Modulation of DNA mediated hole transport by novel substituents on DNA

DNA 上新型取代基对 DNA 介导的空穴传输的调节

• 批准号: 13450351
• 负责人: NAKATANI Kazuhiko
• 金额: $ 8.51万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13450351/
• 关键词: hole transport; DNA; cyclopropyl; ラジカルカチオン; ホール検出手法; ラジカルカオチン

While the mechanism of DNA mediated hole transport is a subject of controversy, it is now evident from remote guanine (G) oxidation of duplex DNAs containing a tethered oxidant that G radical cation (hole) migrates distance through DNA _<TT>-stack. Due to lower ionization potentials of GG and GGG than single G, these stacked G sites function as a thermodynamic sink of holes eventually producing, (piperidine labile sites. In principle, hole migration from hole donor to acceptor competes with hole trapping by water and/or oxygen. Therefore, overall efficiency of hole transfer is primarily determined by the rates of hole migration and hole trapping. When the rate of hole trapping is much slower than hole migration rate, equilibration of hole between donor and acceptor can be achieved. While the rate of hole migration can be attenuated by changing the potential energy gap between hole donor and acceptor, the modulation of hole transport efficiency by changing the rate of hole trapping has never been demonstrated. We report a novel hole-trapping nucleoside N2-cyclopropyl2'-deoxyguanosine 1 (dCPG), which possesses a cyclopropyl group on N2 as a radical-trapping device. One electron oxidation of dCPG by photoexcited riboflavine induces homolytic cyclopropane ring opening as evidenced by the formation of N2-(3-hydroxypropanoyl)dG 2. With the use of dCPG -containing duplex, we have demonstrated that dCPG efficiently terminates DNA mediated hole transport at its own site.

虽然DNA介导的孔传输的机制是一个有争议的主题，但现在可以从远程鸟嘌呤（G）氧化的双链DNA（g）含有束缚氧化剂的双链DNA（g自由基阳离子（孔）通过DNA _ <tt> -Stack迁移的距离。由于GG和GGG的电离电位低于单个G，这些堆叠的G位点起到了最终产生的孔的热力学水槽的作用（哌啶不稳定位点。原则上，孔从孔供体到受体竞争受体竞争，与孔通过水和/或氧气迁移的整体率是孔的整体速率，而在孔中的总体效率是，孔的整体率是孔的整体迁移。供体和受体之间的孔的速率可以通过改变孔供体和受体之间的势能差异来减轻孔的迁移速率，通过改变孔捕获速率的孔传输效率的调节从未证明我们从未证明过核苷N2-cyclopopompyl2'declopoll2'decloply a cyollaper a cy rapoply a。 N2作为一种自由基捕获装置。

项目成果

Nakatani, K. et al.: "Recognition of Guanine-Guanine Mismatch by Dimeric Form of 2-Amino-1,8-naphthyridine"J. Am. Chem. Soc.. 123・50. 12650-12657 (2001)

Nakatani, K. 等：“2-氨基-1,8-萘啶二聚体的鸟嘌呤-鸟嘌呤错配的识别”J. Am. Soc. 123・50 (2001)。

Nakatani, K. et al.: "Design of Hole-Trapping Nucleobase : Termination of DNA Mediated Hole Transport at N^2-Cyclopropyldeoxyguanosine"J. Am. Chem. Soc.. 123・39. 9681-9682 (2001)

Nakatani, K. 等：“空穴捕获核碱基的设计：N^2-环丙基脱氧鸟苷的 DNA 介导的空穴传输”J. Am. 123・39 (2001)。

Nakatani, K. et al.: "Suppression of DNA-Mediated Charge Transport by BamH I Binding"Chem. Bio.. 9. 361-366 (2002)

Nakatani, K. 等人：“BamH I 结合抑制 DNA 介导的电荷传输”Chem。

Nakatani, K. et al.: "Guanine of the Third Strand of C.G^*G Triplex Serves as an Effective Hole Trap"J. Am. Chem. Soc.. 123・49. 9681-9682 (2001)

Nakatani, K. 等：“C.G^*G 三链体的鸟嘌呤作为有效的空穴陷阱”J. Soc. 123・49 (2001)。

Nakatani, K., Sando, S., Kumasawa, H., Kikuchi, J., Saito, I.: "Recognition of Guanine-Guanine Mismatch by Dimeric Form of 2-Amino-l, 8-naphthyridine"J. Am. Chem. Soc. 123. 12650-12657 (2001)

Nakatani, K.、Sando, S.、Kumasawa, H.、Kikuchi, J.、Saito, I.：“通过 2-氨基-1, 8-萘啶二聚形式识别鸟嘌呤-鸟嘌呤错配”J.