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

为了构建具有结合和/或激活氧物种功能的非血红素金属-酶模型配合物，我们根据金属酶活性中心周围的结构设计了一些新的金属配合物。我们最初的配合物的设计理念是金属活性中心被一些非共价相互作用位点如氢键和疏水相互作用基团所包围，作为活性氧配位或底物识别位点。使用这些金属配合物，我们成功地获得了一些有趣的，重要的结果如下。(i)As首次制备了多巴胺β-羟化酶模型化合物--稳定的过氧化氢铜（II）配合物，通过氢键和疏水作用基团使其具有更高的稳定性。我们还成功地活化氢过氧化物离子使用独特的正方形平面铜（II）配合物，其中表现出最高的催化活性之间的氢过氧铜配合物迄今为止制备。(ii)我们成功地制备了具有可逆氧化功能的血红蛋白模型复合物。在此基础上，还发现了血红蛋白中出现的氢氧向超氧的质子转移是通过水分子介导进行的。（iii）以新设计的三齿配体作为甲烷单加氧酶模型，合成了高价双-μ-氧代二铜（III）配合物，该配合物对饱和烃类化合物氧化为羟基化合物表现出较高的氧化活性。(iv)我们还成功地用天然化合物金雀花蛋白合成了高价的具有高度畸变四面体结构的bus-μ-ox双铜（III）配合物。结果（iii）和（iv）包括重要的事实，即双氧分子已被来自金属离子的四个电子还原，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