Cytochrome c Provides an Electron-Funneling Antenna for Efficient Photocurrent Generation in a Reaction Center Biophotocathode.
Cytochrome c Provides an Electron-Funneling Antenna for Efficient Photocurrent Generation in a Reaction Center Biophotocathode.
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DOI：
10.1021/acsami.7b03278
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发表时间：
2017-07-19
影响因子：
9.5
通讯作者：
Frese RN
中科院分区：
文献类型：
--
作者：
Friebe VM;Millo D;Swainsbury DJK;Jones MR;Frese RN
高量子效率的光合反应中心（RC）使他们有吸引力的生物电子和生物光伏应用。然而，大部分天然RC效率在表面结合RC和电极材料之间的通信中丢失。利用细胞色素c（cyt c）作为生物布线剂的最先进的生物光电极最多接近32%的保留RC量子效率。然而，细胞色素c介导的电子转移的瓶颈尚未完全阐明。在这项工作中，蛋白质膜伏安法结合光电化学被用来显示，细胞色素C作为一个电子的funerous天线，穿梭电子从功能化的粗糙银电极的表面固定的RC。两种蛋白质在电极表面上的排列的特征在于，揭示了RC通过疏水相互作用直接连接到电极，并且每个RC的6个cyt c的膜静电结合到电极。我们发现，额外的电连接内的膜的细胞色素C提高了高营业额的要求，表面结合的RC。这导致更大的光电流起始电位、正移的半波还原电位和更高的光电流密度，达到100 μA cm-2。这些发现对于优化利用普遍存在的细胞色素c氧化还原蛋白作为生物导线来利用电极结合酶的生物电子学具有重要意义。
The high quantum efficiency of photosynthetic reaction centers (RCs) makes them attractive for bioelectronic and biophotovoltaic applications. However, much of the native RC efficiency is lost in communication between surface-bound RCs and electrode materials. The state-of-the-art biophotoelectrodes utilizing cytochrome c (cyt c) as a biological wiring agent have at best approached 32% retained RC quantum efficiency. However, bottlenecks in cyt c-mediated electron transfer have not yet been fully elucidated. In this work, protein film voltammetry in conjunction with photoelectrochemistry is used to show that cyt c acts as an electron-funneling antennae that shuttle electrons from a functionalized rough silver electrode to surface-immobilized RCs. The arrangement of the two proteins on the electrode surface is characterized, revealing that RCs attached directly to the electrode via hydrophobic interactions and that a film of six cyt c per RC electrostatically bound to the electrode. We show that the additional electrical connectivity within a film of cyt c improves the high turnover demands of surface-bound RCs. This results in larger photocurrent onset potentials, positively shifted half-wave reduction potentials, and higher photocurrent densities reaching 100 μA cm–2. These findings are fundamental for the optimization of bioelectronics that utilize the ubiquitous cyt c redox proteins as biological wires to exploit electrode-bound enzymes.
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影响因子：
3.9
作者：
den Hollander, Mart-Jan;Magis, J. Gerhard;Frese, Raoul N.
通讯作者：
Frese, Raoul N.
影响因子：
5.5
作者：
Janssen PJ;Lambreva MD;Plumeré N;Bartolucci C;Antonacci A;Buonasera K;Frese RN;Scognamiglio V;Rea G
通讯作者：
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3.3
作者：
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通讯作者：
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作者：
Beissenhirtz, MK;Scheller, FW;Lisdat, F
通讯作者：
Lisdat, F
影响因子：
3.9
作者：
Clark, RA;Bowden, EF
通讯作者：
Bowden, EF