Interfacial redox processes of cytochrome b562.

Interfacial redox processes of cytochrome b562.
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细胞色素 b562 的界面氧化还原过程。

DOI:
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发表时间:
2009
期刊:
Physical Chemistry, Chemical Physics - PCCP
影响因子:
--
通讯作者:
P. Hildebrandt
P. Hildebrandt
中科院分区:
--
文献类型:
--
作者:
P. Zuo;T. Albrecht;P. Barker;D. Murgida;P. Hildebrandt

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将阴离子可溶性血红素蛋白细胞色素 b(562) 静电固定在涂有带正电的氨基末端链烷硫醇自组装单层的银电极上。通过固定和时间分辨表面增强共振拉曼光谱研究血红素袋的结构、氧化还原平衡和电子转移动力学,并辅以界面氧化还原过程的循环伏安法测量。将固定蛋白的构象和氧化还原平衡与固定在带负电的电极涂层上的阳离子血红素蛋白细胞色素 c 的构象和氧化还原平衡进行比较。相似点和差异可以通过氨基和羧基封端电极涂层界面处各自的电场来合理化。细胞色素 b(562) 的异质电子转移率仅随着厚度从约 100 减小而略有增加。参见图20至11A,这意味着电子隧道效应不是速率限制步骤。与羧基封端单层上的细胞色素 c 不同,这种行为不能归因于蛋白质重新定向门控异质电子转移。相反,它可能反映了蛋白质间电子转移和通过蛋白质方向的异质电子转移之间的相互作用,对于与电极的电子交换表现出特别高的隧道概率。
The anionic soluble heme protein cytochrome b(562) was electrostatically immobilised on Ag electrodes coated with positively charged self-assembled monolayers of amino-terminated alkanethiols. The structure of the heme pocket, the redox equilibria, and the electron transfer dynamics were studied by stationary and time-resolved surface enhanced resonance Raman spectroscopy, complemented by cyclic voltammetry measurements of the interfacial redox process. The conformational and redox equilibria of the immobilised protein are compared to those of the cationic heme protein cytochrome c immobilised on negatively charged electrode coatings. Similarities and differences can be rationalised in terms of the respective electric fields at the interfaces of amino- and carboxyl-terminated electrode coatings. The heterogeneous electron transfer rate of cytochrome b(562) only slightly increases with decreasing thickness from ca. 20 to 11 A, implying that the electron tunneling is not the rate-limiting step. In contrast to cytochrome c on carboxyl-terminated monolayers, this behaviour cannot be attributed to protein re-orientation gating the heterogeneous electron transfer. Instead, it may reflect the interplay between interprotein electron transfer and heterogeneous electron transfer via protein orientations exhibiting particularly high tunneling probabilities for the electron exchange with the electrode.
编码大肠杆菌可溶性细胞色素b562的基因的克隆和表达。
DOI: 10.1111/j.1432-1033.1991.tb16377.x
发表时间: 1991
期刊: European journal of biochemistry
影响因子: --
作者:
Nikkila,H;Gennis,RB;Sligar,SG
通讯作者: Sligar,SG