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Excited State Dynamics of 6-Thioguanine

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Department of Chemistry and Biochemistry, University of California, Santa Barbara, Santa Barbara, California 93016-9510, United States
*E-mail [email protected]
Cite this: J. Phys. Chem. A 2017, 121, 28, 5257–5266
Publication Date (Web):June 26, 2017
https://doi.org/10.1021/acs.jpca.7b03036
Copyright © 2017 American Chemical Society
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    Abstract

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    Here we present the excited state dynamics of jet-cooled 6-thioguanine (6-TG), using resonance-enhanced multiphoton ionization (REMPI), IR–UV double resonance spectroscopy, and pump–probe spectroscopy in the nanosecond and picosecond time domains. We report data on two thiol tautomers, which appear to have different excited state dynamics. These decay to a dark state, possibly a triplet state, with rates depending on tautomer form and on excitation wavelength, with the fastest rate on the order of 1010 s–1. We also compare 6-TG with 9-enolguanine, for which we observed decay to a dark state with a 2 orders of magnitude smaller rate. At increased excitation energy (∼+500 cm–1) an additional pathway appears for the predominant thiol tautomer. Moreover, the excited state dynamics for 6-TG thiols is different from that recently predicted for thiones.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpca.7b03036.

    • Singlet and triplet excited state analysis at CCSD/6-31+G(2d,p) for ground state and EOM-CCSD/6-31+G(2d,p) for excited states, nanosecond pump probe trace of 9-enol guanine at its origin (PDF)

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    13. Brennan Ashwood, Marvin Pollum, Carlos E. Crespo‐Hernández. Photochemical and Photodynamical Properties of Sulfur‐Substituted Nucleic Acid Bases,. Photochemistry and Photobiology 2019, 95 (1) , 33-58. https://doi.org/10.1111/php.12975
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    17. Shoma Miyata, Shunsuke Tanabe, Tasuku Isozaki, Yao-Zhong Xu, Tadashi Suzuki. Characteristics of the excited triplet states of thiolated guanosine derivatives and singlet oxygen generation. Photochemical & Photobiological Sciences 2018, 17 (10) , 1469-1476. https://doi.org/10.1039/c8pp00240a
    18. Sebastian Mai, Felix Plasser, Philipp Marquetand, Leticia González. General Trajectory Surface Hopping Method for Ultrafast Nonadiabatic Dynamics. 2018, 348-385. https://doi.org/10.1039/9781788012669-00348
    19. Brennan Ashwood, Luis A. Ortiz-Rodríguez, Carlos E. Crespo-Hernández. Photochemical relaxation pathways of S 6 -methylthioinosine and O 6 -methylguanosine in solution. Faraday Discussions 2018, 207 , 351-374. https://doi.org/10.1039/C7FD00193B
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