Self-assembly is a powerful strategy for creating complex architectures and elucidating the aggregation behaviors of biopolymers. Herein, we investigate the hierarchical assembly of chitin using a bottom-up approach based on synthetic oligosaccharides. We discovered that chitin oligosaccharides self-assemble into platelets, which then form higher-order structures. Subtle changes in experimental conditions drastically altered the self-assembly results, generating a wide array of higher-order architectures. Through systematic investigations employing transmission electron microscopy (TEM), photoinduced force microscopy (PiFM), and atomic force microscopy (AFM), we uncovered the role of water in shaping the different morphologies. This finding gave us the tools to promote the formation of chiral, uniform chitin oligosaccharide bundles. Our work not only sheds light on the fundamental aspects of chitin organization, but also suggests strategies for designing carbohydrate-based materials with tunable structures and properties.
