Supramolecular Chemistry Composed of Porphyrins and Cyclodextrins

1)卟啉过甲基化环糊精配合物：我们发现一些水溶性四芳基卟啉与过o -甲基化β-环糊精（TMe-β-CD）形成非常稳定的1:2包合物。结果表明，该体系可用于制备各种超分子体系。2)卟啉- tme -β-CD配合物的形成机理：研究了极稳定的卟啉- tme -β-CD配合物的形成机理。结果表明，TMe-β-CD可以根据客体的形状改变其形状，从而产生生物系统中发现的“诱导配合型络合”。诱导拟合型包体实现了主、客体间的最佳范德华接触。3)异卟啉阵列的形成：通过对水溶性卟啉与TMe-β-CD络合的研究，建立了一种制备异卟啉阵列的简便方法。支架是四苯基卟啉，其外周苯基的对位由过o甲基化的β-环糊精部分连接。这种卟啉-环糊精缀合物只需与另一种卟啉溶液混合即可形成异卟啉阵列。通过将水溶性阴离子卟啉（ZnTPPS）的锌配合物溶液与ZnTPPS的溶液混合，实现了从锌配合物到共轭物的自由碱卟啉的高效能转移。4) Met-Myogbbin模型：阴离子卟啉（Fe(III)TPPS）的Fe（III）配合物与TMe-β-CD形成非常稳定的1:2包合物。这种复合物可以作为一种met-肌红蛋白模型，其铁（III）中心在水介质中与各种阴离子结合。在没有TMe-β-CD的情况下，水溶液中不发生与Fe(III)TPPS的阴离子结合，TMe-β-CD似乎具有类似于生物系统中蛋白质的功能。Fe(III)TPPS/FMe-β-CD配合物阴离子结合选择性高；即N3-选择性地与络合物结合。阴离子结合Fe(III)TPPS/TMe-β-CD配合物的稳定性主要受其亲水性、碱度和阴离子形状的影响。5) Myogbbin模型和可逆O2结合：用Fe(III)TPPS和过o -甲基化β-环糊精二聚体构建了met-肌红蛋白模型，其中两个环糊精部分通过含有吡啶部分作为近端碱基的桥连接。我们称这种模式为“血强迫症”。用二亚硝酸盐将Met-hemoCD还原为hemoCD （Fe(II)TPPS/环糊精二聚体），并与氧可逆结合。在pH 6.0的磷酸盐缓冲液中，氧血ocd的半衰期为30h。测定其双氧亲和度为17torr。血红蛋白的功能与肌红蛋白相似。本系统是肌红蛋白或血红蛋白在水溶液中工作模型的第一个例子。少

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