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On the Intrinsically Low Quantum Yields of Pyrimidine DNA Photodamages: Evaluating the Reactivity of the Corresponding Minimum Energy Crossing Points

Giussani, A; Worth, GA; (2020) On the Intrinsically Low Quantum Yields of Pyrimidine DNA Photodamages: Evaluating the Reactivity of the Corresponding Minimum Energy Crossing Points. The Journal of Physical Chemistry Letters , 11 (13) pp. 4984-4989. 10.1021/acs.jpclett.0c01264. Green open access

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Abstract

The low quantum yield of photoformation of cyclobutane pyrimidine dimers and pyrimidine-pyrimidone (6-4) adducts in DNA bases is usually associated with the presence of more favorable nonreactive decay paths and with the unlikeliness of exciting the system in a favorable conformation. Here, we prove that the ability of the reactive conical intersection to bring the system either back to the absorbing conformation or to the photoproduct must be considered as a fundamental factor in the low quantum yields of the mentioned photodamage. In support of the proposed model, the one order of magnitude difference in the quantum yield of formation of the cyclobutane thymine dimer with respect to the thymine-thymine (6-4) adduct is rationalized here by comparing the reactive ability of the seam of intersections leading respectively to the cyclobutane thymine dimer and the oxetane precursor of the thymine-thymine (6-4) adduct at the CASPT2 level of theory.

Type: Article
Title: On the Intrinsically Low Quantum Yields of Pyrimidine DNA Photodamages: Evaluating the Reactivity of the Corresponding Minimum Energy Crossing Points
Location: United States
Open access status: An open access version is available from UCL Discovery
DOI: 10.1021/acs.jpclett.0c01264
Publisher version: https://doi.org/10.1021/acs.jpclett.0c01264
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher's terms and conditions.
Keywords: Adducts, Thymine, Oligomers, Chemical structure, Mathematical methods
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10107818
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