Kinetics of helix-handedness inversion: Folding and unfolding in aromatic amide oligomers

Nicolas Delsuc, Takahiro Kawanami, Julien Lefeuvre, Atsuomi Shundo, Hirotaka Ihara, Makoto Takafuji, Ivan Huc

研究成果: ジャーナルへの寄稿学術誌査読

70 被引用数 (Scopus)

抄録

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/CHCl3 solutions is monitored at various temperatures using chiral HPLC. The kinetics of racemization at different temperatures in hexane/CHCl3 (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.

本文言語英語
ページ(範囲)1882-1890
ページ数9
ジャーナルChemPhysChem
9
13
DOI
出版ステータス出版済み - 9月 15 2008
外部発表はい

!!!All Science Journal Classification (ASJC) codes

  • 原子分子物理学および光学
  • 物理化学および理論化学

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