Construction of Non-heme Metalloenzyme Model Complexes with Binding and/or Activation Function for Oxygen Species and Their Regulation

为了构建对氧物种具有结合和/或活化功能的非血红素金属酶模型络合物，我们根据金属酶活性中心周围的结构制备了一些新设计的金属络合物。我们最初的设计理念是，金属活性中心被一些非共价相互作用中心包围，如氢键和疏水相互作用基团作为活性氧配位或底物识别中心。利用这些金属络合物，我们成功地获得了一些有趣而重要的结果如下。(1)首次合成了稳定的过氧化氢铜(II)络合物作为多巴胺β-羟基酶的模型，通过氢键和疏水作用基团获得了较高的稳定性。我们还用独特的方形平面铜(II)络合物成功地活化了过氧化氢离子，这是迄今制备的过氧化氢铜络合物中催化活性最高的。(2)成功地制备了具有可逆氧化功能的氢氰菊酯模型络合物。在此实验的基础上，还发现氢氰菊酯中出现的氢从羟基到超氧的质子转移是通过水分子的中介进行的。(3)作为甲烷单加氧酶模型，利用新设计的三齿配体制备了高价双μ-氧代二铜(III)配合物，该配合物具有较高的氧化活性，可将饱和碳氢化合物氧化为羟基化合物。(4)我们还成功地利用天然化合物Spartein制备了具有高度扭曲的四面体结构的高价Bus-μ-OX双铜(III)配合物。结果(Iii)和(Iv)包含了一个重要的事实，即二氧化氧分子被金属离子还原成四个电子，这是燃料电池的基本原理

In order to construct non-heme metallo-enzyme model complexes with binding and/or activation function for oxygen species, we prepared some newly-designed metal complexes on the basis of the structures around the active centers for metalloenzymes. The design concept of our original complexes is that the metal active center is surrounded by some non-covalent interaction sites such as hydrogen bonding and hydrophobic interaction groups as the acitve oxygen coordination or substrate-recognition site. Using these metal complexes, we succeeded in obtaining some interesting, important results as follows. (i)As a model of dopamine β-hydroxylase, stable hydroperoxo copper(II) complex was first prepared, whose higher stability was achieved by the hydrogen bonding and hydrophobic interaction groups. And we also succeeded in activation of hydroperoxide ion using unique square-planar copper(II) complex, which exhibited the highest catalytic activity among the hydroperoxo copper complexes prepared hitherto. (ii) We succeeded in preparation of hemerythrin model complexes showing reversible oxygenation function. On the basis of this experiment, it was also found out that the proton transfer from hydroxo to superoxo that appeared in hemerythrin is carried out by mediation of water molecules. (iii)As the methane monooxygenase model, high valence bis-μ-oxo dicopper(III) complex was prepared using newly-designed tridentate ligand, which exhibited higher oxidation activity to oxidize the saturated hydrocarbon compounds to the hydroxyl ones. (iv) We also succeeded in preparation of high valence bus-μ-ox dicopper(III) complex with highly-distorted tetrahedron structure using natural compound spartein. The results (iii) and (iv) include important fact that the dioxygen molecule has been reduced by four electrons from metal ions, which is the basic principle for the fuel cell