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Synthesis and Photochemical Properties of Fluorescent Metabolites Generated from Fluorinated Benzoylmenadiones in Living Cells

  • Nathan Trometer
    Nathan Trometer
    Team Bio(IN)organic and Medicinal Chemistry, Laboratoire d’Innovation Moléculaire et Applications (LIMA), UMR7042 Université de Strasbourg−CNRS−UHA, European School of Chemistry, Polymers and Materials (ECPM), 25 Rue Becquerel, F-67087 Strasbourg, France
  • Bogdan Cichocki
    Bogdan Cichocki
    Team Bio(IN)organic and Medicinal Chemistry, Laboratoire d’Innovation Moléculaire et Applications (LIMA), UMR7042 Université de Strasbourg−CNRS−UHA, European School of Chemistry, Polymers and Materials (ECPM), 25 Rue Becquerel, F-67087 Strasbourg, France
  • Quentin Chevalier
    Quentin Chevalier
    Institut De Biologie Moléculaire Des Plantes, Unité Propre de Recherche 2357, Centre National de la Recherche Scientifique−Université de Strasbourg, Strasbourg F-67084, France
  • Jérémy Pécourneau
    Jérémy Pécourneau
    Team Bio(IN)organic and Medicinal Chemistry, Laboratoire d’Innovation Moléculaire et Applications (LIMA), UMR7042 Université de Strasbourg−CNRS−UHA, European School of Chemistry, Polymers and Materials (ECPM), 25 Rue Becquerel, F-67087 Strasbourg, France
  • Jean-Marc Strub
    Jean-Marc Strub
    Laboratoire de Spectrométrie de Masse BioOrganique (LSMBO), UMR7178 Université de Strasbourg−CNRS, IPHC, 25 Rue Becquerel, 67087 Strasbourg, France
  • Andréa Hemmerlin
    Andréa Hemmerlin
    Institut De Biologie Moléculaire Des Plantes, Unité Propre de Recherche 2357, Centre National de la Recherche Scientifique−Université de Strasbourg, Strasbourg F-67084, France
  • Alexandre Specht
    Alexandre Specht
    Conception et Applications des Molécules Bioactives, Faculté de Pharmacie, UMR 7199 CNRS−Université de Strasbourg, 74 Route du Rhin, Illkirch 67401, France
  • Elisabeth Davioud-Charvet
    Elisabeth Davioud-Charvet
    Team Bio(IN)organic and Medicinal Chemistry, Laboratoire d’Innovation Moléculaire et Applications (LIMA), UMR7042 Université de Strasbourg−CNRS−UHA, European School of Chemistry, Polymers and Materials (ECPM), 25 Rue Becquerel, F-67087 Strasbourg, France
  • , and 
  • Mourad Elhabiri*
    Mourad Elhabiri
    Team Bio(IN)organic and Medicinal Chemistry, Laboratoire d’Innovation Moléculaire et Applications (LIMA), UMR7042 Université de Strasbourg−CNRS−UHA, European School of Chemistry, Polymers and Materials (ECPM), 25 Rue Becquerel, F-67087 Strasbourg, France
    *E-mail: [email protected]
Cite this: J. Org. Chem. 2024, 89, 4, 2104–2126
Publication Date (Web):June 2, 2023
https://doi.org/10.1021/acs.joc.3c00620
Copyright © 2023 American Chemical Society

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    Abstract

    Abstract Image

    This work describes the reactivity and properties of fluorinated derivatives (F-PD and F-PDO) of plasmodione (PD) and its metabolite, the plasmodione oxide (PDO). Introduction of a fluorine atom on the 2-methyl group markedly alters the redox properties of the 1,4-naphthoquinone electrophore, making the compound highly oxidizing and particularly photoreactive. A fruitful set of analytical methods (electrochemistry, absorption and emission spectrophotometry, and HRMS-ESI) have been used to highlight the products resulting from UV photoirradiation in the absence or presence of selected nucleophiles. With F-PDO and in the absence of nucleophile, photoreduction generates a highly reactive ortho-quinone methide (o-QM) capable of leading to the formation of a homodimer. In the presence of thiol nucleophiles such as β-mercaptoethanol, which was used as a model, o-QMs are continuously regenerated in sequential photoredox reactions generating mono- or disulfanylation products as well as various unreported sulfanyl products. Besides, these photoreduced adducts derived from F-PDO are characterized by a bright yellowish emission due to an excited-state intramolecular proton transfer (ESIPT) process between the dihydronapthoquinone and benzoyl units. In order to evidence the possibility of an intramolecular coupling of the o-QM intermediate, a synthetic route to the corresponding anthrones is described. Tautomerization of the targeted anthrones occurs and affords highly fluorescent stable hydroxyl-anthraquinones. Although probable to explain the intense visible fluorescence emission also observed in tobacco BY-2 cells used as a cellular model, these coupling products have never been observed during the photochemical reactions performed in this study. Our data suggest that the observed ESIPT-induced fluorescence most likely corresponds to the generation of alkylated products through reduction species, as demonstrated with the β-mercaptoethanol model. In conclusion, F-PDO thus acts as a novel (pro)-fluorescent probe for monitoring redox processes and protein alkylation in living cells.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.joc.3c00620.

    • Methods for the synthesis and physicochemical analyses used to study the investigated compounds, NMR data of new compounds, absorption, emission and ESI-HRMS data of UV-irradiated systems, electrochemical data for major investigated compounds, and spectrophotometric data for major investigated compounds with biological relevant derivatives and models (PDF)

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    Cited By

    This article is cited by 2 publications.

    1. Nathan Trometer, Jérémy Pecourneau, Liwen Feng, José A. Navarro-Huerta, Danielle Lazarin-Bidóia, Sueli de Oliveira Silva Lautenschlager, Louis Maes, Amanda Fortes Francisco, John M. Kelly, Brigitte Meunier, Monica Cal, Pascal Mäser, Marcel Kaiser, Elisabeth Davioud-Charvet. Synthesis and Anti-Chagas Activity Profile of a Redox-Active Lead 3-Benzylmenadione Revealed by High-Content Imaging. ACS Infectious Diseases 2024, 10 (5) , 1808-1838. https://doi.org/10.1021/acsinfecdis.4c00137
    2. Luana S. Gomes, Érica O. Costa, Thuany G. Duarte, Mateus H. Köhler, Bruna M. Rodrigues, Vitor F. Ferreira, Fernando de C. da Silva, Bernardo A. Iglesias, Vanessa Nascimento. Synthesis and evaluation of photophysical, electrochemical, and ROS generation properties of new chalcogen-naphthoquinones-1,2,3-triazole hybrids. RSC Advances 2023, 13 (49) , 34852-34865. https://doi.org/10.1039/D3RA06977J