%0 Journal Article
%T Enzyme-triggered assembly of glycan nanomaterials.
%A van Trijp JP
%A Hribernik N
%A Lim JH
%A Dal Colle MCS
%A Vázquez Mena Y
%A Ogawa Y
%A Delbianco M
%J Angew Chem Int Ed Engl
%V 0
%N 0
%D 2024 Jul 15
%M 39008635
%F 16.823
%R 10.1002/anie.202410634
%X A comprehensive molecular understanding of carbohydrate aggregation is key to optimize carbohydrate utilization and to engineer bioinspired analogues with tailored shape1s and properties. However, the lack of well-defined synthetic standards has substantially hampered advances in this field. Herein, we employ a phosphorylation-assisted strategy to synthesize previously inaccessible long oligomers of cellulose, chitin, and xylan. These oligomers were subjected to enzyme-triggered assembly (ETA) for the on-demand formation of well-defined carbohydrate nanomaterials, including elongated platelets, helical bundles, and hexagonal particles. Cryo-electron microscopy and electron diffraction analysis provided molecular insights into the aggregation behavior of these oligosaccharides, establishing a direct connection between the resulting morphologies and the oligosaccharide primary sequence. Our findings demonstrate that ETA is a powerful approach to elucidate the intrinsic aggregation behavior of carbohydrates in nature. Moreover, the ability to access a diverse array of morphologies, expanded with a non-natural sequence, underscores the potential of ETA, coupled with sequence design, as a robust tool for accessing programmable glycan architectures.