Supramolecular Modulation of the Mechanical Properties of Amino Acid-functionalized Cellulose Nanocrystal Films

Cellulose nanocrystal (CNC) is a promising building block for the bottom-up assembly of novel lightweight renewable materials. The ability to engineer the interfacial properties of CNC is of paramount importance to develop assembled materials for various applications; yet it remains a challenge to manipulate the supramolecular interactions within the cellulosic nanomaterials in a controlled manner. In this context, we demonstrate in this article how the assembly and mechanical properties of cellulose thin films can be controlled by manipulating the interfacial interactions of TEMPO-oxidized cellulose nanocrystals (TOCNCs) grafted with two different amino acids, arginine and tryptophan. The amino acid grafting onto the cellulose scaffold was confirmed in aqueous solutions by 1H NMR spectroscopy and in solid form by FTIR and XPS techniques. The surface functionalization of TOCNCs with simple cationic and aromatic groups provides a strategy for tuning the assembly of the nanostructures based on different supramolecular cross-linking interactions, including hydrogen bonds, π–π stacking, and cation–π interactions. In particular, we show that nanocellulose chains cross-linked by the non-covalent cation–π interactions lead to the formation of a laminated superstructure with high deformation and load standing capabilities. Our work provides a versatile strategy for tuning the surface properties of nanocellulose and represents an important step toward the development of sustainable materials with tailored mechanical properties, which will enable a wider application range of this building block all the way from tissue-engineering scaffolds to flexible devices.