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Tackling a Curious Case: Generation of Charge-Tagged Guanosine Radicals by Gas-Phase Electron Transfer and Their Characterization by UV–vis Photodissociation Action Spectroscopy and Theory

  • Yue Liu
    Yue Liu
    Department of Chemistry, Bagley Hall, Box 351700, University of Washington, Seattle, Washington 98195-1700, United States
    More by Yue Liu
  • Congcong Ma
    Congcong Ma
    Department of Chemistry, Bagley Hall, Box 351700, University of Washington, Seattle, Washington 98195-1700, United States
    More by Congcong Ma
  • Calvin J. A. Leonen
    Calvin J. A. Leonen
    Department of Chemistry, Bagley Hall, Box 351700, University of Washington, Seattle, Washington 98195-1700, United States
  • Champak Chatterjee
    Champak Chatterjee
    Department of Chemistry, Bagley Hall, Box 351700, University of Washington, Seattle, Washington 98195-1700, United States
  • Gabriela Nováková
    Gabriela Nováková
    Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, 16610 Prague 6, Czech Republic
  • Aleš Marek*
    Aleš Marek
    Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, 16610 Prague 6, Czech Republic
    *Email: [email protected]
    More by Aleš Marek
  • , and 
  • František Tureček*
    František Tureček
    Department of Chemistry, Bagley Hall, Box 351700, University of Washington, Seattle, Washington 98195-1700, United States
    Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, 16610 Prague 6, Czech Republic
    *Phone +1-206-685-2041l. Email: [email protected]
Cite this: J. Am. Soc. Mass Spectrom. 2021, 32, 3, 772–785
Publication Date (Web):February 10, 2021
https://doi.org/10.1021/jasms.0c00459
Copyright © 2021 American Society for Mass Spectrometry. Published by American Chemical Society. All rights reserved.

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    Abstract

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    We report the generation of gas-phase riboguanosine radicals that were tagged at ribose with a fixed-charge 6-(trimethylammonium)hexane-1-aminocarbonyl group. The radical generation relied on electron transfer from fluoranthene anion to noncovalent dibenzocrown-ether dication complexes which formed nucleoside cation radicals upon one-electron reduction and crown-ether ligand loss. The cation radicals were characterized by collision-induced dissociation (CID), photodissociation (UVPD), and UV–vis action spectroscopy. Identification of charge-tagged guanosine radicals was challenging because of spontaneous dissociations by loss of a hydrogen atom and guanine that occurred upon storing the ions in the ion trap without further excitation. The loss of H proceeded from an exchangeable position on N-7 in guanine that was established by deuterium labeling and was the lowest energy dissociation of the guanosine radicals according to transition-state energy calculations. Rate constant measurements revealed an inverse isotope effect on the loss of either hydrogen or deuterium with rate constants kH = 0.25–0.26 s–1 and kD = 0.39–0.54 s–1. We used time-dependent density functional theory calculations, including thermal vibronic effects, to predict the absorption spectra of several protomeric radical isomers. The calculated spectra of low-energy N-7-H guanine-radical tautomers closely matched the action spectra. Transition-state-theory calculations of the rate constants for the loss of H-7 and guanine agreed with the experimental rate constants for a narrow range of ion effective temperatures. Our calculations suggest that the observed inverse isotope effect does not arise from the isotope-dependent differences in the transition-state energies. Instead, it may be caused by the dynamics of post-transition-state complexes preceding the product separation.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jasms.0c00459.

    • Description of synthetic procedures, compound characterization, auxiliary figures of mass spectra, TST calculations and discussion of kinetics, molecular orbitals, UV–vis action spectra of cations, and TD-DFT calculated absorption spectra (PDF)

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    Cited By

    This article is cited by 6 publications.

    1. Jiahao Wan, Břetislav Brož, Yue Liu, Shu R. Huang, Aleš Marek, František Tureček. The DNA Radical Code. Resolution of Identity in Dissociations of Trinucleotide Codon Cation Radicals in the Gas Phase. Journal of the American Society for Mass Spectrometry 2023, 34 (2) , 304-319. https://doi.org/10.1021/jasms.2c00322
    2. Yue Liu, Congcong Ma, Gabriela Nováková, Aleš Marek, František Tureček. Charge-Tagged Nucleosides in the Gas Phase: UV–Vis Action Spectroscopy and Structures of Cytidine Cations, Dications, and Cation Radicals. The Journal of Physical Chemistry A 2021, 125 (28) , 6096-6108. https://doi.org/10.1021/acs.jpca.1c03477
    3. František Tureček. Flying DNA Cation Radicals in the Gas Phase: Generation and Action Spectroscopy of Canonical and Noncanonical Nucleobase Forms. The Journal of Physical Chemistry B 2021, 125 (26) , 7090-7100. https://doi.org/10.1021/acs.jpcb.1c03674
    4. Min Kou, Luyang Jiao, Shiyin Xu, Mengying Du, Yameng Hou, Xianglei Kong. Structural Characterization of the Metalized Radical Cations of Adenosine ([Ade+Li-H]•+ and [Ade+Na-H]•+) by Infrared Multiphoton Dissociation Spectroscopy and Theoretical Studies. International Journal of Molecular Sciences 2023, 24 (20) , 15385. https://doi.org/10.3390/ijms242015385
    5. František Tureček. UV‐vis spectroscopy of gas‐phase ions. Mass Spectrometry Reviews 2023, 42 (1) , 206-226. https://doi.org/10.1002/mas.21726
    6. Bojidarka Ivanova, Michael Spiteller. Stochastic dynamic quantitative and 3D structural matrix assisted laser desorption/ionization mass spectrometric analyses of mixture of nucleosides. Journal of Molecular Structure 2022, 1260 , 132701. https://doi.org/10.1016/j.molstruc.2022.132701

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