Nanocellulose-short peptide self-assembly for improved mechanical strength and barrier performance†

Cellulose nanofibers (CNF) are the most abundant renewable nanoscale fibers on Earth, and their use in the design of hybrid materials is ever more acclaimed, although it has been mostly limited, to date, to CNF derivatives obtained via covalent functionalization. Herein, we propose a noncovalent approach employing a set of short peptides – DFNKF, DF(I)NKF, and DF(F₅)NKF – as supramolecular additives to engineer hybrid hydrogels and films based on unfunctionalized CNF. Even at minimal concentrations (from 0.1% to 0.01% w/w), these peptides demonstrate a remarkable ability to enhance CNF rheological properties, increasing both dynamic moduli by more than an order of magnitude. Upon vacuum filtration of the hydrogels, we obtained CNF-peptide films with tailored hydrophobicity and surface wettability, modulated according to the peptide content and halogen type. Notably, the presence of fluorine in the CNF-DF(F₅)NKF film, despite being minimal, strongly enhances CNF water vapor barrier properties and reduces the film water uptake. Overall, this approach offers a modular, straightforward method to create fully bio-based CNF-peptide materials, where the inclusion of DFNKF derivatives allows for facile functionalization and material property modulation, opening their potential use in the design of packaging solutions and biomedical devices.