Fabrication of clickable bamboo-sourced cellulose nanofibrils for diverse surface modifications: Hydrophobicity and fluorescence functionalities

Surface functionalization of cellulose nanofibrils (CNF) is crucial for expanding their practical application. However, most functionalization processes are complicated and laborious. Herein, this work presents a facile surface engineering strategy to create a range of functionalized CNF via thiol-ene click reaction. Initially, clickable CNF was produced by grafting a compound with both carboxylate- and norbornene groups onto bamboo cellulose via norbornene-dicarboxylic anhydride esterification followed by homogenization. The introduction of negatively charged carboxylates facilitated nanofibrillation, resulting in CNF with a diameter of 3 nm and an aspect ratio of up to 600. The introduction of norbornenes enabled diverse functionalization of CNF through click reaction. Subsequently, hexadecanethiol successfully clicked with norbornene-grafting CNF, enhancing its hydrophobicity and dispersion in organic solvents. 7-mercapto-4-methyl coumarin was also able to click with norbornene-grafting CNF, yielding fluorescence-labeled CNF while maintaining excellent aqueous dispersibility. The fluorescence-labeled CNF was demonstrated to be utilized as an eco-friendly sensor for the detection of Fe 3+ ions. Additionally, it could be converted into fluorescent films or intelligent inks suitable for anti-counterfeiting purposes. This study demonstrates that the proposed surface engineering strategy provides an effective approach for producing clickable CNF and fabricating cellulosic materials with diverse functionalities that meet the demands of various applications.