合成H键复合体的序列选择性形成
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
概括
有和二氧化物组的寡合体通过键形成稳定的双重体. 序列补充结构表现出更高的稳定性,特定的不匹配序列显示竞争性结合.
科学领域:
- 超分子化学
- 有机化学
- 化学生物学
背景情况:
- 具有特定功能组的寡合体可以自组成有序结构.
- 键是分子识别和自我组合中的关键相互作用.
- 设计可预测的复杂分子是一个重大的挑战.
研究的目的:
- 合成和描述所有可能的含有和胺N-氧化物的3分子序列.
- 研究溶液中这些寡合体之间的双重形成的热力学.
- 了解序列互补性和分子内相互作用如何影响结合亲和力.
主要方法:
- 降解氨化化学用于寡合物合成.
- 核磁共振 (NMR) 定位实验
- 在中进行NMR稀释实验以确定关联常量.
主要成果:
- 合成了所有8种可能的三分子序列.
- 在10^2到10^5M^-1之间测量了关联常数.
- 观察到反平行序列-补充双重组通常更稳定.
- 通过特定的键供体-接受体相互作用确定不匹配的双重体.
- 发现分子内折叠与双重形成竞争,影响稳定性.
- 序列互补的双重体在混合物中占主导地位,但高保真性要求避免交替序列.
结论:
- 和二氧化物单位之间的结合相互作用驱动双重组的形成.
- 序列互补是稳定的双重组的一个主要因素,但特定的不匹配可能是竞争性的.
- 分子内折叠可以显著影响分子间结合亲和力.
- 谨慎的序列设计,避免交替的模式,对于实现自组装的高保真度至关重要.
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