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化学学报
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化学学报 ›› 1990, Vol. 48 ›› Issue (12): 1164-1170. 上一篇    下一篇

研究论文

廿员大环双核铜(II)配合物的合成和对超氧歧化酶的摸拟

罗勤慧;沈孟长;彭庆芸;高伟;张正   

  1. 南京大学配位化学研究所
  • 发布日期:1990-12-15

Synthesis of six new xo-membered macrocyclic bicopper(II)complexes ad modelling on superoxide dismultase

LUO QINHUI;SHEN MENGCHANG;PENG QINGYUN;GAO WEI;ZHANG ZHENG   

  • Published:1990-12-15

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本文合成了六个新的廿员大环双核铜(II)配合物作为Cu,Zn-SOD模拟物, 其配体是用2,6-二甲酰基吡啶与1,3一丙二胺缩合而成, 以SCN,Cl-Br-,I-,N3-,OH-桥联, 用多种物理方法进行表征, 并用核黄素光照法研究与O2-反应的动力学, 结果表明, 反应速率常数大约在107mol-1.Clm3,S-1其中以SCN为桥的配合物速率常数最高,而含N3-桥的最低, ESR谱研究结果表明前者与O2-为可逆的催化反应, 后者为不可逆的氧化还原反应, 这种情况与作者曾研究过的二乙酰基吡啶缩丙二胺合铜配合物一致, N3-桥对配合物的阻化作用与N3-对SOD的阻化作用类似。

关键词: 紫外分光光度法, 吡啶 P, 红外分光光度法, 电子自旋共振谱法, 反应动力学, 铜络合物, 大环化合物, 超氧化物歧化酶, 双核络合物, 桥环化合物

[Cu(m-X)CuL](ClO4)3譓eOH (X = OH, N3, Br, I; L = I (R = H)) and [Cu(m-X')2CuL] (ClO4)2譓eOH (X' = Cl, SCN) were prepared L was prepared from 2,6-dimethylpyridine with conversion to the dialdehyde followed by condensation with 1,3-propanediamine. Kinetic of the O2- reaction of the 6 complexes are reported as are those for superoxide dismutase and [Cu(m-X)CuL](ClO4)3 (L = I (R = Me)). The results of riboflavin illumination method showed that the rate constants ~107 mol-1譫m3譻-1. Among them the complex with bridging SCN has the highest rate constant and that with bridging N3 has the lowest value. The reactions of complexes with O2- were studied by ESR. The reversible catalysis mechanism takes place in the reaction of SCN bridged complex, and the reaction of N3- bridged complex has irreversible oxidation. mechanism. Inhibition of N3- in this complex is similar to that of N3 to superoxide dismutase.

Key words: ULTRAVIOLET SPECTROPHOTOMETRY, PYRIDINE P, INFRARED SPECTROPHOTOMETRY, ELECTRON SPIN RESONANCE SPECTROMETRY, REACTION KINETICS, COPPER COMPLEX, MACROCYCLIC COMPOUNDS, SUPEROXIDE DISMUTASE, DINUCLEAR COMPLEX, BRIDGE COMPOUNDS

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