Theory and Electrochemistry of Cytochrome c.
Theory and Electrochemistry of Cytochrome c.
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细胞色素的理论和电化学 c．
DOI：
10.1021/acs.jpcb.7b00917
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
D. Matyushov
中科院分区：
文献类型：
--
作者：
Salman S Seyedi;Morteza M. Waskasi;D. Matyushov
对溶液中细胞色素 c 进行广泛的模拟，以解决通常由原子模拟报告的蛋白质电子转移的大重组能与蛋白质电化学产生的小得多的值之间的明显矛盾。通过推导电化学反应的活化势垒来协调这两组数据，该活化势垒由一半斯托克斯位移（表征响应电子转移的介质极化）和方差重组能（表征静电波动的宽度）组成。这种有效的重组能远小于贡献它的两个组分中的每一个，并且与电化学测量完全一致。 280 至 360 K 温度范围内的计算将长时间的经典分子动力学模拟与蛋白质活性位点的量子计算相结合。结果与反应速率的阿伦尼乌斯图以及固定在自组装单层上的细胞色素 c 的循环伏安法一致。小的有效重组能以及由此产生的小活化势垒是蛋白质电子转移的一般现象，允许在生物能量链内快速电子转移。
Extensive simulations of cytochrome c in solution are performed to address the apparent contradiction between large reorganization energies of protein electron transfer typically reported by atomistic simulations and much smaller values produced by protein electrochemistry. The two sets of data are reconciled by deriving the activation barrier for electrochemical reaction in terms of an effective reorganization energy composed of half the Stokes shift (characterizing the medium polarization in response to electron transfer) and the variance reorganization energy (characterizing the breadth of electrostatic fluctuations). This effective reorganization energy is much smaller than each of the two components contributing to it and is fully consistent with electrochemical measurements. Calculations in the range of temperatures between 280 and 360 K combine long, classical molecular dynamics simulations with quantum calculations of the protein active site. The results agree with the Arrhenius plots for the reaction rates and with cyclic voltammetry of cytochrome c immobilized on self-assembled monolayers. Small effective reorganization energy, and the resulting small activation barrier, is a general phenomenology of protein electron transfer allowing fast electron transport within biological energy chains.
DOI：
10.1016/j.bbapap.2006.08.007
发表时间：
2006-11
期刊：
Biochimica et biophysica acta
影响因子：
--
作者：
A. Warshel;P. K. Sharma;Mitsunori Kato;W. W. Parson-W.
通讯作者：
A. Warshel;P. K. Sharma;Mitsunori Kato;W. W. Parson-W.
影响因子：
15
作者：
Fedurco, M;Augustynski, J;Dawson, JH
通讯作者：
Dawson, JH
影响因子：
62.1
作者：
Liu, Jing;Chakraborty, Saumen;Hosseinzadeh, Parisa;Yu, Yang;Tian, Shiliang;Petrik, Igor;Bhagi, Ambika;Lu, Yi
通讯作者：
Lu, Yi