合成H結合複合体の配列選択的形成
Alexander E Stross1, Giulia Iadevaia1, Diego Núñez-Villanueva1
1Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge CB2 1EW, U.K.
Journal of the American Chemical Society
|September 1, 2017
まとめ
フェノールとピリジンのN酸化基を持つオリゴマーは,水素結合によって安定した二重結合を形成する. 配列相補構造はより高い安定性を示し,特定の不一致配列は競争的結合を示す.
科学分野:
- 超分子化学
- 有機化学
- 化学生物学
背景:
- 特定の機能群を持つオリゴーマーが,自己組織化して秩序ある構造を形成します.
- 水素結合は分子認識と自己組織化における重要な相互作用である.
- 予測可能な複合体の形成のための合成分子を設計することは重要な課題です.
研究 の 目的:
- フェノールとピリジンN-オキシドを含む全ての可能な3メア配列を合成し,特徴づけること.
- 溶液中のこれらのオリゴマーの間の二重形成の熱力学を調査する.
- 配列の互補性と分子内相互作用が結合親和性にどのように影響するかを理解する.
主な方法:
- オリゴーマー合成のための還元性アミネーション化学.
- 核磁気共鳴 (NMR) 定位実験
- アソシエーション定数を定めるため,トルーエンのNMR稀縮実験.
主要な成果:
- 合成した8つの3メア配列
- 10^2から10^5M^-1までの測定された関連定数.
- 反並列配列複合体は一般的により安定していることが観察されました.
- 特定の水素結合のドナーと受容体の相互作用によって不一致の二重体の安定化が確認された.
- 分子内折り合いは 複合形成と競合し 安定性に影響する
- 配列互補の二重性は混合物において優位だが,高精度には交互配列を避ける必要がある.
結論:
- フェノールとピリジンN酸化物の間の水素結合の相互作用が二重結合を形成する.
- シーケンス互補性は安定した複合体の主要な要因ですが,特定の不一致は競争力があります.
- 分子内折り合いは,分子間結合親和性に大きく影響する.
- 順番を慎重に設計し,交互にパターンを避けることは,自己組み立てで高精度を達成するために不可欠です.
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