Vasák M, Kägi J H, Holmquist B, Vallee B L
Biochemistry. 1981 Nov 10;20(23):6659-64. doi: 10.1021/bi00526a021.
The zinc and cadmium of native rabbit metallothionein-1 were replaced stoichiometrically with either cobalt (II) or nickel (II). The electronic, magnetic circular dichroic (MCD), and electron spin resonance spectra of Co (II)-metallothionein reflect distorted tetrahedral coordination of the cobalt atoms. Both the d-d and charge-transfer spectral regions closely resemble those of simple cobalt-tetrathiolate complexes, implying that their coordination chemistry is analogous. Ni (II) complex ions and Ni (II)-metallothionein similarly exhibit analogous MCD bands in the d-d region. The circular dichroic bands associated with ligand-metal charge-transfer transitions in the non-d-d region of Co (II)- and Ni (II)-metallothionein afford additional evidence for the similarity in tetrahedral microsymmetry of the two metal derivatives. The known ratio of 20 thiolate ligands to 7 metal ions, in conjunction with the spectral evidence for tetrathiolate coordination in metallothionein, represents good evidence that these metal thiolates are organized in clusters.
天然兔金属硫蛋白-1中的锌和镉被化学计量的钴(II)或镍(II)取代。钴(II)-金属硫蛋白的电子、磁圆二色性(MCD)和电子自旋共振光谱反映了钴原子的扭曲四面体配位。d-d和电荷转移光谱区域都与简单的钴-四硫醇盐配合物非常相似,这意味着它们的配位化学是类似的。镍(II)络合离子和镍(II)-金属硫蛋白在d-d区域同样表现出类似的MCD带。与钴(II)-和镍(II)-金属硫蛋白的非d-d区域中的配体-金属电荷转移跃迁相关的圆二色带为这两种金属衍生物的四面体微对称性相似性提供了额外证据。已知的20个硫醇盐配体与7个金属离子的比例,结合金属硫蛋白中四硫醇盐配位的光谱证据,充分证明这些金属硫醇盐以簇的形式排列。