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
Entity
UAM. Departamento de QuímicaPublisher
American Chemical SocietyDate
2022-02-22Citation
10.1021/acs.jpclett.2c00052
The Journal of Physical Chemistry Letters 13.8 (2022): 2000-2006
ISSN
1948-7185 (online)DOI
10.1021/acs.jpclett.2c00052Funded by
This 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)Editor's Version
https://doi.org/10.1021/acs.jpclett.2c00052Subjects
Absorption; Absorption spectroscopy; Nucleobases; Potential energy; Pyrimidine; QuímicaRights
© 2022 The AuthorsAbstract
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
Files in this item
Google Scholar:Vos Esteban, Eva
-
Hoehn, Sean J.
-
Krul, Sarah E.
-
Crespo Hernández, Carlos E.
-
González Vázquez, Jesús
-
Corral Pérez, Inés
This item appears in the following Collection(s)
Related items
Showing items related by title, author, creator and subject.
-
The origin of efficient triplet state population in sulfur-substituted nucleobases
Mai, Sebastian; Pollum, Marvin; Martínez-Fernández, Lara; Dunn, Nicholas; Marquetand, Philipp; Corral, Inés; Crespo-Hernández, Carlos E.; González, Leticia
2016-10-05