Increasing the Size of an Aromatic Helical Foldamer Cavity by Strand Intercalation

Abstract

The postsynthetic modulation of capsules based on helical aromatic oligoamide foldamers would be a powerful approach for controlling their receptor properties without altering the initial monomer sequences. With the goal of developing a method to increase the size of a cavity within a helix, a single-helical foldamer capsule was synthesized with a wide-diameter central segment that was designed to intercalate with a second shorter helical strand. Despite the formation of stable double-helical homodimers (K(dim)>10(7) M(-1)) by the shorter strand, when it was mixed with the single-helical capsule sequence, a cross-hybridized double helix was formed with K(a)>10(5) M(-1). This strategy makes it possible to direct the formation of double-helical heterodimers. On the basis of solution- and solid-state structural data, this intercalation resulted in an increase in the central-cavity size to give a new interior volume of approximately 150 Å(3).

Emergent supramolecular assembly properties of a recognition-encoded oligoester

“…[1][2][3][4][5][6][7][8] The relationship between sequence, folding and function has been extensively explored by Huc in families of amide oligomers. [9][10][11] These results suggest that sequenceencoded synthetic oligomers will be capable of showing the sophisticated recognition, self-assembly, catalysis and replication properties exhibited by biological oligomers. 12 We have been investigating the properties of synthetic oligomers based on the nucleic acid blueprint: an oligomeric backbone equipped with side-chains containing complementary hydrogen bonding recognition sites ( Fig.…”

Metal‐Coordination‐Assisted Folding and Guest Binding in Helical Aromatic Oligoamide Molecular Capsules

“…The modular nature of foldamer sequences constitute a key feature: sequence variants with added, deleted, or mutated monomers can quickly be produced to iteratively improve binding properties ,. Modulation of recognition has also been achieved through strand intercalation or in situ modification of a monomer, both of which can alter cavity size and recognition. Since binding properties are directly related to features imparted by the monomers, the development of foldamer‐based receptors can be said to be monomer‐driven.…”

Coordination complexes and biomolecules: A wise wedding for catalysis upgrade

“…artificial folded molecular architectures inspired by the structures and functions of biopolymers (glycoproteins [112,113] and peptide analogues [114]), is also of great potential [115]. Foldamers are already being used for organocatalysis [116][117][118], and can coordinate metallic ions [119], or form cavities [120]. Yet, to the best of our knowledge, no example was described for chemistrybased catalysis hosted by foldamer scaffolds, but this is likely to appear in a very close future.…”