《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(8):2119-2123

Peptide foldamers containing both cis ‐β‐aminocyclopentanecarboxylic acid and α‐amino acid residues combined in various sequence patterns (ααβ, αααβ, αβααβ, and ααβαααβ) were screened using CD and NMR spectroscopy for the tendency to form helices. ααβ‐Peptides were found to fold into an unprecedented and well‐defined 16/17/15/18/14/17‐helix. By extending the length of the sequence or shifting a fragment of the sequence from one terminus to another in ααβ‐peptides, the balance between left‐handed and right‐handed helix populations present in the solution can be controlled. Engineering of the peptide sequence could lead to compounds with either a strong propensity for the selected helix sense or a mixture of helical conformations of opposite senses.  相似文献   

    

《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(12):3397-3401

A linear molecular architecture equipped with complementary three‐fold hydrogen‐bonding units embedded with a photoswitchable trans ‐tetrafluoroazobenzene moiety was synthesized. The trans to cis photoisomerism of the azobenzene unit induced drastic changes in the molecular architecture as a result of intramolecular hydrogen bonding as evidenced by NMR spectroscopy and size exclusion chromatography. A minute stereogenic element in the linear trans state enabled stereoselective folding into the cis state, thus producing a globular architecture with enhanced chiroptical property.  相似文献   

    

《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(24):6927-6931

The development of foldamer‐based receptors is driven by the design of monomers with specific properties. Herein, we introduce a pyridazine‐pyridine‐pyridazine diacid monomer and its incorporation into helical aromatic oligoamide foldamer containers. This monomer codes for a wide helix diameter and can sequester metal ions on the inner wall of the helix cavity. Crystallographic studies and NMR titrations show that part of the metal coordination sphere remains available and may then promote the binding of a guest within the cavity. In addition to metal coordination, binding of the guest is assisted by cooperative interactions with the helix host, thereby resulting in significant enhancements depending on the foldamer sequence, and in slow guest capture and release on the NMR time scale. In the absence of metal ions, the pyridazine‐pyridine‐pyridazine monomer promotes an extended conformation of the foldamer that results in aggregation, including the formation of an intertwined duplex.  相似文献   

    

Xiang Wang  Quan Gan  Barbara Wicher  Yann Ferrand  Ivan Huc 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(13):4249-4253

We have investigated the self‐assembly of a dissymmetrical aromatic oligoamide helix on linear amido‐carbamate rods. A dissymmetric sequence bearing two differentiated ends is able to wrap around dissymmetric dumbbell guest molecules. Structural and thermodynamic investigations allowed us to decipher the mode of binding of the helix that can bind specifically to the amide and carbamate groups of the rod. In parallel kinetic studies of threading and sliding of the helix along linear axles were also monitored by ¹H NMR. Results show that threading of a dissymmetrical host can be kinetically biased by the nature of the guest terminus allowing a preferential sense of sliding of the helix. The study presented below further demonstrates the valuable potential of foldaxanes to combine designed molecular recognition patterns with fine control of self‐assembly kinetics to conceive complex supramolecular events.  相似文献