Disclosing the role of C4-Oxo substitution in the photochemistry of DNA and RNA pyrimidine monomers: formation of photoproducts from the vibrationally excited ground state
EntityUAM. Departamento de Química
PublisherAmerican Chemical Society
10.1021/acs.jpclett.2c00052The Journal of Physical Chemistry Letters 13.8 (2022): 2000-2006
Funded byThis Letter was supported by project PGC2018-094644-B-C21 of the Ministerio de Ciencia, Innovación y Universidades of Spain, the Ramón y Cajal program, and a Formación de Profesorado Universitario contract from the Ministerio de Economía, Industria y Competitividad of Spain. Thanks are also extended to the Red Española de Supercomputación, the Mare Nostrum and Cesga Supercomputer Centers, and the Centro de Computación Científica of the UAM (CCC-UAM) for the generous allocation of computer time and for their continued technical support. Very useful discussions with Dr. Enrique M. Arpa are also acknowledged. S.J.H., S.E.K., and C.E.C.-H. acknowledge the National Science Foundation (Grant No. CHE-1800052)
SubjectsAbsorption; Absorption spectroscopy; Nucleobases; Potential energy; Pyrimidine; Química
Rights© 2022 The Authors
Esta obra está bajo una Licencia Creative Commons Atribución 4.0 Internacional.
Oxo and amino substituted purines and pyrimidines have been suggested as protonucleobases participating in ancient pre-RNA forms. Considering electromagnetic radiation as a key environmental selection pressure on early Earth, the investigation of the photophysics of modified nucleobases is crucial to determine their viability as nucleobases’ ancestors and to understand the factors that rule the photostability of natural nucleobases. In this Letter, we combine femtosecond transient absorption spectroscopy and quantum mechanical simulations to reveal the photochemistry of 4-pyrimidinone, a close relative of uracil. Irradiation of 4- pyrimidinone with ultraviolet radiation populates the S1(ππ*) state, which decays to the vibrationally excited ground state in a few hundred femtoseconds. Analysis of the postirradiated sample in water reveals the formation of a 6-hydroxy-5H-photohydrate and 3-(N-(iminomethyl)- imino)propanoic acid as the primary photoproducts. 3-(N-(Iminomethyl)imino)propanoic acid originates from the hydrolysis of an unstable ketene species generated from the C4−N3 photofragmentation of the pyrimidine core
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Google Scholar:Vos Esteban, Eva - Hoehn, Sean J. - Krul, Sarah E. - Crespo Hernández, Carlos E. - González Vázquez, Jesús - Corral Pérez, Inés
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Mai, Sebastian; Pollum, Marvin; Martínez-Fernández, Lara; Dunn, Nicholas; Marquetand, Philipp; Corral, Inés; Crespo-Hernández, Carlos E.; González, Leticia