title: Kinetics of helix-handedness inversion: folding and unfolding in aromatic amide oligomers.
abstract: A series of helically folded oligoamides of 8-amino-2-quinoline carboxylic acid possessing 6, 7, 8, 9, 10 or 16 units are prepared following convergent synthetic schemes. The right-handed (P) and the left-handed (M) helical conformers of these oligomers undergo an exchange slow enough to allow their chromatographic separation on a chiral stationary phase. Thus, the M conformer is isolated for each of these oligomers and its slow racemization in hexane/CHCl(3) solutions is monitored at various temperatures using chiral HPLC. The kinetics of racemization at different temperatures in hexane/CHCl(3) (75:25 vol/vol) are fitted to a first order kinetic model to yield the kinetic constant and the Gibbs energy of activation for oligomers having 6, 7, 8, 9, 10 or 16 quinoline units. This energy gives the first quantitative measure of the exceptional stability of the helical conformers of an aromatic amide foldamer with respect to its partly unfolded conformations that occur between an M helix and a P helix. The trend of the Gibbs energy as a function of oligomer length suggests that helix-handedness inversion does not require a complete unfolding of a helical strand and may instead occur through the propagation of a local unfolding separating two segments of opposite handedness.
authors: Institut Européen de Chimie et Biologie, Université de Bordeaux - CNRS UMR 5248, 2 rue Escarpit, 33607 Pessac, France.
authors: Nicolas
authors: N
authors: Delsuc
authors: Takahiro
authors: T
authors: Kawanami
authors: Julien
authors: J
authors: Lefeuvre
authors: Atsuomi
authors: A
authors: Shundo
authors: Hirotaka
authors: H
authors: Ihara
authors: Makoto
authors: M
authors: Takafuji
authors: Ivan
authors: I
authors: Huc
mesh_terms: D000577:Amides / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D011804:Quinolines / Q000737:chemistry; D013237:Stereoisomerism; D013696:Temperature; D013816:Thermodynamics
chemical_list: D000577:Amides; D011804:Quinolines; C037219:quinoline