过氧化氢酶和辣根过氧化物酶的化合物I：π-阳离子自由基。
Compounds I of catalase and horse radish peroxidase: pi-cation radicals.
作者信息
Dolphin D, Forman A, Borg D C, Fajer J, Felton R H
出版信息
Proc Natl Acad Sci U S A. 1971 Mar;68(3):614-8. doi: 10.1073/pnas.68.3.614.
Abstract
Two-electron oxidation of cobaltous octaethylporphyrin [Co(II)(Et)(8)P] yields a stable pi-cation radical Co(III)(Et)(8)P, the optical spectrum of which exhibits spectral changes dependent upon the nature of the counterion. Comparison of these spectra with those of Compounds I of horseradish peroxidase and catalase leads us to propose that these Compounds I contain a pi-cation radical of the heme prosthetic group. This proposal explains the oxidation level, optical spectra, and stability of the primary compounds without recourse to properties such as stoichiometric mixtures of special porphyrins, stable Fe(V) porphyrins, or unique conformers of heme porphyrins. Explanations are advanced to account for the missing electron spin resonance signal of Compound I of horseradish peroxidase.
摘要
八乙基钴卟啉[Co(II)(Et)(8)P]的双电子氧化产生稳定的π-阳离子自由基Co(III)(Et)(8)P，其光谱表现出取决于抗衡离子性质的光谱变化。将这些光谱与辣根过氧化物酶和过氧化氢酶的化合物I的光谱进行比较，使我们提出这些化合物I含有血红素辅基的π-阳离子自由基。这一提议解释了初级化合物的氧化水平、光谱和稳定性，而无需借助特殊卟啉的化学计量混合物、稳定的Fe(V)卟啉或血红素卟啉的独特构象等性质。对辣根过氧化物酶化合物I缺失的电子自旋共振信号给出了解释。
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