水溶性萘基四内酰胺大环的合成及其分子识别研究

分子识别在自然界中普遍存在，是许多生命现象与生物功能的基础。如何在水相中选择性识别极性分子或极性基团是超分子化学发展亟待解决的难题之一。设计并合成能够特异性高效识别客体分子的主体体系是超分子化学的研究热点。其中，四内酰胺大环具有较大的非极性疏水表面和包含极性官能团的内部空腔，类似于自然界中许多蛋白质的两亲性结合口袋。这类大环在水相或者有机溶剂中能选择性地识别大量不同结构的客体分子，在超分子方面具有非常广阔的应用前景。但是，目前文献报道的四内酰胺大环通常以苯基或者蒽基作为芳香侧壁，但其构象单一且空腔较为狭窄，可识别的客体分子受限。

为解决这一问题，本文引入2,6位桥接的萘基作为芳香侧壁，构筑新型萘基四内酰胺大环。所合成大环将具有比苯基或蒽基大环更大的空腔；且萘环通过翻转可以产生两种较为稳定的构象，在键合客体时可以选择优势构象以达到最大强度键合。本论文首先合成了新型水溶性萘基四内酰胺大环WNT，并研究了其对核黄素的光保护性能；随后考察了大环WNT在水溶液中对各类染料的主客体化学。具体分为以下两个部分：

（一）通过引入2,6-位桥接的萘作为芳香侧壁，构筑了新型水溶性萘基四内酰胺大环WNT。核磁、紫外、荧光和等温滴定量热等实验研究发现：WNT利用氢键和疏水效应协同作用，实现了对核黄素的选择性键合，键合常数高达1.2 × 10⁷ M^-1，远高于环糊精和葫芦脲等经典大环。此外，与游离的核黄素相比，主客体复合物中核黄素的光稳定性得到了显著增强。这一特性使得大环主体WNT可作为核黄素类化合物的光稳定剂，并进一步用于药物或添加剂中。

（二）本论文还考察了大环WNT和水溶性有机染料分子的主客体化学。实验结果表明，大环WNT对常见的芳香染料具有较强的键合能力，键合常数在10⁴ ~ 10⁶ M^-1之间。此外，染料与大环WNT的键合伴随明显的荧光增强或猝灭，这一特性为超分子染料体系在生物成像等方面提供了参考。

Molecular recognition is ubiquitous in nature and it is the basis of many life phenomena. How to selectively recognize polar molecules or polar groups in water is one of the urgent problems for the development of supramolecular chemistry. Therefore to design and synthesize of new host systems that can recognize guests with specificity and high efficiency is a research hotspot at the moment. Tetralactam macrocycles have large nonpolar hydrophobic surface and a cavity containing many polar functional groups, similar to the amphiphilic binding pocket of many proteins in nature. These macrocycles can selectively recognize a large number of guests with different structures in aqueous phase or organic solvent and have a very broad prospect in supramolecular applications. However, tetralactam macrocycles reported in literature usually have phenyl or anthracene group as the side wall which has only one conformation. And their cavity is relatively narrow, so the guests that can be recognized are limited.

By introducing the 2,6-position bridged naphthalene group as the construction unit, the macrocycle will have a larger cavity than the phenyl- or anthracene-based macrocycles. Furthermore, the naphthalene can produce two mainly conformations by flipping, so the preferred conformation may be selected to achieve the maximum binding strength. In this paper, a novel water-soluble naphthotetralactam macrocycle WNT was synthesized and its photoprotection ability for riboflavin was studied. Subsequently, the host-guest chemistry of WNT for various dyes in aqueous solution was investigated. Specifically divided into the following two parts:

First, a a novel water-soluble naphthotetralactam macrocycle WNT was constructed by introducing 2,6-bridged naphthalene as aromatic side wall. Experimental studies on NMR, UV, fluorescence and isothermal titration have found that host WNT achieves selective binding with riboflavin in water mainly through hydrophobic effect and hydrogen bonding. The binding constant is up to 1.2 × 10⁷ M^-1, which is much higher than that with cyclodextrin and cucurbituril. Meanwhile, the photostability of riboflavin in host-guest complex is enhanced compared with that of free riboflavin. This property allows the host WNT to be used as a light stabilizer for riboflavin compounds and further used in drugs or additives.

Second, the host-guest chemistry between host WNT and water-soluble organic dyes were also investigated. The experimental results showed that host WNT has strong binding ability to a series of common aromatic dyes, and the binding constants range from 10⁴ to 10⁶ M^-1. In addition, the binding of dye to host WNT was accompanied by significant fluorescence enhancement or quenching. This property provides a reference for supramolecular dyes in biological imaging.

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