Narayanan S J Jishnu, Tripathi Divya, Verma Pooja, Adhikary Amitava, Dutta Achintya Kumar
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
Department of Chemistry, Oakland University, 146 Library Drive, Rochester, Michigan 48309, United States.
ACS Omega. 2023 Mar 15;8(12):10669-10689. doi: 10.1021/acsomega.2c06776. eCollection 2023 Mar 28.
Reactions of radiation-produced secondary electrons (SEs) with biomacromolecules (e.g., DNA) are considered one of the primary causes of radiation-induced cell death. In this Review, we summarize the latest developments in the modeling of SE attachment-induced radiation damage. The initial attachment of electrons to genetic materials has traditionally been attributed to the temporary bound or resonance states. Recent studies have, however, indicated an alternative possibility with two steps. First, the dipole-bound states act as a doorway for electron capture. Subsequently, the electron gets transferred to the valence-bound state, in which the electron is localized on the nucleobase. The transfer from the dipole-bound to valence-bound state happens through a mixing of electronic and nuclear degrees of freedom. In the presence of aqueous media, the water-bound states act as the doorway state, which is similar to that of the presolvated electron. Electron transfer from the initial doorway state to the nucleobase-bound state in the presence of bulk aqueous media happens on an ultrafast time scale, and it can account for the decrease in DNA strand breaks in aqueous environments. Analyses of the theoretically obtained results along with experimental data have also been discussed.
辐射产生的二次电子(SEs)与生物大分子(如DNA)的反应被认为是辐射诱导细胞死亡的主要原因之一。在本综述中,我们总结了SE附着诱导辐射损伤建模的最新进展。传统上,电子与遗传物质的初始附着归因于临时束缚态或共振态。然而,最近的研究表明了另一种两步的可能性。首先,偶极束缚态充当电子捕获的通道。随后,电子转移到价束缚态,其中电子定域在核碱基上。从偶极束缚态到价束缚态的转移是通过电子和核自由度的混合发生的。在水性介质存在的情况下,水束缚态充当通道态,这与预溶剂化电子的情况类似。在大量水性介质存在的情况下,电子从初始通道态转移到核碱基束缚态发生在超快时间尺度上,这可以解释水性环境中DNA链断裂的减少。还讨论了对理论获得的结果以及实验数据的分析。