在合成宏分子中对序列识别的符合性调制.
Zhixue Zhu1, Christine J Cardin, Yu Gan
1Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD, United Kingdom. zhixue.zhu.rdg@googlemail.com
Journal of the American Chemical Society
|October 25, 2011
概括
具有不同乙醇-和乙醇-硫连接的芳香性共聚胺对以为基础的 tweezer 分子表现出明显的结合亲和力. 这些差异源于影响二次π-π-堆叠相互作用的形状变化.
科学领域:
- 聚合物化学 聚合物化学
- 超分子化学 超分子化学
- 材料科学 材料科学 材料科学
背景情况:
- 高分子量芳香型共聚胺具有pyromellitimide单位.
- 这些单元是以基 (K) 或硫 (S) 残留物,形成KIK,KIS和SIS等三重序列.
- 基于pyrene的 tweezer-molecules通过π-π堆积和键结合与这些聚合物结合.
研究的目的:
- 为了研究基于pyrene的 tweezer-molecules对不同芳香的聚胺三重序列的各种结合强度.
- 阐明控制这些结合亲和力的分子机制.
- 为了将共聚胺的结构特征与它们的结合能力相关联.
主要方法:
- 核磁共振 (NMR) 光谱法用于测量复杂化转移.
- 子-聚合物结合常数的确定.
- 子-聚合物相互作用的计算建模.
- 子复合体的单晶X射线衍射分析.
主要成果:
- 约束力按照以下顺序进行:SIS > KIS > KIK.
- (1) H NMR复杂化转移和结合常数量化这些差异.
- 计算模型和X射线晶体学显示,在二基和二硫连接处的形状偏好是关键.
- 这些偏好决定了链条折叠和二次π-π堆叠的发生.
结论:
- 芳香环在以太-和以太-硫连接中的形状灵活性显著影响了针-分子结合.
- 二次π-π-堆积相互作用在观察到的结合强度变化中起着至关重要的作用.
- 了解这些结构-性质关系,可以设计先进的超分子材料.
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