Preparation of Box-shaped Cyclophane Compounds Recognizing Endocrine Disruptors and their Immobilization

大环环番化合物在水中与客体分子的络合反应一直是人们研究的热点，因为它可以模拟生物体系中的基本分子识别过程。虽然改性环糊精在水介质中的包合、识别和催化等方面已经得到了广泛的研究，但其结构的通用性有限。相反，水溶性杯芳烃和环芳烃在分子设计方面具有很大的优势。另一方面，据报道，被称为内分泌干扰物的化合物可能会对人类产生意想不到的影响。因此，人们提出了一种新型的具有与某些内分泌干扰物结合能力的环芳烃类化合物。我们给出了这类大环衍生物的简便合成方法。这些大环环番化合物包括荧组分、萘组分、蒽组分或芘组分。为了识别EN…更多的药物破坏分子间的弱相互作用，如CH-π相互作用、π-π相互作用、氢键等可能是非常重要的。我们已经阐明了这些环番的构象性质，表明环的反转高度依赖于它们的分子结构，特别是内部取代基和桥联部分的长度。氢键对构象也起决定性作用。一些环芳烃通过将分子内氢键转换为分子间氢键而表现出非常有趣的性质。在这个过程中，晶体结构发生了变化。在含有荧组分的环番中，观察到荧光能量转移，这取决于分子的刚性和两个芳香族组分的取向。由菲或菲单元组成的环番在氨基和芳香族单元之间表现出独特的CH-π相互作用，这对构象有影响。现在，我们正在利用在这里获得的弱相互作用知识来开发所需的系统。较少

Complexation of macrocyclic cyclophane compounds with guest molecules in water has always attracted a major interest since it can mimic the molecular recognition which is a basic process in biological systems. Although modified cyclodextrins have been extensively investigated in terms of inclusion, recognition, and catalysis in aqueous media, versatility of their structure is limited. On the contrary water-soluble calixarenes and cyclophanes have a great advantage of molecular design. On the other hand it has been reported that the chemical compounds known as endocrine disrupters could have an unexpected influence on human beings. Thus, novel cyclophans consisting of fluorene, naphthalene, anthracene or pyrene component which could exhibit a binding ability against some kinds of endocrine disrupters have been proposed. We have shown the facile synthetic methods of such macrocyclic cyclophanes containing fluorene, naphthalene, anthracene or pyrene component. In order to recognize the en … More docrine disrupters weak intermolecular interactions such as CH-π interaction, π-π interaction, hydrogen bondings and so on could be very important. We have clarified the conformational properties of these cyclophanes, indicating that the ring inversion is highly dependent on their molecular structures, especially the inner substituents and the length of the bridging part. Hydrogen bondings also play a decisive role on the conformation. Some cyclophanes exhibit a very interesting properties by switching an intramolecular hydrogen bonding to an intermolecular one. During this process crystal structure changes. In the cyclophanes having the fluorene component fluorescence energy transfer is observed, depending the rigidity of the molecule and the orientation of two aromatic components. The cyclophanes consisting of anthracene or pyrene unit exhibit a unique CH-π interaction between the amino group and the aromatic unit, which has an influence on the conformation. Now we are developing the desired system using the knowledge of weak interactions obtained here. Less