Biomimetic Studies on Energy and Information Transduction

能量与信息传递的仿生研究

• 批准号: 03650697
• 负责人: KOBUKE Yoshiaki
• 金额: $ 0.26万
• 依托单位: Shizuoka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03650697/
• 关键词: beta-diketone; Catechol; Polyether; Cooperativity; Ion Flux; エネルギー変換; βージケトン; 構造ー機能変換; イオンー電子共役輸送; ポリエ-テル; ホスト-ゲスト

We have tried to establish coupled electron-ion fluxes across the membrane. For this purpose, basic ideas of molecular organization have been developed, where alkali or alkaline earth metal ions were entrapped by the hosts organized by the complexation with transition metal ions. Therefore, linear as well as macrocyclic catechol-polyether host,L were synthesized. Anionic oxygen atoms from catechol parts participated into a complex formation with boron, M_1 to leave an excess anionic charge. Then partly anionic oxygen atoms from the catechol part together with neutral oxygens from polyether part were nicely arranged into a crown type configuration, into which monovalent cation, M_2 was entrapped to afford a neutral triple complex L・M_1・M_2.Novel podands having beta-diketone units at both terminals of oligoethylene glycols have been synthesized. The podands were converted into coronands through the intramolecular complexation of two beta-ketoenolates with Zn(II) and Cu(II) ions. These metal-assisted coronands were capable of accepting additional metal ions into a macrocyclic crown ether moiety newly organized by enolate oxygens and neutral ether oxygens. Therefore, the Cu complex cooperatively extracted metal picrates from aqueous to organic phase, showing the typical selectivity of the match between the hole and ion sizes.These hosts afforded basic devices for the transduction of biological energy and information through the coupled electron-ion fluxes.

我们试图建立跨膜的电子-离子耦合通量。为此目的，已经发展了分子组织的基本思想，其中碱金属或碱土金属离子被通过与过渡金属离子络合而组织的主体捕获。因此，线性以及大环儿茶酚-聚醚主体，L的合成。邻苯二酚部分的阴离子氧原子与硼M_1形成络合物，留下过量的阴离子电荷。邻苯二酚部分的阴离子氧原子与聚醚部分的中性氧原子形成冠醚型结构，一价阳离子M_2被捕获到冠醚型结构中，形成中性三元配合物L·M_1·M_2。podands转化为冠通过分子内络合的两个β-酮烯醇与Zn（II）和Cu（II）离子。这些金属辅助冠醚能够接受额外的金属离子进入一个大环冠醚部分新组织的烯醇化氧和中性醚氧。因此，Cu配合物协同萃取金属苦味酸盐从水相到有机相，表现出典型的空穴和离子尺寸匹配的选择性，这些主体通过电子-离子耦合流提供了生物能量和信息传递的基本器件。

项目成果

Y. Kobuke: "Positive Cooperativity in Cation Binding by Novel Polyethe Bis(βーdiketone)Hosts" J. Am. Chem. Soc.114. 789-790 (1992)

Y. Kobuke：“新型聚醚二酮主体的阳离子结合”J. Am. 789-790 (1992)。

Y. Kobuke: "Metalーassisted Organization rather than Preorganization for the Design of Macrocyclic Hosts" Angew. Chem. Int. Ed.,Engl.30. 1496-1498 (1991)

Y. Kobuke：“大环主体的设计采用金属辅助组织而不是预组织”，Angew，Ed.30（1991）。

Y.Kobuke, M.Yamanishi, I.Hamachi, H.Kagawa, and H.Ogoshi: "A Novel Transmembrane Electron Channel Containing Flavin Units" J.Chem. Soc., Chem. Commun.13. 895-897 (1991)

Y.Kobuke、M.Yamanishi、I.Hamachi、H.Kakawa 和 H.Ogoshi：“一种包含黄素单元的新型跨膜电子通道”J.Chem。

Y.Kobuke, Y.Sumida, M.Hayashi, and H.Ogoshi: "Metal Assisted Organization rather than Preorganization for the Design of Macrocyclic Hosts" Angew. Chem. Int. Ed. Eng.30(11). 1496-1498 (1991)

Y.Kobuke、Y.Sumida、M.Hayashi 和 H.Ogoshi：“用于大环主体设计的金属辅助组织而不是预组织”Angew。

Y.Kobuke and Y.Satoh: "Positive Cooperativity of Cation Binding by Novel Polyether-bis(b-diketone) Hosts" J.Am. Chem. Soc. 114(2). 789-790 (1992)

Y.Kobuke 和 Y.Satoh：“新型聚醚双（b-二酮）主体的阳离子结合的正协同性”J.Am。