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Dual-Fluorescence Probe of Environment Basicity (Hydrogen Bond Accepting Ability) Displaying no Sensitivity to Polarity

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Abstract

3-Hydroxyquinolones (3HQs) are a new class of water soluble dual fluorescence probes that can monitor both polarity and basicity (H-bond accepting ability) parameters. Both parameters play an important role in proteins and lipid membranes. Nevertheless, no method exists actually to measure the basicity parameter separately from the polarity. To achieve this aim, we synthesized 2-benzofuryl-3-hydroxy-4(1H)-quinolone (3HQ-Bf) and characterized its photophysical properties by UV, steady-state and time-resolved fluorescence spectroscopy. Due to its extended conjugation and totally planar conformation, 3HQ-Bf is characterized by a high fluorescence quantum yield. In solution, this dye shows an excited state intramolecular proton transfer (ESIPT) reaction resulting in two tautomer bands in the emission spectra. The ESIPT reaction can be considered as irreversible and is governed by rate constants from 0.6 to 8 × 109 s−1, depending on the solvent. The analysis of the spectral properties of 3HQ-Bf in a series of organic solvents revealed a marginal sensitivity to the solvent polarity, but an exquisite sensitivity to solvent basicity, as shown by the linear dependence of the logarithm of the emission bands intensity ratio, log(IN*/IT*), as well as the absorption or emission maxima wavenumbers as a function of the solvent basicity parameter. This probe may find useful applications through coupling to a protein ligand, for characterizing the H-bond acceptor ability at the ligand binding site as well as for studying the basicity changes of lipid membranes during their chemo- and thermotropic conversions.

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Acknowledgments

This work was supported by the ECO-NET and ARCUS programs from the French Ministère des Affaires Etrangères. DAY and VVS are recipients of a high-level Eiffel Fellowship. VGP was supported by a fellowship from University Louis Pasteur. We are also thankful to Andrey Klymchenko for useful discussion and to Etienne Piémont for help with time-resolved measurements.

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Authors and Affiliations

  1. Organic Chemistry Department, Chemistry Faculty, National Taras Shevchenko University of Kyiv, Kyiv, 01601, Ukraine

    Mykhailo D. Bilokin’, Volodymyr V. Shvadchak, Dmytro A. Yushchenko & Vasyl G. Pivovarenko

  2. Photophysique des Interactions Biomoléculaires, UMR 7175 du CNRS, Institut Gilbert Laustriat, Faculté de Pharmacie, Université Louis Pasteur, Illkirch, 67401, France

    Volodymyr V. Shvadchak, Dmytro A. Yushchenko, Guy Duportail, Yves Mély & Vasyl G. Pivovarenko

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  1. Mykhailo D. Bilokin’
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  2. Volodymyr V. Shvadchak
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  3. Dmytro A. Yushchenko
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  5. Yves Mély
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  6. Vasyl G. Pivovarenko
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Correspondence to Vasyl G. Pivovarenko.

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Bilokin’, M.D., Shvadchak, V.V., Yushchenko, D.A. et al. Dual-Fluorescence Probe of Environment Basicity (Hydrogen Bond Accepting Ability) Displaying no Sensitivity to Polarity. J Fluoresc 19, 545–553 (2009). https://doi.org/10.1007/s10895-008-0443-x

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