Modeling the Ultrafast Electron Attachment Dynamics of Solvated Uracil
Modeling the Ultrafast Electron Attachment Dynamics of Solvated Uracil
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DOI：
10.1021/acs.jpca.1c05288
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发表时间：
2021-08-04
影响因子：
2.9
通讯作者：
Matsika, Spiridoula
中科院分区：
文献类型：
--
作者：
Anstoter, Cate S.;DelloStritto, Mark;Matsika, Spiridoula
低能电子附着在DNA上会导致DNA损伤，因此从根本上理解电子如何与溶液中的核酸组分相互作用是一个开放的挑战。在溶液中，低能电子可以产生预溶剂化电子e（pre）（-），其被嘧啶核碱基有效地清除以形成瞬时负离子，能够弛豫为稳定的价键结合阴离子或经历解离电子脱离或转移到DNA/RNA的其他部分，导致链断裂。为了理解初始电子附着动力学，本文提出了一个联合的分子动力学和高层次的电子结构研究溶剂化的尿嘧啶阴离子的电子态的行为。研究了溶剂化尿嘧啶体系的价π * 和非价e（pre）（-）态，并将溶剂环境和尿嘧啶核的几何结构的影响解偶联，以深入了解溶剂化尿嘧啶阴离子稳定化的物理起源.溶剂重组被发现发挥主导作用，其次是放松的尿嘧啶核心。
Electron attachment to DNA by low energy electrons can lead to DNA damage, so a fundamental understanding of how electrons interact with the components of nucleic acids in solution is an open challenge. In solution, low energy electrons can generate presolvated electrons, e(pre)(-), which are efficiently scavanged by pyrimidine nucleobases to form transient negative ions, able to relax to either stable valence bound anions or undergo dissociative electron detachment or transfer to other parts of DNA/RNA leading to strand breakages. In order to understand the initial electron attachment dynamics, this paper presents a joint molecular dynamics and high-level electronic structure study into the behavior of the electronic states of the solvated uracil anion. Both the valence pi* and nonvalence e(pre)(-) states of the solvated uracil system are studied, and the effect of the solvent environment and the geometric structure of the uracil core are uncoupled to gain insight into the physical origin of the stabilization of the solvated uracil anion. Solvent reorganization is found to play a dominant role followed by relaxation of the uracil core.