Control of Crystallinity and Stereocomplexation of Synthetic Carbohydrate Polymers from D- and L-Xylose

Thomas McGuire; Jessica Bowles; Edward Deane; Elliot Farrar; Matthew Grayson; Antoine Buchard

doi:10.1002/anie.202013562

Control of Crystallinity and Stereocomplexation of Synthetic Carbohydrate Polymers from D- and L-Xylose

Thomas McGuire, Jessica Bowles, Edward Deane, Elliot Farrar, Matthew Grayson, Antoine Buchard

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

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 cocrystallization 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 polymers hydroxyl groups are amenable to post-polymerization 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.

Original language	English
Pages (from-to)	4524 –4528
Journal	Angewandte chemie-International edition
Volume	60
Issue number	0
Early online date	7 Jan 2021
DOIs	https://doi.org/10.1002/anie.202013562
Publication status	Published - 23 Feb 2021

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10.1002/anie.202013562Licence: CC BY

Cite this

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abstract = "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 cocrystallization 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 polymers hydroxyl groups are amenable to post-polymerization 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.",

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T1 - Control of Crystallinity and Stereocomplexation of Synthetic Carbohydrate Polymers from D- and L-Xylose

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AU - Bowles, Jessica

AU - Deane, Edward

AU - Farrar, Elliot

AU - Grayson, Matthew

AU - Buchard, Antoine

PY - 2021/2/23

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AB - 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 cocrystallization 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 polymers hydroxyl groups are amenable to post-polymerization 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.

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