Younes M, Pilz W, Weser U
J Inorg Biochem. 1979 Feb;10(1):29-39. doi: 10.1016/s0162-0134(00)81003-x.
The oxidation state of copper in several model compounds containing copper coordinated to sulfur, some of which are suggested model compounds for naturally occurring Cu-S chromophores, was determined employing x-ray photoelectron spectrometry. Copper was found to be present in a 3d10 state, which is characteristic for Cu(I). An initial photoreduction is excluded, as Cu(ethylenediamine)2 (SCN)2, in which a Cu-S bond is also present, was found to contain Cu(II) (3d9). As was the case with native parsley plastocyanin, the model compounds reacted effectively with superoxide anion radicals. We suggest that the electrons of the metal-sulfur chromophore in blue copper proteins are delocalized and that an equilibrium: RS--Cu(II) in equilibrium or formed from RS.Cu(I) exists.
利用X射线光电子能谱法测定了几种含与硫配位的铜的模型化合物中铜的氧化态，其中一些被认为是天然存在的铜 - 硫发色团的模型化合物。发现铜以3d10状态存在，这是Cu（I）的特征。由于发现含有Cu - S键的Cu（乙二胺）2（SCN）2含有Cu（II）（3d9），排除了初始光还原的可能性。与天然欧芹质体蓝素的情况一样，模型化合物与超氧阴离子自由基有效反应。我们认为蓝铜蛋白中金属 - 硫发色团的电子是离域的，并且存在平衡：RS--Cu（II）处于平衡状态或由RS.Cu（I）形成。
