Intelligent Cellulose Nanofibers with Excellent Biocompatibility Enable Sustained Antibacterial and Drug Release via a pH-Responsive Mechanism

Novel nanosized biomass-based pH-responsive cellulose nanofibers (CNF-PEI) with excellent biocompatibility were tailored by grafting polyethylenimine (PEI) onto carboxylated cellulose nanofibers (CNF-COOH); the active site (−COOH, 0.96 mmol/g) was anchored on cellulose nanofibers (CNFs) to introduce PEI with a high density (10.57 mmol/g) of amino groups. The as-prepared CNF-PEI not only maintained the good properties of CNFs but also possessed excellent biocompatibility and pH-responsive properties, offering interesting possibilities for pH-induced sustained drug release and medical dressing. The CNF-PEI showed rapid wettability conversion from hydrophilic, underwater superoleophobic (WCA = 20.7°, OCA = 159.3°) to hydrophobic, superoleophilic (WCA = 129.6°, OCA = 29.7°) in response to pH change from acidic conditions to alkaline conditions. The antibacterial activity of CNF-PEI toward Escherichia coli and Listeria monocytogenes was 100% and 94.6% under acidic conditions, respectively. Furthermore, the pH-responsive mechanism of CNF-PEI was revealed by XPS, 13C NMR, 1H NMR, and AFM analyses.