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.
摘要：
对碳水化合物聚集的全面分子理解是优化碳水化合物利用和设计具有定制形状和特性的生物启发类似物的关键。然而,缺乏明确的合成标准大大阻碍了这一领域的进展。在这里，我们采用磷酸化辅助策略来合成以前难以接近的纤维素长低聚物，甲壳素,还有木聚糖.这些低聚物进行酶触发组装（ETA），用于按需形成明确定义的碳水化合物纳米材料，包括细长的血小板，螺旋束,和六角形颗粒。低温电子显微镜和电子衍射分析为这些寡糖的聚集行为提供了分子见解，在所得形态和寡糖一级序列之间建立直接连接。我们的发现表明，ETA是阐明自然界中碳水化合物固有聚集行为的有力方法。此外，能够获得各种各样的形态，用非自然序列展开，强调了ETA的潜力，再加上序列设计，作为访问可编程聚糖架构的强大工具。
