血蓝蛋白模型化合物的合成和性质

SYNTHESIS AND PROPERTIES OF HEMOCYANIN MODEL COMPOUNDS

由反式-环己烷邻-二氨基四乙酸和邻苯二胺缩合而成的双核配体邻-二[N,N-二(2′-苯并咪唑甲基)氨基]-反式-环己烷(O-CTB)。它与[Cu(CH_3CN)_4]ClO_4和Cu(ClO_4)_2·6H_2O反应分别得到Cu(Ⅰ)和Cu(Ⅱ)的双核配合物。并测定了配体和配合物的~1HNMR,^(13)CNMR、IR、UV-VIS谱及配合物电导和元素含量。我们发现配合物[Cu_2(O-CTB)](ClO_4)_2·6H_4O(Ⅰ)可以摸拟血蓝蛋白与氧的反应;配合物(Ⅰ)的无色DMF溶液吸氧后呈蓝色;用抗环血酸(AA)还原成无色,如此可循环六次以上。并能分离出氧合物[Cu_2(O-CTB)(O_2^(2-))](ClO_4)_2·4H_2O(Ⅱ)。

The dinucleating ligand ortho-bis [N, N-bis (2'-benzoimidazolyl methyl) amino]-trans-cyclohexane (O-CTB) is prepared by condensatiom of ophenylenediamine and orthobisamino-trans-cyclohexane-N, N, N', N'-tetraacetic acid. The ligand appears to yield dinuclear complexes with [Cu (CH_3CN)ClO_4] and Cu (ClO_4)_2·6H_2O respectively. The ~1HNMR, ^(13)CNMR, IR, UV-VIS spectra of the ligand and its coordination compounds and conductivities and elemental analysis of these complexes have been determined. We have discovered that the coordination compound[Cu I 2(O—CTB)] (ClO_4)_2·6H_2O(Ⅰ) can mimic to a reaction with oxygen of hemocyanin(Hc). The colorless solution of complex(Ⅰ) in dimethylformamide(DMF)shows an uptake of oxygen to give a blue solution with a characteristic electronic spectrum of Cu(Ⅱ) in an ice-salt bath. Addition of ascorbic acid(AA), results in decolorization of the solution, and the cycle can be repeated over six times. This is similar to the effect of AA on Hc. The dioxygen adduct could be isolated from the solution.