Efficient diversification of GM3 gangliosides via late-stage sialylation and dynamic glycan structural studies with 19F solid-state NMR
Efficient diversification of GM3 gangliosides via late-stage sialylation and dynamic glycan structural studies with 19F solid-state NMR
复制标题
通过后期唾液酸化和 19F 固态 NMR 动态聚糖结构研究实现 GM3 神经节苷脂的有效多样化
DOI：
10.1039/d0ob00437e
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发表时间：
2020
影响因子：
3.2
通讯作者：
Ando Hiromune
中科院分区：
文献类型：
--
作者：
Takahashi Maina;Shirasaki Junya;Komura Naoko;Sasaki Katsuaki;Tanaka Hide-Nori;Imamura Akihiro;Ishida Hideharu;Hanashima Shinya;Murata Michio;Ando Hiromune
含唾液酸的糖缀合物参与重要的生物学过程，例如免疫应答、癌症转移和病毒感染。然而，它们的化学合成一直具有挑战性，主要是由于寡糖的α-唾液酸化的困难。最近，我们建立了一个完全立体选择性的唾液酸化方法，使用大双环唾液酸供体。在此，我们描述了一种合理和有效的合成唾液酸糖脂通过直接唾液酸化的糖脂在后期阶段，基于我们的新的唾液酸化方法。该合成方法使得能够开发具有唾液酸基部分的各种C5修饰的GM 3神经节苷脂类似物。此外，合成的类似物进行固态19 F NMR分析的模型膜，它揭示了胆固醇对聚糖动力学的影响。
Sialic acid-containing glycoconjugates are involved in important biological processes such as immune response, cancer metastasis, and viral infection. However, their chemical syntheses have been challenging, mainly due to the difficulties in the α-sialylation of oligosaccharides. Very recently, we established a completely stereoselective sialidation method using a macrobicyclic sialyl donor. Herein, we describe a rational and efficient synthesis of sialoglycolipids via direct sialylation of a glycolipid at a late-stage, based on our novel sialidation method. The synthetic method enabled the development of GM3 ganglioside analogs with various C5-modifications of the sialosyl moiety. Furthermore, the synthesized analog was subjected to solid-state 19F NMR analysis on the model membranes and it revealed the influence of cholesterol on glycan dynamics.