Unified Description of Ultrafast Excited State Decay Processes in Epigenetic Deoxycytidine Derivatives
| Autor: | Thomas Carell, Giulio Cerullo, Irene Conti, Marco Garavelli, Eveliina Ponkkonen, Piotr Kabacinski, Vishal K. Jaiswal, Marco Romanelli |
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| Přispěvatelé: | Kabaciński, Piotr, Romanelli, Marco, Ponkkonen, Eveliina, Jaiswal, Vishal Kumar, Carell, Thoma, Garavelli, Marco, Cerullo, Giulio, Conti, Irene |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Letter
intersystem crossing CASPT2/MM transient absorption 010402 general chemistry 01 natural sciences Deoxycytidine Epigenesis Genetic ultrafast spectroscopy chemistry.chemical_compound Gene expression General Materials Science Epigenetics Physical and Theoretical Chemistry conical intersections 010405 organic chemistry DNA Internal conversion (chemistry) 0104 chemical sciences Intersystem crossing chemistry Excited state Biophysics Nucleic Acid Conformation Ground state Epigenetic base |
| Zdroj: | The Journal of Physical Chemistry Letters |
| ISSN: | 1948-7185 |
| Popis: | Epigenetic DNA modifications play a fundamental role in modulating gene expression and regulating cellular and developmental biological processes, thereby forming a second layer of information in DNA. The epigenetic 2′-deoxycytidine modification 5-methyl-2′-deoxycytidine, together with its enzymatic oxidation products (5-hydroxymethyl-2′-deoxycytidine, 5-formyl-2′-deoxycytidine, and 5-carboxyl-2′-deox- ycytidine), are closely related to deactivation and reactivation of DNA transcription. Here, we combine sub-30-fs transient absorption spectroscopy with high-level correlated multiconfigurational CASPT2/MM computational methods, explicitly including the solvent, to obtain a unified picture of the photophysics of deoxycytidine-derived epigenetic DNA nucleosides. We assign all the observed time constants and identify the excited state relaxation pathways, including the competition of intersystem crossing and internal conversion for 5-formyl-2′-deoxycytidine and ballistic decay to the ground state for 5-carboxy-2′-deoxycytidine. Our work contributes to shed light on the role of epigenetic derivatives in DNA photodamage as well as on their possible therapeutic use. |
| Databáze: | OpenAIRE |
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