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Precision native polysaccharides from living polymerization of anhydrosugars

Nature Chemistry volume 15, pages 1276–1284 (2023)Cite this article

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Abstract

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, including d-glucan, d-mannan and an unusual l-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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Fig. 1: Living cationic ring-opening polymerization of 1,6-anhydrosugars.
Fig. 2: Preparation and characterization of precision polysaccharides.
Fig. 3: Monomer scope and computational studies.
Fig. 4: Synthesis of biologically relevant precision polysaccharides.
Fig. 5: Chemical recycling and material properties of precision polysaccharides.

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Data availability

All data are available in the manuscript or the Supplementary Information. Experimental data and characterization data for all new compounds prepared during these studies are provided in the Supplementary Information of this paper. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Arnold and Mabel Beckman Foundation through a Beckman Young Investigator Award to J.N. NMR characterizations were supported by the National Science Foundation Major Research Instrumentation (NSF-MRI) Program, under award number CHE-2117246. We thank W. Z. Fan for assistance with the computational studies and J. B. Matson, S. Blosch, M. J. Zhong, M. X. Cao, C. F. Ke, Q. M. Lin, T. S. Emerick, T. Goodwin, M. W. Grinstaff, S. EI-Arid, M. Zhou, C. J. Yang, C. Liu, T. Jayasundera, M. Domin, S.-Y. Liu, J. A. Byers and J. Morken for characterization assistance and helpful discussions.

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Authors and Affiliations

  1. Department of Chemistry, Boston College, Chestnut Hill, MA, USA

    Lianqian Wu, Zefeng Zhou, Shoshana Dym, Zhensheng Zhao & Jia Niu

  2. School of Polymer Science and Polymer Engineering, University of Akron, Akron, OH, USA

    Devavrat Sathe, Junfeng Zhou & Junpeng Wang

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Contributions

L.W. and J.N. conceived and designed the project. J.N. oversaw the project. L.W., S.D. and Z. Zhao performed the experiments. Z. Zhou performed the computational studies. D.S., J.Z. and J.W. performed tensile testing. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Jia Niu.

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Competing interests

A PCT patent application (PCT/US2022/078036) based on this work has been filed by Boston College. J.N. and L.W. are listed as inventors in this application. The remaining authors declare no competing interests.

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Peer review information

Nature Chemistry thanks Brooks Abel, Cassandra Callmann and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–150, Tables 1–9 and synthetic Procedures.

Supplementary Data 1

The XYZ coordinates for the DFT calculations.

Source data

Source Data Fig. 2

MALDI-MS, SEC and kinetic data.

Source Data Fig. 4

SEC data for enzymatic degradation.

Source Data Fig. 5

SEC, TGA, DSC, PXRD and tensile test data.

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Wu, L., Zhou, Z., Sathe, D. et al. Precision native polysaccharides from living polymerization of anhydrosugars. Nat. Chem. 15, 1276–1284 (2023). https://doi.org/10.1038/s41557-023-01193-2

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