基于电子自旋弛豫数据对辣根过氧化物酶中Fe3+以及辣根过氧化物酶化合物I中Fe4+的零场分裂
Zero-field splitting of Fe3+ in horseradish peroxidase and of Fe4+ in horseradish peroxidase compound I from electron spin relaxation data.
作者信息
Colvin J T, Rutter R, Stapleton H J, Hager L P
出版信息
Biophys J. 1983 Feb;41(2):105-8. doi: 10.1016/S0006-3495(83)84412-9.
Abstract
From the temperature dependence of the Orbach relaxation rate of the paramagnetic center in horseradish peroxidase (HRP), we deduce an excited-state energy of 40.9 +/- 1.1 K. Similar studies on the broad EPR signal of HRP compound I indicate a much weaker Orbach relaxation process involving an excited state at 36.8 +/- 2.5 K. The strength of the Orbach process in HRP-I is weaker than one would normally estimate by 2-4 orders of magnitude. This fact lends support to the model of HRP-I involving a spin 1/2 free radical coupled to a spin 1 Fe4+ heme iron via a weak exchange interaction. Such a system should exhibit an Orbach relaxation process involving delta E, the excited state of the Fe4+ ion, but reduced in strength by (Jyy/delta E)2, where Jyy is related to the strength of the exchange interaction between the two spin systems.
摘要
从辣根过氧化物酶（HRP）中顺磁中心的奥巴赫弛豫速率与温度的依赖关系，我们推断出激发态能量为40.9±1.1K。对HRP化合物I的宽EPR信号进行的类似研究表明，存在一个弱得多的奥巴赫弛豫过程，涉及36.8±2.5K的激发态。HRP-I中奥巴赫过程的强度比正常估计值弱2至4个数量级。这一事实支持了HRP-I的模型，该模型涉及一个自旋为1/2的自由基通过弱交换相互作用与自旋为1的Fe4+血红素铁耦合。这样一个系统应该表现出一个涉及δE（Fe4+离子的激发态）的奥巴赫弛豫过程，但其强度会因（Jyy/δE）2而降低，其中Jyy与两个自旋系统之间交换相互作用的强度有关。
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