF) of the divalent cation Ca 2+, which acts as the cross-linker, at two optimized weight ratios ( r ) of ToCNF and Fmoc-FF ( r = 4.5 and 6.5). The rheological measurements show that the yield strength of the ToCNF/Fmoc-FF-Ca 2+ gel is almost double that of the hydrogel composite without Ca 2+ ions, especially at the concentration ( C ) of 10 mM CaCl 2 . This finding is further verified by 3D gel printing, which produced good quality prints with the cation cross-linked hydrogel. The structural analysis by Field Emission Scanning Electron Microscopy shows that the calcium ions can cross-link the ToCNF and also enhance the self-assembly of Fmoc-FF, which leads to the formation of rigid compact nanofibers even at physiological pH. The electrostatic interaction of the positively charged Ca 2+ ions onto the negatively charged surface carboxylate groups of ToCNF an...