Control of Crystallinity and Stereocomplexation of Synthetic Carbohydrate Polymers from d - and l -Xylose
Control of Crystallinity and Stereocomplexation of Synthetic Carbohydrate Polymers from d - and l -Xylose
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d-和 l-木糖合成碳水化合物聚合物的结晶度和立体络合控制
DOI：
10.1002/ange.202013562
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发表时间：
2021
影响因子：
--
通讯作者：
McGuire T
中科院分区：
文献类型：
--
作者：
McGuire T
操纵聚合物的立体化学是改变其物理性质的有力方法。尽管单糖具有手性，但关于立体化学对天然多糖和合成碳水化合物聚合物的影响的报道仍然缺乏。本文中，我们报道了由木糖和木糖衍生的区域聚醚和立体规则聚醚的共结晶，与对映纯聚合物相比，它们的热性能得到了增强。据我们所知，这是第一个手性相反的碳水化合物聚合物之间形成立体配合物的例子。相反，由单体的外消旋混合物得到的无规聚合物是无定形的。我们还表明，聚合物羟基易于聚合后功能化。这些策略提供了一系列碳水化合物聚醚，其物理和化学性质都可以控制，并为生物医学应用或作为先进材料的多糖模拟物开辟了新的可能性。
Manipulating the stereochemistry of polymers is a powerful method to alter their physical properties. Despite the chirality of monosaccharides, reports on the impact of stereochemistry in natural polysaccharides and synthetic carbohydrate polymers remain absent. Herein, we report the cocrystallisation of regio‐ and stereoregular polyethers derived fromd‐ andl‐xylose, leading to enhanced thermal properties compared to the enantiopure polymers. To the best of our knowledge, this is the first example of a stereocomplex between carbohydrate polymers of opposite chirality. In contrast, atactic polymers obtained from a racemic mixture of monomers are amorphous. We also show that the polymer hydroxyl groups are amenable to post‐polymerisation functionalization. These strategies afford a family of carbohydrate polyethers, the physical and chemical properties of which can both be controlled, and which opens new possibilities for polysaccharide mimics in biomedical applications or as advanced materials.