Quantum Mechanical Studies on the Photophysics and the Photochemistry of Nucleic Acids and Nucleobases
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- 作者：Roberto Improta ; Fabrizio Santoro ; Lluís Blancafort
- 刊名：Chemical Reviews
- 出版年：2016
- 出版时间：March 23, 2016
- 年：2016
- 卷：116
- 期：6
- 页码：3540-3593
- 全文大小：1974K
- 年卷期：Roberto Improta was born in Naples on May 12, 1970. He graduated and received a Ph.D. in chemistry in 1998 from the University of Naples “Federico II”. He spent his postodoctoral fellowships in Pisa, in Houston, and in Naples. In 2001 he got a permament position at the Italian National Research Council at IBB in Naples, where he has been senior research scientist since 2007. He is a member of the Executive Committee of the European Photochemical Association. Beyond the theoretical study of the excited state dynamics of nucleic acids, his main research interest concerns the development, validation, and application of theoretical models and computational methods for the study of large size molecules, mainly based on DFT/TD-DFT calculations and continuum solvation models, with special attention to photochemical and photophysical processes in condensed phase.Fabrizio Santoro got his Ph.D. in chemical sciences in 1999 at the Universities of Siena and Perugia. He was postdoc at the University of Siena and at the University of Würzburg. In 2001 he was appointed research scientist at the Italian National Research Council in Pisa, where he has been senior research scientist since 2007. His research interests are in computational and theoretical chemistry and focus on fundamental properties and dynamical processes in molecular excited states in gas and condensed phases. He develops methods for vibronic spectroscopy of linear and nonlinear spectroscopies and studies the quantum dynamics of nonadiabatic processes triggered by light absorption with a special focus on biologically relevant systems like nucleobases and their oligomers. He has published more than 100 papers in peer-reviewed journals.Lluı́s Blancafort received his degree in chemical engineering at the Institut Quı́mic de Sarrià (Barcelona) in 1991. He obtained his Ph.D. in 1996 from the University of Würzburg, for research on the reactivity of α-peroxylactones. From 1997 to 2002 he carried out a postdoctoral stay at King’s College London, working on the computation of excited-state mechanisms. In 2002, he joined the University of Girona as a Ramón y Cajal fellow and became associate professor in 2007. He was Director of the Institut de Quı́mica Computacional i Catàlisi from 2007 to 2015. His main research interests are the theory and computation of excited states and nonadiabatic processes, including excited-state potential energy surfaces and dynamics.
- ISSN：1520-6890
文摘
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.