Protein Photoconductors and Photodiodes

Protein Photoconductors and Photodiodes
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DOI:
10.1002/anie.201103341
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发表时间:
2011-01-01
影响因子:
16.6
通讯作者:
Watanabe, Yoshihito
Watanabe, Yoshihito
中科院分区:
化学1区
文献类型:
--
作者:
Tokita, Yuichi;Yamada, Seiji;Watanabe, Yoshihito

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通过蛋白质的远程电子转移(ET)在生命系统中起着重要作用。ET蛋白可以被视为具有“掺杂剂”(氧化还原或光活性物质)的宽带隙分子半导体,提供电子或空穴定位位点,尽管蛋白质支架具有绝缘特性。[1-10]为了阐明控制这些非绝热反应速率的因素,许多研究小组对蛋白质中的分子内ET进行了详细的研究。[1 - 9,11 - 13] Dutton及其同事提出了一个方形势垒ET速率模型[11,12],而Gray及其同事则表明ET取决于电子供体和受体之间的介质结构。[5-9]我们研究了锌取代细胞色素b562 (Zn-cytb562)和锌取代细胞色素c (Zn-cytc)两种蛋白的光诱导ET,它们的半导体特性取决于其分子表面的电荷分布:Zn-cytb562具有n型半导体特性,而Zn-cytc为p型半导体,尽管这两种体系的活性中心几乎相同。这一发现可能会打开基于蛋白质的电子学的世界,因为蛋白质的半导体特性可以通过表面电荷的变化来控制。
Long-range electron transfer (ET) through proteins plays important roles in living systems. ET proteins can be regarded as wide-band-gap molecular semiconductors with “dopants”(redox or photoactive species) that provide an electron-or hole-localizing site, though the protein scaffold has insulating character.[1–10] Intramolecular ET in proteins has been investigated in detail by many groups to elucidate the factors that control the rates of these nonadiabatic reactions.[1–9, 11–13] Dutton and co-workers proposed a square barrier ET rate model,[11, 12] while Gray and colleagues showed that ET depends on the structure of the medium between an electron donor and acceptor.[5–9]We have investigated photoinduced ET in two proteins, zinc-substituted cytochrome b562 (Zn-cytb562) and zinc-substituted cytochrome c (Zn-cytc), the semiconductor properties of which depend on the charge distribution on their molecular surfaces: Zn-cytb562 has n-type semiconductor character while Zn-cytc is p-type, although the active center of the two systems is virtually identical. This finding may open up the world of protein-based electronics, because the semiconductor character of proteins could be controlled by variations in surface charge.