Precision native polysaccharides from living polymerization of anhydrosugars
Precision native polysaccharides from living polymerization of anhydrosugars
复制标题
来自脱水糖活性聚合的精密天然多糖
DOI：
10.1038/s41557-023-01193-2
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发表时间：
2023
期刊：
影响因子：
21.8
通讯作者：
Niu, Jia
中科院分区：
文献类型：
--
作者：
Wu, Lianqian;Zhou, Zefeng;Sathe, Devavrat;Zhou, Junfeng;Dym, Shoshana;Zhao, Zhensheng;Wang, Junpeng;Niu, Jia
多糖的糖苷链的组成、序列、长度和类型深刻地影响着多糖的生物学和物理性质。然而，多糖的结构-功能关系的研究受到难以获得足够数量的明确定义的多糖的阻碍。在这里，我们报告了一种化学方法，通过1,6-无水糖的活性阳离子开环聚合来获得具有天然糖苷键的精密多糖。我们用三氟化硼醚催化剂和氟化糖基引发剂合成了分子量可调、分散性低、区域选择性和立体选择性好的、性质明确的多糖。计算研究表明，该反应通过对氧羰基单体α-加成进行扩散，并受扩散的氧羰基可逆失活控制，形成氟糖基休眠种。我们的方法提供了一个简单和可扩展的途径，多种生物相关的精密多糖，包括d-葡聚糖，d-甘露聚糖和一种不寻常的葡聚糖。我们证明了精密多糖的催化解聚有效地再生了单体，这表明它们作为一类具有定制热性能和机械性能的化学可回收材料的潜在用途。
The composition, sequence, length and type of glycosidic linkage of polysaccharides profoundly affect their biological and physical properties. However, investigation of the structure–function relationship of polysaccharides is hampered by difficulties in accessing well-defined polysaccharides in sufficient quantities. Here we report a chemical approach to precision polysaccharides with native glycosidic linkages via living cationic ring-opening polymerization of 1,6-anhydrosugars. We synthesized well-defined polysaccharides with tunable molecular weight, low dispersity and excellent regio- and stereo-selectivity using a boron trifluoride etherate catalyst and glycosyl fluoride initiators. Computational studies revealed that the reaction propagated through the monomer α-addition to the oxocarbenium and was controlled by the reversible deactivation of the propagating oxocarbenium to form the glycosyl fluoride dormant species. Our method afforded a facile and scalable pathway to multiple biologically relevant precision polysaccharides, includingd-glucan,d-mannan and an unusuall-glucan. We demonstrated that catalytic depolymerization of precision polysaccharides efficiently regenerated monomers, suggesting their potential utility as a class of chemically recyclable materials with tailored thermal and mechanical properties.
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影响因子：
56.9
作者：
Zhu, Jian-Bo;Watson, Eli M.;Chen, Eugene Y. -X.
通讯作者：
Chen, Eugene Y. -X.
影响因子：
3.6
作者：
RUCKEL, ER;SCHUERCH, C
通讯作者：
SCHUERCH, C
影响因子：
62.1
作者：
Panza M;Pistorio SG;Stine KJ;Demchenko AV
通讯作者：
Demchenko AV
影响因子：
21.8
作者：
Sathe, Devavrat;Zhou, Junfeng;Wang, Junpeng
通讯作者：
Wang, Junpeng
DOI：
--
发表时间：
2004
期刊：
影响因子：
--
作者：
Nukaya;M;et al.;Tetsuo Kondo(共著)
通讯作者：
Tetsuo Kondo(共著)