Cooperative duplex formation by synthetic H-bonding oligomers.
Cooperative duplex formation by synthetic H-bonding oligomers.
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DOI：
10.1039/c5sc03414k
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发表时间：
2016-01-01
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
柔性苯酚-氧化膦低聚物有望成为一类新型合成信息分子。采用还原胺化化学合成了一系列配备苯酚氢键供体和氧化膦氢键受体的柔性低聚物。互补低聚物之间的氢键相互作用导致双链复合物的形成，并通过 NMR 滴定和热变性实验对其进行了表征。链上每添加一个氢键基团，双链体的稳定性就会增加一个数量级。类似地，双链体组装的焓变和双链体变性的熔化温度都随着链长度的增加而增加。这些观察结果表明，尽管具有柔性主链，但沿着低聚物的氢键形成是协作的，并且分子内氢键形成的有效摩尔浓度（14 mM）足以使用这种方法传播更长双链体的形成。用于量化螯合协同性的乘积 K EM 为 5，这意味着组装的双链体中每个氢键的数量超过 80%。这些寡聚物的模块化设计代表了合成信息分子设计的一般策略，这些分子可能以与核酸相同的方式编码和复制化学信息。
Flexible phenol-phosphine oxide oligomers show promise as a new class of synthetic information molecule. A series of flexible oligomers equipped with phenol H-bond donors and phosphine oxide H-bond acceptors have been synthesised using reductive amination chemistry. H-bonding interactions between complementary oligomers leads to the formation of double-stranded complexes which were characterised using NMR titrations and thermal denaturation experiments. The stability of the duplex increases by one order of magnitude for every H-bonding group added to the chain. Similarly, the enthalpy change for duplex assembly and the melting temperature for duplex denaturation both increase with increasing chain length. These observations indicate that H-bond formation along the oligomers is cooperative despite the flexible backbone, and the effective molarity for intramolecular H-bond formation (14 mM) is sufficient to propagate the formation of longer duplexes using this approach. The product K EM, which is used to quantify chelate cooperativity is 5, which means that each H-bond is more than 80% populated in the assembled duplex. The modular design of these oligomers represents a general strategy for the design of synthetic information molecules that could potentially encode and replicate chemical information in the same way as nucleic acids.
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