From reactants to products via simple hydrogen-bonding networks: Information transmission in chemical reactions
From reactants to products via simple hydrogen-bonding networks: Information transmission in chemical reactions
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DOI：
10.1073/pnas.072695799
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发表时间：
2002-04-16
影响因子：
11.1
通讯作者：
Zerbetto, F
中科院分区：
文献类型：
--
作者：
Brancato, G;Coutrot, F;Zerbetto, F
信息的传递在自然界中无处不在，并且通常通过超分子氢键过程发生。在这里，我们报告说，有一个显着的相关性，在合成过程中的效率之间的氢键导向组装肽基轮烷[2]和对称性畸变的大环在最终产品的结构。据透露，柔性大环前体包裹在不对称氢键模板周围的能力影响反应产率和产物中大环的对称性畸变的可定量测量。当肽轮烷形成反应的产率高时，大环中的对称性畸变也是如此;当产率低时，表明组分之间的拟合差，大环对称性相对不受螺纹的影响。因此，在合成序列中，如在复杂的生物组装过程中，氢键可以编码和传输“信息”-在这种情况下，通过超分子驱动的多组分组装过程，化学实体之间的扭曲。如果这种现象是普遍的，它可能对有机化学中超分子导向反应的使用产生深远的影响。
The transmission of information is ubiquitous in nature and often occurs through supramolecular hydrogen bonding processes. Here we report that there is a remarkable correlation during synthesis between the efficiency of the hydrogen-bond-directed assembly of peptide-based [2]rotaxanes and the symmetry distortion of the macrocycle in the structure of the final product. It transpires that the ability of the flexible macrocycle-precursor to wrap around an unsymmetrical hydrogen bonding template affects both the reaction yield and a quantifiable measure of the symmetry distortion of the macrocycle in the product. When the yields of peptide rotaxane-forming reactions are high, so is the symmetry distortion in the macrocycle; when the yields are low, indicating a poor fit between the components, the macrocycle symmetry is relatively unaffected by the thread. Thus during a synthetic sequence, as in complex biological assembly processes, hydrogen bonding can code and transmit "information"-in this case a distortion from symmetry-between chemical entities by means of a supramolecularly driven multicomponent assembly process. If this phenomenon is general, it could have far reaching consequences for the use of supramolecular-directed reactions in organic chemistry.