Synthetic carbohydrate-based materials – a cellulose story Martina Delbianco Max Planck Institute of Colloids and Interfaces, Germany Polysaccharides are the most abundant organic materials in nature, yet correlations between their three- dimensional structures and macroscopic properties have not been established. With automated glycan assembly (AGA), we prepared well-defined oligo- and polysaccharides resembling natural as well as unnatural structures. [1] These synthetic glycans are ideal probes for the fundamental study of polysaccharides, shedding light on how the primary sequence affects the polysaccharide properties (i.e. solubility and crystallinity). Molecular dynamics simulations, NMR spectroscopy, and single molecule imaging allowed for the visualization of polysaccharides’ conformation and revealed that some polymers form helices while others adopt rod-like structures.[2] Modifications in specific positions of the oligosaccharide chains permitted to tune the three-dimensional structure, solubility, and aggregation of such compounds.[3] Following a bottom-up approach, we used well-defined cellulose oligomers as tools to understand the transfer of chirality from the single oligomer to supramolecular assemblies, beyond the single cellulose crystal.[4] We discovered that synthetic cellulose oligomers self-assembled into thin micrometer-sized platelets with controllable thicknesses. These platelets further assembled into bundles displaying intrinsic chiral features, directly correlated to the monosaccharide chirality. Altering the stereochemistry of the oligomer termini influenced the chirality of the self-assembled bundles and allowed for the manipulation of the cellulose assemblies at the molecular level. References 1. M. Delbianco, A. Kononov, A. Poveda, Y. Yu, T. Diercks, J. Jiménez-Barbero, P. H. Seeberger, J. Am. Chem. Soc. 2018, 140, 5421-5426. 2. Wu, M. Delbianco, K. Anggara, T. Michnowicz, A. Pardo-Vargas, P. Bharate, S. Sen, M. Pristl, S. Rauschenbach, U. Schlickum, S. Abb, P. H. Seeberger, K. Kern, Nature 2020, 582, 375-378. 3. Y. Yu, T. Tyrikos-Ergas, Y. Zhu, G. Fittolani, V. Bordoni, A. Singhal, R. J. Fair, A. Grafmüller, P. H. Seeberger, M. Delbianco, Angew. Chem., Int. Ed. 2019, 58, 1433-7851. 4. G. Fittolani, D. Vargová, P. H. Seeberger, Y. Ogawa, M. Delbianco, J. Am. Chem. Soc. 2022, 144, 12469-12475.
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