Synthetic molecules for biomimetic information handling

通过结合生物学的信息存储和复制策略，即核碱基之间的特定氢键，以及新型“可折叠文件夹”中氢键重组的潜力，我们建议开发一种新的、人工的、生物启发的化学系统信息传递机制。基于初步的建模研究，我们将重点关注两种类型的聚脲结构，由“Nowick”式和“Guichard”式基元构建，它们在溶液中自发折叠，形成分子内极化氢键网络。在加入简单的化学添加剂后，与折叠体形成竞争性的分子间氢键，这些网络的方向性可以被改变，将构象混合物转变为定义良好的单向网络。分子事件，如可逆开关，化学传感，远距离信息通信将被研究。然后，将研究诸如核碱基之类的仿生添加剂，并分析它们对低聚物折叠的影响。最后，将构建与添加剂相互作用的非光谱“读出”结构，例如表现出“关闭”的荧光或“关闭”的催化活性。本文还将研究这些材料在光化学可切换分子器件中的应用。

By combining biology's information storage and replication strategies, namely specific hydrogen-bonding between nucleobases, with the potential for hydrogen-bond reorganisation in novel 'refoldable foldamers', we propose to develop a new, artificial but bio-inspired mechanism for the transfer of information in chemical systems. Based on preliminary modelling studies, we will focus on two types of polyurea structures, built from 'Nowick'-style and 'Guichard'-style motifs, which spontaneously fold in solution, forming intramolecular polarized hydrogen-bond networks. Upon addition of simple chemical additives forming competitive intermolecular hydrogen bonds with the foldamer, the directionality of these networks could be modified, transforming a conformational mixture to a well-defined unidirectional network. Molecular events such as reversible switching, chemical sensing, and long-distance information communication will be studied. Then, biomimetic additives such as nucleobases will be investigated, and their impact on the folding of the oligomers will be analysed. Finally, structures that give a non-spectroscopic 'readout' of the interaction with the additive will be built, which for example exhibit 'off-on' fluorescence or 'off-on' catalytic activity. The application of these foldamers in the construction of photochemically switchable molecular devices will also be investigated.