Duracková Z, Mendiola M A, Sevilla M T, Valent A
Department of Medical Chemistry, Biochemistry and Clinical Biochemistry, Comenius University, Bratislava, Slovak Republic.
Bioelectrochem Bioenerg. 1999 Feb;48(1):109-16. doi: 10.1016/s0302-4598(98)00231-1.
The redox behaviour of copper(II) complexes with the open chain ligand, benzilbisthiosemicarbazone, and the macrocyclic one [3,4,10,11-tetraphenyl-1,2,5,8,9,12,13-octaazacyclotetradeca-7,14- dithione- 2,4,9,11-tetraene] has been explored by cyclic voltammetry. The half-wave potential values for the copper(II)/copper(I) redox couple and the spectral data obtained on dimethylsulfoxide (DMSO) solution agree with the superoxide dismutase (SOD)-mimetic activity of the complexes. The macrocyclic complexes show more positive reduction potential and more activity than the open chain derivatives. From our results it follows that the structure and conformation of ligand has influence on the redox potential of central atom in coordination compound. The changes in the coordination sphere are connected with the change of biological function of compounds represented by SOD-mimic activity. In addition, the L1H6 derivatives show quasireversible waves associated to Cu(II)/Cu(III) process.
通过循环伏安法研究了铜(II)与开链配体苯偶酰双硫代半卡巴腙以及大环配体[3,4,10,11-四苯基-1,2,5,8,9,12,13-八氮杂环十四碳-7,14-二硫酮-2,4,9,11-四烯]形成的配合物的氧化还原行为。铜(II)/铜(I)氧化还原对的半波电位值以及在二甲基亚砜(DMSO)溶液中获得的光谱数据与配合物的超氧化物歧化酶(SOD)模拟活性一致。大环配合物比开链衍生物表现出更正的还原电位和更高的活性。从我们的结果可以看出,配体的结构和构象对配位化合物中中心原子的氧化还原电位有影响。配位球的变化与以SOD模拟活性为代表的化合物的生物学功能变化有关。此外,L1H6衍生物显示出与Cu(II)/Cu(III)过程相关的准可逆波。