Electrochemistry of Protein Electron Transfer
Electrochemistry of Protein Electron Transfer
复制标题
蛋白质电子转移的电化学
DOI：
10.1149/1945-7111/ac60f1
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发表时间：
2022
影响因子：
3.9
通讯作者：
Matyushov, Dmitry V.
中科院分区：
文献类型：
--
作者：
Matyushov, Dmitry V.
蛋白质折叠和慢弛豫时间对蛋白质采样的构型施加约束。不完整的采样导致违反波动耗散关系的电子转移的传统理论。电子转移的有效重组能大大降低，从而导致更低的势垒和更快的速率（催化效应）。电化学动力学测量支持蛋白质电子转移的低活化势垒。速率常数的距离依赖性显示从短距离的平台到长距离的指数衰减的交叉。这两种状态之间的转换是由蛋白质动力学控制的。
Protein fold and slow relaxation times impose constraints on configurations sampled by the protein. Incomplete sampling leads to the violation of fluctuation-dissipation relations underlying the traditional theories of electron transfer. The effective reorganization energy of electron transfer is strongly reduced thus leading to lower barriers and faster rates (catalytic effect). Electrochemical kinetic measurements support low activation barriers for protein electron transfer. The distance dependence of the rate constant displays a crossover from a plateau at short distances to a long-distance exponential decay. The transition between these two regimes is controlled by the protein dynamics.