Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 136, Issue 42, Pages 14801-14810Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja5063955
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Funding
- Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy
- National Science Foundation [CHE-1361516, CHE-0840513]
- National Institutes of Health [GM-59230]
- German Research Foundation
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1361516] Funding Source: National Science Foundation
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Cyclobutane thymine dimer, one of the major lesions in DNA formed by exposure to UV sunlight, is repaired in a photoreactivation process, which is essential to maintain life. The molecular mechanism of the central step, i.e., intradimer C-C bond splitting, still remains an open question. In a simulation study, we demonstrate how the time evolution of characteristic marker bands (C-O and C-C/C-C stretch vibrations) of cyclobutane thymine dimer and thymine dinucleotide radical anion, thymidylyl(3'-> 5')thymidine, can be directly probed with femtosecond stimulated Raman spectroscopy (FSRS). We construct a DFT(M05-2X) potential energy surface with two minor barriers for the intradimer C-5-C-5' splitting and a main barrier for the C-6-C-6' splitting, and identify the appearance of two C-5-C-6 stretch vibrations due to the C-6-C-6' splitting as a spectroscopic signature of the underlying bond splitting mechanism. The sequential mechanism shows only absorptive features in the simulated FSRS signals, whereas the fast concerted mechanism shows characteristic dispersive line shapes.
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