Long-Range Electron Transfer in Engineered Azurins Exhibits Marcus Inverted Region Behavior
Long-Range Electron Transfer in Engineered Azurins Exhibits Marcus Inverted Region Behavior
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DOI：
10.1021/jz5022685
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发表时间：
2015-01-01
影响因子：
5.7
通讯作者：
Pecht, Israel
中科院分区：
文献类型：
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作者：
Farver, Ole;Hosseinzadeh, Parisa;Pecht, Israel
马库斯电子转移理论预测，虽然电子转移速率常数随着驱动力的增加而增加，直到它等于反应的重组能，但在较高的驱动力下，电子转移速率下降，已到达马库斯反转区。虽然已经报道了有机和无机ET反应以及与辅助氧化还原部分结合的蛋白质的倒置区域的实验证据，但在“纯蛋白质”系统中倒置区域的证据仍然难以捉摸。在此，我们在一系列非衍生物蛋白质中提供了这样的证据。这些结果可能有助于设计用于未来应用的ET中心，例如先进的能量转换。
The Marcus theory of electron transfer (ET) predicts that while the ET rate constants increase with rising driving force until it equals a reaction's reorganization energy, at higher driving force the ET rate decreases, having reached the Marcus inverted region. While experimental evidence of the inverted region has been reported for organic and inorganic ET reactions as well as for proteins conjugated with ancillary redox moieties, evidence of the inverted region in a "protein-only" system has remained elusive. We herein provide such evidence in a series of nonderivatized proteins. These results may facilitate the design of ET centers for future applications such as advanced energy conversions.