Mix and match recognition modules for the formation of H-bonded duplexes.
Mix and match recognition modules for the formation of H-bonded duplexes.
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DOI：
10.1039/c6sc01884j
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发表时间：
2016-09-01
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：
Stross AE;Iadevaia G;Hunter CA
在低聚分子中配置不同的氢键受体模块可以调节在非极性溶剂中形成的氢键双键的稳定性。具有互补氢键识别位点的低聚分子在非极性溶剂中形成稳定的双相化合物。在一个好的氢键供体和一个好的氢键受体之间使用单个氢键作为附加在非极性主链上的识别基序，导致具有可互换识别字母的结构。比较了三个不同家族的氢键受体低聚物（吡啶、吡啶n -氧化物或氧化膦识别模块）与一个家族的氢键给体低聚物（苯酚识别模块）的相互作用。所有三种供体-受体组合形成稳定的双链化合物，其中1:1复合物的稳定性随着识别模块数量的增加而增加。分子内氢键形成的有效摩尔浓度随着识别模块的灵活性降低而增加，从而导致双相（EM）的压缩：通过柔性连接剂连接到主链的磷化氢氧化物的有效摩尔浓度为14 mM；扭转自由度少三个的吡啶n -氧化物为40毫米，氢键的几何形状更有方向性的吡啶为80毫米。然而，吡啶-苯酚氢键比其他两种类型的氢键弱一个数量级，因此总体而言，吡啶- n -氧化物形成了最稳定的双相化合物，具有最高的协同度。结果表明，在相同的双工结构中使用不同的识别基序是可能的，这使得通过改变组分来调整配合物的整体稳定性成为可能。
Equipping oligomeric molecules with different H-bond acceptor modules modulates the stabilities of the H-bonded duplexes formed in non-polar solvents. Oligomeric molecules equipped with complementary H-bond recognition sites form stable duplexes in non-polar solvents. The use of a single H-bond between a good H-bond donor and a good H-bond acceptor as the recognition motif appended to a non-polar backbone leads to an architecture with interchangeable recognition alphabets. The interactions of three different families of H-bond acceptor oligomers (pyridine, pyridine N-oxide or phosphine oxide recognition module) with a family of H-bond donor oligomers (phenol recognition module) are compared. All three donor–acceptor combinations form stable duplexes, where the stability of the 1 : 1 complex increases with increasing numbers of recognition modules. The effective molarity for formation of intramolecular H-bonds that lead to zipping up of the duplex (EM) increases with decreasing flexibility of the recognition modules: 14 mM for the phosphine oxides which are connected to the backbone via a flexible linker; 40 mM for the pyridine N-oxides which have three fewer degrees of torsional freedom, and 80 mM for the pyridines where the geometry of the H-bond is more directional. However, the pyridine–phenol H-bond is an order of magnitude weaker than the other two types of H-bond, so overall the pyridine N-oxides form the most stable duplexes with the highest degree of cooperativity. The results show that it is possible to use different recognition motifs with the same duplex architecture, and this makes it possible to tune overall stabilities of the complexes by varying the components.
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影响因子：
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