The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.
J Am Chem Soc. 2010 Jan 20;132(2):627-30. doi: 10.1021/ja907409z.
A positive charge migrates along DNA mainly via a series of short-range charge transfer (CT) processes between G-C base pairs, which have relatively high HOMO levels. As such, the CT efficiency sharply decreases with the insertion of A-T base pairs between the G-C base pairs. We have previously demonstrated that the CT efficiency through DNA can be dramatically increased by using deazaadenine (Z), an analogue of A, to adjust the HOMO levels of the A-T base pairs closer to those of the G-C base pairs (Nat. Chem. 2009, 1, 156). In the present study, we have expanded this approach to show that the CT efficiency can also be increased by replacing A bases with diaminopurine (D).
正电荷主要通过 G-C 碱基对之间一系列短程电荷转移 (CT) 过程沿 DNA 迁移,G-C 碱基对具有相对较高的 HOMO 能级。因此,随着 A-T 碱基对插入 G-C 碱基对之间,CT 效率急剧下降。我们之前已经证明,通过使用腺嘌呤类似物去氮腺嘌呤 (Z) 来调整 A-T 碱基对的 HOMO 能级更接近 G-C 碱基对的 HOMO 能级,可以显著提高通过 DNA 的 CT 效率(Nat. Chem. 2009, 1, 156)。在本研究中,我们扩展了这种方法,表明通过用二氨基嘌呤 (D) 替代 A 碱基也可以提高 CT 效率。