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根据芳环上酰胺和氢键受体位置的不同,氢键介质的芳酰胺和酰肼折叠体可以产生折叠、螺旋、“之”字型、直线型及其他扩展型的构象。由于氢键具有较高的稳定性及芳酰胺固有的平面性特征,这一系列的芳酰胺寡聚体拥有较高的可预测的构象。芳酰胺骨架本身可以通过简单的酰胺键偶合反应构筑,而不同的官能团也可以选择性地引入到特定的骨架内部或其侧链内。因此,在过去几年内,我们重点研究了它们在构筑新的分子镊,形成凝胶、囊泡和液晶等有序功能超分子体系及促进大环分子体系合成方面的应用。近期我们又发现,氢键驱动的折叠片段能够并入到聚合物中,通过分子内氢键的断裂和恢复可逆调控聚合物的力学性质。本文主要介绍我们实验室在氢键驱动的芳酰胺折叠体结构–性质关系研究方面取得的进展。
Depending on the position of the amide and hydrogen bond acceptor on the aromatic ring, the aramid and hydrazide folds of the hydrogen bond mediator can produce folded, helical, lenticular, linear, and other extended conformations. Due to the high stability of hydrogen bonds and the inherent planarity characteristics of aramides, this series of aramid oligomers possess a higher predictable conformation. The aromatic amide skeleton itself can be constructed by a simple amide bond coupling reaction, and different functional groups can also be selectively introduced into a specific skeleton or within its side chain. Therefore, in the past few years, we have focused on their application in the construction of new molecular tweezers, the formation of ordered functional supramolecular systems such as gels, vesicles and liquid crystals, and the promotion of the synthesis of macrocyclic molecular systems. We have recently found that hydrogen-bonded folded fragments can be incorporated into polymers that reversibly modulate the mechanical properties of polymers by breaking and restoring intramolecular hydrogen bonds. This article describes the progress our lab has made in the structural-property-related studies of hydrogen-bonded aromatic polyamide sheets.