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Tug‐of‐War in a Dynamic Helical Peptide: Solvent‐Induced Helix‐Helix Transition of a Lactam‐Bridged Peptide Composed of Point‐ and Axial Chiralities Remote from Each Other
Author(s) -
Urushima Akio,
Ousaka Naoki,
Yashima Eiji
Publication year - 2018
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201801111
Subject(s) - oligopeptide , helix (gastropod) , chirality (physics) , chemistry , stereochemistry , peptide , crystallography , moiety , solvent , biochemistry , physics , chiral symmetry , biology , ecology , quantum mechanics , snail , nambu–jona lasinio model , quark
The dynamic axial chirality of oligopeptide‐bound 2,2′‐bipyridine (bpy) residues can be remote‐controlled and diastereoselectively locked. A right‐handed ( P )‐3 10 ‐helix is first induced in the dynamic helical oligopeptide by an l ‐valine ( l ‐Val) far from the bpy moiety and the induced axial bpy chirality is diastereoselectively dioxidized. The resulting l ‐Val‐containing linear oligopeptides at the 3,3′‐positions retain their ( P )‐3 10 ‐helices independent of the axial chirality (a R or a S ) of the N‐terminal N , N′ ‐dioxide‐bpy unit, while a lactam‐bridged dynamic helical oligopeptide exhibits a unique solvent‐induced helix‐helix transition as a result of competitive helix‐inducing biases between the l ‐Val and (a R ) or (a S )‐ N , N′ ‐dioxide‐bpy residues remote from each other along the entire oligopeptide chain in a tug‐of‐war like manner.