{Reference Type}: Journal Article
{Title}: Enzyme-triggered assembly of glycan nanomaterials.
{Author}: van Trijp JP;Hribernik N;Lim JH;Dal Colle MCS;Vázquez Mena Y;Ogawa Y;Delbianco M;
{Journal}: Angew Chem Int Ed Engl
{Volume}: 0
{Issue}: 0
{Year}: 2024 Jul 15
{Factor}: 16.823
{DOI}: 10.1002/anie.202410634
{Abstract}: 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.