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Fluorophore spectroscopy in aqueous glycerol solution: the interactions of glycerol with the fluorophore

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Abstract

A common perception exists that glycerol provides an inert-like environment modifying viscosity and index of refraction by its various concentrations in aqueous solution. Said perception is herein challenged by investigating the effects of the glycerol environment on the spectroscopic properties of fluorescein, as a representative fluorophore, using steady-state and time-resolved techniques and computational chemistry. Results strongly suggest that the fluorescence quantum yield, measured fluorescence lifetime (FLT), natural lifetime and calculated fluorescence lifetime are all highly sensitive to the presence of glycerol. Glycerol was found to impact both the ground and first excited states of fluorescein, quenching and modifying both absorption and emission spectra, affecting the fundamental electrical dipoles of the ground and first excited singlet states, and lowering FLT and quantum yield. Furthermore, the Stern–Volmer, Lippert–Mataga, Perrin and Strickler–Berg relations indicate that glycerol acts upon fluorescein in aqueous solution as a quencher and alters the fluorescein geometry. Predictions made by computational chemistry impressively correspond to experimental results, both indicating changes in the properties of fluorescein at around 35% v/v aqueous glycerol, a clear indication that glycerol is not an innocent medium. This study proposes the Strickler–Berg relation as a means of detecting non-negligible effects of a hosting medium on its host fluorophore. These new insights on the molecular structures, the interactions between glycerol and its host fluorophore, and the effects of one on the other may be essential for understanding fundamental phenomena in chemistry and related fields.

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Notes

  1. We are not aware of pKa measurements for fluorescein in nonaqueous solutions and binary solvent mixtures. Thus, we cannot be definite regarding the protonation state of the fluorophore. However, it is reasonable to assume that in solvents with a large proportion of water, the behaviour of the solution will more resemble that of the aqueous solution—and it is at these predominantly aqueous solutions where the spectrochemical behaviour of fluorescein is seen to change. It should also be noted that deprotonation provides a larger conjugated π-system, which is a significant stabilizing effect. Regardless, the hydroxy (–OH) group is still a good hydrogen-bond partner. In principle one could calculate the pKa of fluorescein in all the various solutions. However, calculating pKa is notoriously finicky due to the logarithmic nature of pKa, which will magnify any small errors in the calculation. Three potential sources of error are the inherent errors in the (DFT) calculation method, the unknown solvation properties of the proton in various media, and deviations from the assumed linear monotonicity of the Gibbs free energy between 100% water and 100% glycerol.

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Acknowledgements

This study was endowed by the Bequest of Moshe-Shimon and Judith Weisbrodt.

Funding

This study was endowed by the Bequest of Moshe-Shimon and Judith Weisbrodt.

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Authors and Affiliations

  1. Physics Department, The Biophysical Interdisciplinary Schottenstein Center for the Research and Technology of the Cellome, Bar Ilan University, 5290002, Ramat Gan, Israel

    Haim Feldman, Sergei Moshkov, Naomi Zurgil, Elena Afrimzon & Mordechai Deutsch

  2. Computational Chemistry Unit, Department of Chemical Research Support, Weizmann Institute of Science, 7610001, Rehovot, Israel

    Mark A. Iron

  3. Faculty of Engineering and the Institute of Nanotechnology and Advanced Materials, Bar Ilan University, 5290002, Ramat Gan, Israel

    Dror Fixler

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  1. Haim Feldman
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  2. Mark A. Iron
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  3. Dror Fixler
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  4. Sergei Moshkov
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  5. Naomi Zurgil
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  7. Mordechai Deutsch
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Contributions

HF: M.Sc. student who performed the study and helped write the manuscript. MAI: carried out the computational chemistry researched and helped write the manuscript. DF: supervised the lifetime measurements. SM: biochemist who was in charge of solution preparation. NZ: microbiologist who was in charge of the biotechnological aspects of the study and help write the manuscript. EA: helped in macroscopic measurements of the fluorescent solutions. MD: supervised the entire study and helped write the manuscript.

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Correspondence to Mark A. Iron or Mordechai Deutsch.

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Feldman, H., Iron, M.A., Fixler, D. et al. Fluorophore spectroscopy in aqueous glycerol solution: the interactions of glycerol with the fluorophore. Photochem Photobiol Sci 20, 1397–1418 (2021). https://doi.org/10.1007/s43630-021-00096-w

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