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Article Dans Une Revue Angewandte Chemie International Edition Année : 2020

Allosteric Recognition of Homomeric and Heteromeric Pairs of Monosaccharides by a Foldamer Capsule

Résumé

The recognition of either homomeric or heteromeric pairs of pentoses in an aromatic oligoamide double helical foldamer capsule was evidenced by circular dichroism (CD), NMR and X-ray crystallography. The foldamer was obtained readily by combining in a sequence aromatic amino-acids that code both for structural features such as strand curvature and self-assembly properties, together with functional features such as hydrogen bond donors and acceptors. The cavity of the host was predicted to be large enough to accommodate simultaneously two xylose molecules and form a 1:2 complex (one container, two saccharides). Solution and solid state data revealed the selective recognition of the α-4 C1-D-xylopyranose tautomer, which is bound at two identical sites in the foldamer cavity. Circular dichroism titrations demonstrated a positive cooperativity between the first and second binding events. Recognition is diastereoselective, i.e. P double helical handedness is quantitatively induced by D xylopyranose. In parallel, we found that the foldamer capsule also binds to arabinose with a 1:1 stoichiometry (one container, one saccharide). A step further was then achieved by sequestrating a heteromeric pair of pentoses, i.e. one molecule of α-4 C1-D-xylopyranose and one molecule of -1 C4-D-arabinopyranose despite the symmetrical nature of the host and despite the similar size of the guests. The 1:1:1 heterocomplex (one container, two different saccharides) was characterized by CD and multidimensional NMR to establish the hydrogen bonding network between the guests and the cavity wall. Subtle and novel induced-fit and allosteric effects are responsible for the outstanding selectivites observed. Altogether, these results further validate helical aromatic amide backbones as a solution of choice to elicit selective carbohydrate recognition.
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hal-03007647 , version 1 (23-11-2020)

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Pedro Mateus, Nagula Chandramouli, Cameron Mackereth, Brice Kauffmann, Yann Ferrand, et al.. Allosteric Recognition of Homomeric and Heteromeric Pairs of Monosaccharides by a Foldamer Capsule. Angewandte Chemie International Edition, 2020, 59 (14), pp.5797-5805. ⟨10.1002/anie.201914929⟩. ⟨hal-03007647⟩

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