A threading receptor for polysaccharides

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Abstract

Cellulose, chitin and related polysaccharides are key renewable sources of organic molecules and materials. However, poor solubility tends to hamper their exploitation. Synthetic receptors could aid dissolution provided they are capable of cooperative action, for example by multiple threading on a single polysaccharide molecule. Here we report a synthetic receptor designed to form threaded complexes (polypseudorotaxanes) with these natural polymers. The receptor binds fragments of the polysaccharides in aqueous solution with high affinities (Ka up to 19,000 M−1), and is shown—by nuclear Overhauser effect spectroscopy—to adopt the threading geometry. Evidence from induced circular dichroism and atomic force microscopy implies that the receptor also forms polypseudorotaxanes with cellulose and its polycationic analogue chitosan. The results hold promise for polysaccharide solubilization under mild conditions, as well as for new approaches to the design of biologically active molecules.

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Figure 1: Receptor design.
Figure 2: 1H NMR evidence for receptor 4 binding oligosaccharides.
Figure 3: Representative ITC data and analysis curves.
Figure 4: AFM studies of receptor 4 + cellulose.
Figure 5: AFM studies of receptor 4 + chitosan.

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Acknowledgements

This work was supported by the European Commission (Marie Curie Fellowship to J.M.C.-S.), and by the Engineering and Physical Sciences Research Council (EPSRC) through grant number EP/I028501/1 and a studentship to C.M.R. funded via the Bristol Chemical Synthesis Doctoral Training Centre (EP/G036764/1). PeakForce AFM was carried out in the Chemical Imaging Facility, University of Bristol, with equipment funded by the Engineering and Physical Sciences Research Council under grant ‘Atoms to Applications’ grant ref. (EP/K035746/1).

Author information

J.M.C.-S. and T.J.M. performed the synthetic work. T.J.M. performed NMR and ITC binding studies, C.M.R. performed some ITC studies and T.S.C. performed the ICD measurements. T.J.M. and M.P.C. were responsible for the structural NMR work. T.J.M. and R.L.H. performed the AFM analyses. The paper was written by T.J.M. and A.P.D. with input from the other authors. A.P.D. designed the receptor and directed the study.

Correspondence to Anthony P. Davis.

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The authors declare no competing financial interests.

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Mooibroek, T., Casas-Solvas, J., Harniman, R. et al. A threading receptor for polysaccharides. Nature Chem 8, 69–74 (2016) doi:10.1038/nchem.2395

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