Supramolecular Chemistry Composed of Porphyrins and Cyclodextrins

卟啉和环糊精组成的超分子化学

• 批准号: 14340224
• 负责人: KANO Koji
• 金额: $ 9.66万
• 依托单位: DOSHISHA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14340224/
• 关键词: water-soluble porphyrin; per-O-methyylated cyclodextrin; inclusion complex; induced-fit type complexation; heteroporphyrin array; energy transfer; met-myogolobin model; myogolobin model; 超分子; 水溶性鉄ポルフィリン; 可逆的酸素捕捉; 酸素親和性; パーメチル化β-シクロデキストリン; 包接機; water-soluble porphyrin; per-O-methyylated cyclodextrin; inclusion complex; induced-fit type complexation; heteroporphyrin array; energy transfer; met-myogolobin model; myogolobin model; 超分子; 水溶性鉄ポルフィリン; 可逆的酸素捕捉; 酸素親和性; パーメチル化β-シクロデキストリン; 包接機

1) Porphyrin Permethylated Cyclodextrin Complexes : We found that some water-soluble tetraarylporphyrins form extremely stable 1:2 inclusion complexes with per-O-methylated β-cyclodextrin (TMe-β-CD). The complexes were formed quantitatively in aqueous solutions even when the concentrations of both host and guest were 10-6 M. The results strongly suggest the possibility of this system to be utilized for preparing various supramolecular systems2) Mechanism for Formation of Porphyrin-TMe-β-CD Complexes : Mechanism for formation of extremely stable porphyrin-TMe-β-CD complexes was studied. As a result, it was clarified that TMe-β-CD can alter its shape according to the shape of a guest resulting in "induced-fit type complexation" as is found in biological systems. The optimum van der Waals contacts between the host and the guest are achieved by the induced-fit type inclusion.3) Formation of Heteroporphyrin Arrays : A very convenient method to prepare heteroporphyrin arrays was developed by … More applying the results on complexation of water-soluble porphyrins and TMe-β-CD. A scaffold is the tetraphenylporphyrin whose para-positions of the peripheral phenyl groups are attached by per-O-methylated β-cyclodextrin moieties. Such a porphyrin-cyclodextrin conjugate can form heteroporphyrin array just by mixing with another porphyrin solution. Very efficient energy transfer from zinc complex of water-soluble anionic porphyrin (ZnTPPS) to the free base porphyrin of the conjugate was achieved just by mixing the solution of the conjugate with that of ZnTPPS.4) Met-Myogbbin Model : Fe(III) complex of the anionic porphyrin (Fe(III)TPPS) forms a very stable 1:2 inclusion complex with TMe-β-CD. Such a complex can act as a met-myoglobin model whose Fe(III) center is bound to various anions in aqueous media. The fact that no anion binding to Fe(III)TPPS occurs in aqueous solution in the absence of TMe-β-CD, TMe-β-CD seems to show the function similar to proteins in biological system. High selectivity was found in anion binding to Fe(III)TPPS/FMe-β-CD complex; namely N3- is selectively bound to the complex. Hydrophilicity, basicity, and shape of an anion are the factors to determine the stability of the anion-bound Fe(III)TPPS/TMe-β-CD complex.5) Myogbbin Model and Reversible O2 Binding : A met-myoglobin model was constructed by Fe(III)TPPS and a per-O-methylated β-cyclodextrin dimer where two cyclodextrin moieties were linked with a bridge containing a pyridine moiety as a proximal base. We call such a model "met-hemoCD". Met-hemoCD was reduced by dithionite to form hemoCD (Fe(II)TPPS/cyclodextrin dimer), which bound dioxygen reversibly. The half life time of oxy-hemoCD was 30h in pH 6.0 phosphate buffer. The dioxygen affinity was determined to be 17 Torr. HemoCD shows the functions similar to myoglobin. The present system is the first example of the model of myoglobin or hemoglobin that works in aqueous solution. Less

1）卟啉二甲基化环糊精络合物：我们发现，某些水溶性四边形孢林蛋白具有极高稳定的1：2包含复合物，具有每甲基化的β-环糊精（TME-β-CD）。即使宿主和来宾的浓度均为10-6 M，在水溶液中定量形成了这些复合物。结果强烈表明该系统可以用于制备各种超分子系统的可能性2）形成卟啉-TME-tme-β-CD复合物的机制：形成了极为稳定的孢子素 - β-β-c-c-c-cypsife的机制。结果，澄清说，TME-β-CD可以根据客人的形状改变其形状，从而导致“诱导型型络合”，如生物系统中所示。通过诱导的拟合式包含在宿主和来宾之间的最佳范德华接触。3）形成异源性核蛋白阵列：一种非常方便的准备杂多肾上腺素阵列的方法，通过…更多地应用结果，将结果应用于水 - 溶 - - 溶 - 溶卟啉和TME-β-cd的络合。脚手架是四苯基卟啉，其外周苯基的隔离是由每甲基化的β-环糊精部分连接的。阵列仅与另一种卟啉溶液混合。从水溶性阴离子卟啉（Zntpps）的锌复合物转移到结合物的游离卟啉的能量转移仅通过将结合物的溶液与Zntpppss的溶液混合在一起而实现TME-β-CD。这样的复杂可以充当元叶绿素模型，该模型的Fe（III）中心与水性介质的各种阴离子绑定在一起。在没有TME-β-CD的情况下，在水溶液中没有与Fe（III）TPP结合的阴离子结合，TME-β-CD似乎显示出类似于生物系统中蛋白质的功能。在阴离子与Fe（III）TPPS/FME-β-CD复合物结合的阴离子中发现了高选择性。即N3-选择性地与复合物结合。 Hydrophilicity, basicity, and Shape of an anion are the factors to determine the stability of the anion-bound Fe(III)TPPS/TMe-β-CD complex.5) Myobbin Model and Reversible O2 Binding: A met-myoglobin model was constructed by Fe(III)TPPS and a per-O-methylated β-cyclodextrin dimer where two cyclodextrin moieties were linked带有一个包含吡啶部分作为近端基座的桥。我们将这样的模型称为“ Met-Hemocd”。通过二硫代石将MET-HEMOCD降低，形成HemoCD（Fe（II）TPPS/Cyclodextrin二聚体），该二聚体可逆地结合二氧化物。氧气 - 高含量的半寿命为3.0 pH 6.0磷酸盐缓冲液。二氧化物亲和力确定为17托尔。 HemOCD显示了类似于肌红蛋白的功能。本系统是在水溶液中起作用的肌红蛋白或血红蛋白模型的第一个例子。较少的