Efficient Electron Transfer in i-Motif DNA with a Tetraplex Structure
Efficient Electron Transfer in i-Motif DNA with a Tetraplex Structure
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DOI：
10.1002/anie.201306017
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发表时间：
2013-12-02
影响因子：
16.6
通讯作者：
Majima, Tetsuro
中科院分区：
文献类型：
--
作者：
Choi, Jungkweon;Tanaka, Atsushi;Majima, Tetsuro
DNA的氧化和还原分别与DNA的损伤和损伤DNA的修复密切相关。 DNA因其作为电子载体的能力及其导电性而被认为是开发基于DNA的分子电子器件的优良材料。因此，了解DNA介导的电荷转移是DNA在生物医学和生物纳米技术中应用的先决条件。 DNA介导的电荷转移已通过理论和实验进行了广泛的研究。[1]然而，大多数关于DNA介导的电荷转移的研究都集中在DNA中的氧化空穴转移，而对还原电子转移的研究相对较少。一般来说，DNA介导的空穴转移发生的距离超过200 [2]，并且沿DNA的空穴转移涉及堆叠的鸟嘌呤(G)碱基之间的许多短距离电荷转移步骤，因为G在四种天然DNA碱基中对氧化最敏感。 [3]空穴转移速率取决于 GC 碱基对之间插入的核碱基。此外，还报道了沿着 DNA 茎堆叠的 G 碱基上的电荷离域。同时，多余电子的转移距离比DNA中空穴的转移距离短。最近，我们课题组证实，多余电子可以通过碱基对迁移超过34个[4]，并且多余电子在连续胸腺嘧啶（T）之间的跳跃速率比腺嘌呤（A）和Gs之间的空穴捕获速率更快。 [5]此外，我们还证明了供体 (D) 之间的单步电子转移（通过超交换机制）
The oxidation and reduction of DNA is closely related to the damage of DNA and the repair of damaged DNA, respectively. DNA has been also regarded as an excellent material for developing DNA-based molecular electronic devices because of its ability as electron carrier and its electrical conductance. Thus, understanding DNA-mediated charge transfer is a prerequisite for the application of DNA in biomedical science and bio-nanotechnology. DNA-mediated charge transfer has been extensively studied by theory and experiments.[1] However, most studies on DNA-mediated charge transfer have focused on the oxidative hole transfer in DNA, whereas relatively few studies have been done on reductive electron transfer.Generally, DNA-mediated hole transfer occurs over a distance longer than 200 [2] and hole transfer along DNA involves many steps of short-distance charge transfer between stacked guanine (G) bases because G among the four natural DNA bases is most sensitive to oxidation.[3] The hole transfer rate depends on the inserted nucleobase between GC base pairs. In addition, delocalization of the charge over the stacked G bases along the DNA stem has been reported. Meanwhile, the distance for transfer of an excess electron is shorter than that for a hole in DNA. Recently, our group confirmed that an excess electron can migrate over 34 through base pairs [4] and the hopping rate of the excess electron among consecutive thymines (T) is faster than the hole trapping rate among adenines (A) and Gs.[5] Furthermore, we showed that single-step electron transfer (through a superexchange mechanism) between a donor (D) in the