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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DOI：
10.1002/anie.202013562
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发表时间：
2021-02-23
期刊：
影响因子：
--
通讯作者：
Buchard A
中科院分区：
文献类型：
--
作者：
McGuire TM;Bowles J;Deane E;Farrar EHE;Grayson MN;Buchard A
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，但关于天然多糖和合成碳水化合物聚合物中立体化学影响的报道仍然缺乏。在这里，我们报告的共结晶的区域和立体有规的聚醚衍生自d-和l-木糖，导致增强的热性能相比，对映体纯聚合物。据我们所知，这是手性相反的碳水化合物聚合物之间的立体复合物的第一个例子。相反，由单体的外消旋混合物获得的无规立构聚合物是无定形的。我们还表明，聚合物羟基基团适合于聚合后官能化。这些策略提供了一个家庭的碳水化合物聚醚，其物理和化学性质都可以控制，并打开了新的可能性，多糖模拟物在生物医学应用或作为先进的材料。作为多糖模拟物的合成碳水化合物聚醚通过由d-或l-木糖产生的氧杂环丁烷的区域规则阴离子开环聚合来合成。通过利用木糖的手性和不同的立体化学组成，可以控制所得材料的结晶度。将相反构型的纯手性聚合物混合在一起产生具有增强的热性质的立体复合物。
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 from d‐ and l‐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. Synthetic carbohydrate polyethers, which are polysaccharide mimics, are synthesised by regioregular anionic ring‐opening polymerisation of oxetanes produced from d‐ or l‐xylose. By exploiting the chirality of xylose and varying stereochemical composition, the crystallinity of the resulting materials can be controlled. Mixing together homochiral polymers of opposite configuration results in a stereocomplex with enhanced thermal properties.
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