Dipartimento di Chimica e Biologia "A. Zambelli", Università di Salerno, via Giovanni Paolo II, 132, I-84084 Fisciano (SA), Italy.
Molecules. 2019 Nov 7;24(22):4044. doi: 10.3390/molecules24224044.
High-energy radiation and oxidizing agents can ionize DNA. One electron oxidation gives rise to a radical cation whose charge (hole) can migrate through DNA covering several hundreds of Å, eventually leading to irreversible oxidative damage and consequent disease. Understanding the thermodynamic, kinetic and chemical aspects of the hole transport in DNA is important not only for its biological consequences, but also for assessing the properties of DNA in redox sensing or labeling. Furthermore, due to hole migration, DNA could potentially play an important role in nanoelectronics, by acting as both a template and active component. Herein, we review our work on the dynamics of hole transfer in DNA carried out in the last decade. After retrieving the thermodynamic parameters needed to address the dynamics of hole transfer by voltammetric and spectroscopic experiments and quantum chemical computations, we develop a theoretical methodology which allows for a faithful interpretation of the kinetics of the hole transport in DNA and is also capable of taking into account sequence-specific effects.
高能辐射和氧化剂可以使 DNA 发生电离。单电子氧化会产生自由基阳离子，其电荷（空穴）可以通过 DNA 迁移几百埃，最终导致不可逆转的氧化损伤和随之而来的疾病。了解 DNA 中空穴传输的热力学、动力学和化学方面不仅对于其生物学后果很重要，而且对于评估 DNA 在氧化还原传感或标记中的性质也很重要。此外，由于空穴迁移，DNA 有可能通过充当模板和活性成分在纳米电子学中发挥重要作用。在此，我们回顾了过去十年中我们在 DNA 中空穴转移动力学方面的工作。在通过伏安法和光谱实验以及量子化学计算检索到解决空穴转移动力学所需的热力学参数之后，我们开发了一种理论方法，该方法能够忠实地解释 DNA 中空穴输运的动力学，并且还能够考虑到序列特异性效应。
