Synthesis of Pseudocyclophanes Bearing Multi-recognition Sites and the allosteric Control of Their Recognition Ability

具有多识别位点的拟环芳烷的合成及其识别能力的变构控制

• 批准号: 09640622
• 负责人: NABESHIMA Tatsuya
• 金额: $ 1.15万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640622/
• 关键词: Allosteric Effect; Molecular Recognition; Cyclophane; Flavin; C-AMP; Bipyridine; Cu (I) Complex; c-AMP; アロステリ-

In this study a new allosteric host was designed and synthesized. Allosteric host 1 consists of two 2,2'-bipyridine moieties, two bisphenol A skeletons, and an ammonium moiety. Host 1 binds a Cu(I) ion to give the corresponding tetrahedral complex, pseudocyclophane, which has a binding cavity and the ammonium group in close proximity. In solvent extraction, 1-Cu(I) complex showed a higher affinity toward flavin mononucleotide sodium salt (FMN) than 1. However, meaningful effect of Cu(I) is not found in a similar host, which does not have an ammonium moiety. These results strongly suggest that cooperative interactions between the cavity and the charged moiety of 1-Cu(I) are important for the FMN binding. After extraction of FMN with 1-Cu(I), the guest was moved to the aqueous phase again by the addition of bathocuproine or triethylamine hydrochloride. Bathocuproine strongly binds to Cu(I) to destroy 1-Cu(I) quantitatively. Triethylamine hydrochloride interacts with the guest to inhibit interaction between 1-Cu(I) and the phosphate moiety of the guest. These results indicated that the framework and the ammonium moiety of the pseudocyclophane are important for the recognition of the guest. In addition, the results show that on-and-off control of molecular recognition is achieved by using this system. A similar allosteric recognition of c-AMP was also performed successfully.We believe that this study provided a new and fundamental way to construct a sophisticated on-and-off system for recognition of complicated organic molecules in artificial systems.

本研究设计并合成了一种新的变构宿主。变构宿主1由两个2,2'-联吡啶部分，两个双酚A骨架和一个铵部分组成。宿主1结合一个Cu(I)离子生成相应的四面体配合物——伪环环烷，该配合物具有一个结合腔，紧邻铵基。溶剂萃取时，1- cu (I)配合物对黄素单核苷酸钠盐（FMN）的亲和力高于1- cu (I)配合物。然而，Cu(I)在没有铵基的类似宿主中没有明显的作用。这些结果强烈表明，空腔与1-Cu(I)的带电部分之间的协同相互作用对于FMN的结合是重要的。用1-Cu(I)萃取FMN后，再加入根碱或盐酸三乙胺将客体移至水相。Bathocuproine与Cu(I)强结合，定量破坏1-Cu(I)。盐酸三乙胺与客体相互作用，抑制1-Cu(I)与客体的磷酸盐部分之间的相互作用。这些结果表明，伪环环烷的结构和铵基部分对识别客体具有重要意义。此外，该系统还实现了分子识别的开关控制。c-AMP的类似变构识别也成功进行。我们相信本研究为构建复杂的开关系统来识别人工系统中的复杂有机分子提供了一种新的和基本的方法。

项目成果

Tatsuya Nabeshima: "On-and-off Control of Allosteric Affinity toward Flavin Mononuclectide by the Use of a Pseudo cyclophane Formed with Cu (I) as an Effector" J.Org.Chem・. 63. 2788-2789 (1998)

Tatsuya Nabeshima：“通过使用以 Cu (I) 作为效应物形成的伪环烷对黄素单核苷酸的变构亲和力进行断断续续的控制”J.Org.Chem·63. 2788-2789 (1998)

Tatsuya Nabeshima: "On-and-off Control of Allosteric Affinity toward Flavin Mononucleotide by the Use of a Pseudoeyclophane Formed with Cu(I) as an Effector" J.Org.Chem.63. 2788-2789 (1998)

Tatsuya Nabeshima：“使用以 Cu(I) 形成的伪环烷作为效应物对黄素单核苷酸的变构亲和力进行断断续续的控制”J.Org.Chem.63。

Tatsuya Nabeshima: "On-and-off Control of Allosteric Affinity toward Flavin Mononucleatide by the Use of a Pseudecyclophane Formed with Cu(I) as an Effecter" J.Org.Chem.63. 2788-2789 (1998)

Tatsuya Nabeshima：“使用以 Cu(I) 形成的伪环烷作为效应物对黄素单核苷酸的变构亲和力进行断断续续的控制”J.Org.Chem.63。

鍋島達弥: "On-and-off Control of Allosteric Affinity toward Flavin Mononucleotide by the Use of a Pseudocyclophane Formed with Cu(I) as an Effector" J.Org.Chem.63(印刷中). (1998)

Tatsuya Nabeshima：“使用以 Cu(I) 形成的伪环烷作为效应物对黄素单核苷酸的变构亲和力进行断断续续的控制”J.Org.Chem.63（出版中）。