Controlling Dipole Orientation through Curvature: Aromatic Foldamer Bent β-Sheets and Helix-Sheet-Helix Architectures - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Journal of the American Chemical Society Année : 2017

Controlling Dipole Orientation through Curvature: Aromatic Foldamer Bent β-Sheets and Helix-Sheet-Helix Architectures

Résumé

The helix, turn and beta-strand motifs of biopolymer folded structures have been found to prevail also in non-natural backbones. In contrast, foldamers with aryl rings in their main chains possess distinct conformations that may give access to folded objects beyond the reach of peptidic and nucleotidic backbones. In search for such original architectures we have explored the effect of bending aromatic amide beta-sheets using building blocks that impart curvature. Cyclic and multi-turn noncyclic sequences were synthesized and their structures were characterized in solution and in the solid state. Stable bent-sheet conformations were shown to prevail in chlorinated solvents. In these structures, folding overcomes intramolecular electrostatic repulsions and forces local dipoles in each layer of the stacked strands to align in a parallel fashion. Sequences having helical segments flanking a central bent aromatic beta-sheet were then synthesized and shown to form well-defined helix-turn-helix architectures in which helical and sheet sub-components conserve their respective integrity. These objects have a unique basket shape; they possess a cavity the depth and width of which reflects the curvature of the beta-sheet segment. They can be compared to previously described helical closed-shell receptors in which a window has been open thus providing a means to control guest binding and release pathways and kinetics. As a proof of concept, guest binding to one of the helix-sheet-helix structure is indeed found to be fast on the NMR time scale while it is generally slow in the case of helical capsules.

Domaines

Chimie organique
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Dates et versions

hal-01848980 , version 1 (25-07-2018)

Identifiants

Citer

Arthur Lamouroux, Laure Sebaoun, Barbara Wicher, Brice Kauffmann, Yann Ferrand, et al.. Controlling Dipole Orientation through Curvature: Aromatic Foldamer Bent β-Sheets and Helix-Sheet-Helix Architectures. Journal of the American Chemical Society, 2017, 139 (41), pp.14668614675. ⟨10.1021/jacs.7b07961⟩. ⟨hal-01848980⟩

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