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Singlet O2 Reactions with Radical Cations of 8-Bromoguanine and 8-Bromoguanosine: Guided-Ion Beam Mass Spectrometric Measurements and Theoretical Treatments
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    A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters

    Singlet O2 Reactions with Radical Cations of 8-Bromoguanine and 8-Bromoguanosine: Guided-Ion Beam Mass Spectrometric Measurements and Theoretical Treatments
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    • Jonathan Benny
      Jonathan Benny
      Department of Chemistry and Biochemistry, Queens College of the City University of New York, 65-30 Kissena Blvd., Queens, New York 11367, United States
      Ph.D. Program in Chemistry, The Graduate Center of the City University of New York, 365 5th Avenue, New York, New York 10016, United States
    • Toru Saito*
      Toru Saito
      Department of Biomedical Information Science, Graduate School of Information Science, Hiroshima City University, 3-4-1 Ozuka-Higashi, Asa-Minami-Ku, 731-3194 Hiroshima, Japan
      *Email: [email protected]
      More by Toru Saito
    • May Myat Moe
      May Myat Moe
      Department of Chemistry and Biochemistry, Queens College of the City University of New York, 65-30 Kissena Blvd., Queens, New York 11367, United States
      Ph.D. Program in Chemistry, The Graduate Center of the City University of New York, 365 5th Avenue, New York, New York 10016, United States
      More by May Myat Moe
    • , and 
    • Jianbo Liu*
      Jianbo Liu
      Department of Chemistry and Biochemistry, Queens College of the City University of New York, 65-30 Kissena Blvd., Queens, New York 11367, United States
      Ph.D. Program in Chemistry, The Graduate Center of the City University of New York, 365 5th Avenue, New York, New York 10016, United States
      *Email: [email protected]. Phone: 1-718-997-3271.
      More by Jianbo Liu
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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2022, 126, 1, 68–79
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    https://doi.org/10.1021/acs.jpca.1c09552
    Published December 23, 2021
    Copyright © 2021 American Chemical Society

    Abstract

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    8-Bromoguanosine is generated in vivo as a biomarker for early inflammation. Its formation and secondary reactions lead to a variety of biological sequelae at inflammation sites, most of which are mutagenic and linked to cancer. Herein, we report the formation of radical cations of 8-bromoguanine (8BrG•+) and 8-bromoguanosine (8BrGuo•+) and their reactions toward the lowest excited singlet molecular oxygen (1O2)─a common reactive oxygen species generated in biological systems. This work aims to investigate synergistic, oxidatively generated damage of 8-brominated guanine and guanosine that may occur upon ionizing radiation, one-electron oxidation, and 1O2 oxidation. Capitalizing on measurements of reaction product ions and cross sections of 8BrG•+ and 8BrGuo•+ with 1O2 using guided-ion beam tandem mass spectrometry and augmented by computational modeling of the prototype reaction system, 8BrG•+ + 1O2, using the approximately spin-projected ωB97XD/6-31+G(d,p) density functional theory, the coupled cluster DLPNO-CCSD(T)/aug-cc-pVTZ and the multireference CASPT2(21,15)/6-31G**, probable reaction products, and potential energy surfaces (PESs) were mapped out. 8BrG•+ and 8BrGuo•+ present similar exothermic oxidation products, and their reaction efficiencies with 1O2 increase with decreasing collision energy. Both single- and multireference theories predicted that the two most energetically favorable reaction pathways correspond to 1O2-addition to the C8 and C5-positions of 8BrG•+, respectively. The CASPT2-calculated PES represents the best quantitative agreement with the experimental benchmark, in that the oxidation exothermicity is close to the water hydration energy of product ions and, thus, is able to eliminate a water ligand in the product ions.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.1c09552.

    • 8BrG•+ tautomers and Cartesian coordinates for the calculated structures (PDF)

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    This article is cited by 6 publications.

    1. May Myat Moe, Toru Saito, Midas Tsai, Jianbo Liu. Singlet O2 Oxidation of the Radical Cation versus the Dehydrogenated Neutral Radical of 9-Methylguanine in a Watson–Crick Base Pair. Consequences of Structural Context. The Journal of Physical Chemistry B 2022, 126 (29) , 5458-5472. https://doi.org/10.1021/acs.jpcb.2c03748
    2. Belaid Malek, Wenchao Lu, Prabhu Prasad Mohapatra, Niluksha Walalawela, Shakeela Jabeen, Jianbo Liu, Alexander Greer. Probing the Transition State-to-Intermediate Continuum: Mechanistic Distinction between a Dry versus Wet Perepoxide in the Singlet Oxygen “Ene” Reaction at the Air–Water Interface. Langmuir 2022, 38 (19) , 6036-6048. https://doi.org/10.1021/acs.langmuir.2c00279
    3. Nicole Eyet, Shaun G. Ard, Nicholas S. Shuman, Albert A. Viggiano. Ion‐molecule studies of energetic oxygen allotropes in flow tubes: O2(v),O2(aΔg1),O3,andO. Mass Spectrometry Reviews 2025, 44 (2) , 185-209. https://doi.org/10.1002/mas.21846
    4. Zai-Qun Liu. Potentiality of Nucleoside as Antioxidant by Analysis on Oxidative Susceptibility, Drug Discovery, and Synthesis. Current Medicinal Chemistry 2025, 32 (5) , 880-906. https://doi.org/10.2174/0109298673264900231023050108
    5. Jonathan Benny, Toru Saito, Jianbo Liu. Nitrosation mechanisms, kinetics, and dynamics of the guanine and 9-methylguanine radical cations by nitric oxide—Radical–radical combination at different electron configurations. The Journal of Chemical Physics 2024, 161 (12) https://doi.org/10.1063/5.0230367
    6. May Myat Moe, Midas Tsai, Jianbo Liu. Effects of Intra‐Base Pair Proton Transfer on Dissociation and Singlet Oxygenation of 9‐Methyl‐8‐Oxoguanine−1‐Methyl‐Cytosine Base‐Pair Radical Cations. ChemPhysChem 2023, 24 (23) https://doi.org/10.1002/cphc.202300511

    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2022, 126, 1, 68–79
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.1c09552
    Published December 23, 2021
    Copyright © 2021 American Chemical Society

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