The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.
J Am Chem Soc. 2012 Mar 14;134(10):4806-11. doi: 10.1021/ja2109213. Epub 2012 Feb 29.
DNA consists of two type of base-pairs, G-C and A-T, in which the highest occupied molecular orbital (HOMO) localizes on the purine bases G and A. While the hole transfer through consecutive Gs or As occurs faster than 10(9) s(-1), a significant drop in the hole transfer rate was observed for G-C and A-T mixed random sequences. In this study, by using various natural and artificial nucleobases having different HOMO levels, the effect of the HOMO-energy gap between bases (Δ(HOMO)) on the hole-transfer kinetics in DNA was investigated. The results demonstrated that the hole transfer rate can be increased by decreasing the Δ(HOMO) and can be finely tuned over 3 orders of magnitude by varying the Δ(HOMO).
DNA 由两种碱基对组成，G-C 和 A-T，其中嘌呤碱基 G 和 A 上的最高占据分子轨道（HOMO）定位。虽然通过连续的 Gs 或 As 的空穴转移速度比 10(9) s(-1)快，但在 G-C 和 A-T 混合随机序列中观察到空穴转移速率显著下降。在这项研究中，通过使用具有不同 HOMO 水平的各种天然和人工碱基，研究了碱基之间的 HOMO 能隙（Δ（HOMO））对 DNA 中空穴转移动力学的影响。结果表明，通过降低 Δ（HOMO）可以提高空穴转移速率，并且通过改变 Δ（HOMO）可以在 3 个数量级内进行精细调节。
