Istituto di Biostrutture Biommagini (IBB-CNR), CNR-Consiglio Nazionale delle Ricerche , Via Mezzocannone 16, I-80134, Napoli, Italy.
Area della Ricerca di Pisa, Istituto di Chimica dei Composti Organo Metallici (ICCOM-CNR), CNR-Consiglio Nazionale delle Ricerche , Via G. Moruzzi 1, I-56124 Pisa, Italy.
Chem Rev. 2016 Mar 23;116(6):3540-93. doi: 10.1021/acs.chemrev.5b00444. Epub 2016 Mar 1.
The photophysics and photochemistry of DNA is of great importance due to the potential damage of the genetic code by UV light. Quantum mechanical studies have played a key role in interpretating the results of modern time-resolved pump-probe spectroscopy, and in elucidating the main photoactivated reactive paths. This review provides a concise, complete picture of the computational studies carried out, approximately, in the past decade. We start with an overview of the photophysics of the nucleobases in the gas phase and in solution. We discuss the proposed mechanisms for ultrafast decay to the ground state, that involve conical intersections, consider the role of triplet states, and analyze how the solvent modulates the photophysics. Then we move to larger systems, from dinucleotides to single- and double-stranded oligonucleotides. We focus on the possible role of charge transfer and delocalized or excitonic states in the photophysics of these systems and discuss the main photochemical paths. We finish with an outlook on the current challenges in the field and future directions of research.
由于紫外线可能会破坏遗传密码，因此 DNA 的光物理和光化学性质非常重要。量子力学研究在解释现代时间分辨泵浦探针光谱学的结果以及阐明主要光激活反应途径方面发挥了关键作用。本篇综述简要而全面地介绍了过去十年中进行的计算研究。我们首先概述了气相和溶液中核碱基的光物理性质。我们讨论了超快衰减到基态的拟议机制，其中涉及到锥形交叉，考虑三重态的作用，并分析了溶剂如何调节光物理性质。然后，我们研究更大的系统，从二核苷酸到单链和双链寡核苷酸。我们专注于电荷转移和离域或激子态在这些系统的光物理性质中的可能作用，并讨论主要的光化学反应途径。最后，我们展望了该领域当前的挑战和未来的研究方向。
