Understanding the Molecular-Level Interactions of Glucosamine-Glycerol Assemblies: A Model System for Chitosan Plasticization

[Image: see text] Glycerol is the most widely used plasticizer for the biopolymer chitosan. However, there remains a lack of understanding of the molecular-level interactions between chitosan and glycerol. Here, we describe an in-depth spectroscopic study of the intermolecular interactions between the monomeric repeating unit of chitosan, glucosamine, and the plasticizer glycerol. Infrared and nuclear magnetic resonance spectroscopy were used to probe glucosamine assembly at high and low concentrations to establish diagnostic signals for intra- and intermolecular glucosamine interactions. Systematic addition of glycerol was found to disrupt intramolecular glucosamine hydrogen bonds and promote glucosamine self-assembly. Furthermore, we observed a significant preference for glycerol binding to the amine functionality of glucosamine. These findings indicate that the plasticization of chitosan with glycerol requires a specific binding motif and likely occurs via the gel theory mechanism.