Conformational Switching of a Foldamer in a Multicomponent System by pH-Filtered Selection between Competing Noncovalent Interactions.
Biomolecular systems are able to respond to their chemical environment through reversible, selective, noncovalent intermolecular interactions. Typically, these interactions induce conformational changes that initiate a signaling cascade, allowing the regulation of biochemical pathways. In this work, we describe an artificial molecular system that mimics this ability to translate selective noncovalent interactions into reversible conformational changes. An achiral but helical foldamer carrying a basic binding site interacts selectively with the most acidic member of a suite of chiral ligands. As a consequence of this noncovalent interaction, a global absolute screw sense preference, detectable by (13)C NMR, is induced in the foldamer. Addition of base, or acid, to the mixture of ligands competitively modulates their interaction with the binding site, and reversibly switches the foldamer chain between its left and right-handed conformations. As a result, the foldamer-ligand mixture behaves as a biomimetic chemical system with emergent properties, functioning as a "proton-counting" molecular device capable of providing a tunable, pH-dependent conformational response to its environment.
†School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom.
Julien
J
Brioche
†School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom.
Sarah J
SJ
Pike
‡Institute of Chemistry, University of Tartu, Ravila 14a, Tartu 50411, Estonia.
Sofja
S
Tshepelevitsh
‡Institute of Chemistry, University of Tartu, Ravila 14a, Tartu 50411, Estonia.
Ivo
I
Leito
†School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom.
Gareth A
GA
Morris
†School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom.|§Manchester Institute of Biotechnology, University of Manchester, 131 Princess Street, Manchester M1 7DN, United Kingdom.
Simon J
SJ
Webb
†School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom.
Jonathan
J
Clayden
D001665:Binding Sites; D040761:Biomimetic Materials / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D008024:Ligands; D008968:Molecular Conformation; D015394:Molecular Structure
D008024:Ligands