芳香折叠体的动态共价组装研究

To develop novel aggregates with ordered structures，and to innovate their specialized functions is one of intensively hot topics in the field of supramolecular chemistry and material science. In this project, we will design and synthesize a series of novel foldamer systems with defined structures and functions via dynamic combinatorial chemistry. Induced by guest templates, self-organized units with aldehyde and hydrazide functional groups could be selectively combined with guests via intermolecular hydrogen bonds and hydrophobic interactions, and thus ultimately assemble to foldamers through reversible covalent bonds. The target of this project will focus on the investigation of the cooperative effect of guest induction and hydrogen bond. Furthermore, the recognition ability of the resulting foldamers will also be explored due to the helical cavity. These studies would help to provide new horizon to the field of new foldamers with characteristic functions.

开发新型的结构有序的聚集体，探索其特殊的功能是当前超分子化学和材料科学研究的主要热点之一。本申请项目拟通过动态共价组装化学，设计和合成一系列有特殊结构和功能的新型折叠体。我们计划使用带有特定官能团（醛基、酰肼）的预组织结构基元，在客体模板的诱导作用下，利用分子间氢键及疏水作用使结构基元选择性地与客体分子相络合，并通过可逆共价键最终组装成功能性的螺旋折叠体。本课题的目标是发掘客体诱导与氢键预组织的协同作用在动态共价组装中的影响规律，在此基础上，进一步研究螺旋结构空腔在分子识别等方面的性质。本研究将有助于为探究有特殊功能的新型螺旋折叠体提供新思路。

本项目利用动态共价组装方式构筑螺旋折叠分子，发展了其高效、动态构建方法，实现了其结构、性能的可调控性。取得主要成果如下：一是利用能够形成分子内氢键的腙键（酰腙键）构筑螺旋折叠分子，分子内氢键使得腙键（酰腙键）采取顺式优势构型，诱导整个分子序列形成螺旋结构。从而简化了以往酰胺螺旋分子的繁杂合成步骤，这为进一步发展人工分子体系的高级组装结构提供了重要的参考意义。二是通过二硫键实现了折叠分子的高效连接及序列的动态转化。进一步，在折叠分子末端引入手性基团，这种顺平行-反平行序列动态转化能有效调控折叠分子的螺手性，实现手性信号的调节。共发表论文6篇，授权专利1件。