Interaction mechanism between low molecular weight chitosan nanofilm and functionalized surfaces in aqueous solutions

Low-molecular-weight chitosan (LMW chitosan, <10 kDa) have a significant potential for biomedical applications (e.g., antimicrobial and gene/drug delivery) because of their higher water solubility at pH values ranging from 3.0 to 8.5, compared to that of the high-molecular-weight (>100 kDa) chitosan. A comprehensive understanding of the LMW interaction mechanism with specific functional groups is necessary to predict their binding efficiency to other molecules for effectively utilizing their potential within biological systems. In this study, we used a surface forces apparatus (SFA) to investigate molecular interactions between LMW chitosan and four different functionalized self-assembled monolayers (SAMs) in aqueous solutions at pH values of 3.0, 6.5, and 8.5. Chitosan exhibited the strongest interaction energy with methyl-terminated SAM (CH₃-SAM), indicating the significance of hydrophobic interaction. Many chitin/chitosan fibers in nature bind polyphenols (e.g., eumelanin) to form robust composites, which can be attributed to the strong attraction between chitosan and phenyl-SAM, presumably caused by cation-π interactions. These findings demonstrate the potential of modulating the magnitude of the interaction energy by controlling the solution pH and types of targeted functional groups to realize the optimal design of chitosan-based hybrid composites with other biomolecules or synthetic materials.