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Analysis of the optical absorption and magnetic-circular-dichroism spectra of peanut peroxidase: electronic structure of a peroxidase with biochemical properties similar to those of horseradish peroxidase.

机译:花生过氧化物酶的光吸收和圆二色性光谱分析:过氧化物酶的电子结构,其生化特性与辣根过氧化物酶相似。

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摘要

The electronic structures of the cationic isoenzyme of peanut peroxidase, horseradish peroxidase (isoenzyme C) and bovine liver catalase are compared through analysis of their optical absorption and magnetic c.d. (m.c.d.) spectral properties. The spectral data for the native resting states and compounds I and II of peanut peroxidase (PeP) are reported. The absorption and m.c.d. data for the native PeP exhibit bands characteristic of the high-spin ferric haem. The absorption spectrum of PeP compound I closely resembles that observed for the HRP compound I species. The m.c.d. data for PeP I clearly identifies that ring oxidation has occurred. One-electron reduction forms the PeP compound II species. The absorption and m.c.d. spectra recorded for PeP II exhibit the well-resolved spectral characteristics previously observed for both HRP compound II and catalase compound II. The spectral data of PeP with HRP and catalase are compared. The data clearly indicate that the m.c.d. spectral patterns of both plant peroxidases (PeP and HRP) are very similar and, therefore, the electronic structures of their resting states, and as well their primary and secondary compounds, must be similar. The m.c.d. data suggest that, while the compound I species of PeP and HRP belong to one electronic class, catalase compound I belongs to a different class. These data emphasize how the ground states of these two classes of oxidized haem, may be characterized as predominantly 2A2u (PeP I and HRP I) or 2A1u (catalase I). Peanut peroxidase is the second plant peroxidase for which the electronic structure of the compound I intermediate has been studied using the m.c.d. technique. The similarities with horseradish peroxidase allow us to suggest that plant peroxidases may operate by the same general mechanism, in spite of the low degree of sequence similarity between their polypeptide chains.
机译:通过对花生过氧化物酶,辣根过氧化物酶(同工酶C)和牛肝过氧化氢酶的阳离子同工酶的电子结构进行了比较,分析了它们的吸光度和磁性。 (m.c.d.)光谱特性。报告了花生过氧化物酶(PeP)的天然静止状态以及化合物I和II的光谱数据。吸收和m.c.d.天然PeP的数据显示出高纺铁血红素特征的条带。 PeP化合物I的吸收光谱与HRP化合物I物种的吸收光谱非常相似。邮编PeP I的数据清楚地表明已发生环氧化。单电子还原形成PeP化合物II物种。吸收和m.c.d. PeP II记录的质谱图显示了以前对HRP化合物II和过氧化氢酶化合物II都观察到的良好分辨的光谱特性。比较了具有HRP和过氧化氢酶的PeP的光谱数据。数据清楚地表明了两种植物过氧化物酶(PeP和HRP)的光谱图非常相似,因此其静止状态的电子结构以及其一级和二级化合物必须相似。邮编数据表明,虽然PeP和HRP的化合物I属于一个电子类别,但过氧化氢酶化合物I属于不同的类别。这些数据强调了这两类氧化血红素的基态如何主要表征为2A2u(PeP I和HRP I)或2A1u(过氧化氢酶I)。花生过氧化物酶是第二种植物过氧化物酶,已经使用m.c.d研究了化合物I中间体的电子结构。技术。与辣根过氧化物酶的相似性使我们建议,尽管植物过氧化物酶的多肽链之间的序列相似性较低,但它们可能以相同的通用机制起作用。

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