Mix and match backbones for the formation of H-bonded duplexes.
Mix and match backbones for the formation of H-bonded duplexes.
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DOI：
10.1039/c5sc04467g
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发表时间：
2016-03-01
期刊：
影响因子：
8.4
通讯作者：
Hunter CA
中科院分区：
文献类型：
--
作者：
Iadevaia G;Stross AE;Neumann A;Hunter CA
六种异构体骨架组合可互换使用以构建具有相似稳定性的稳定H键合双链体。定义明确的超分子组装体的形成涉及分子间和分子内相互作用之间的竞争，这是量化的有效摩尔浓度。在两个寡聚体之间形成双链体，所述两个寡聚体装备有沿非相互作用主链沿着显示的识别位点，这要求一旦形成一种分子间相互作用，则所有后续相互作用都以分子内意义发生。该过程的效率由连接识别位点的骨架的几何互补性和构象灵活性决定。在这里，我们报告了一系列的氧化膦氢键受体AA 2-聚体和苯酚氢键供体DD 2-聚体，其中两个识别位点连接的异构骨架模块，在几何形状和灵活性不同。所有AA和DD的组合形成稳定的AA·DD双链体，其中两个合作的H-键导致的稳定性增加了一个数量级相比，相应的A·D复合物，只能形成一个H-键。对于所有六种可能的骨架组合，双链体形成的有效摩尔浓度大致恒定（7-20 mM）。因此，严格的互补性和高度的preorganisation是不需要有效的超分子组装。只要有一定的灵活性，完全不同的骨架模块可以互换使用，以构建稳定的氢键双链体。
Six isomeric backbone combinations can be used interchangeably to construct stable H-bonded duplexes of similar stability. The formation of well-defined supramolecular assemblies involves competition between intermolecular and intramolecular interactions, which is quantified by effective molarity. Formation of a duplex between two oligomers equipped with recognition sites displayed along a non-interacting backbone requires that once one intermolecular interaction has been formed, all subsequent interactions take place in an intramolecular sense. The efficiency of this process is governed by the geometric complementarity and conformational flexibility of the backbone linking the recognition sites. Here we report a series of phosphine oxide H-bond acceptor AA 2-mers and phenol H-bond donor DD 2-mers, where the two recognition sites are connected by isomeric backbone modules that vary in geometry and flexibility. All AA and DD combinations form stable AA·DD duplexes, where two cooperative H-bonds lead to an increase in stability of an order of magnitude compared with the corresponding A·D complexes that can only form one H-bond. For all six possible backbone combinations, the effective molarity for duplex formation is approximately constant (7–20 mM). Thus strict complementarity and high degrees of preorganisation are not required for efficient supramolecular assembly. Provided there is some flexibility, quite different backbone modules can be used interchangeably to construct stable H-bonded duplexes.
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