Deciphering the protonation and tautomeric equilibria of firefly oxyluciferin by molecular engineering and multivariate curve resolution

Mateusz Rebarz, Boris Marko Kukovec, Oleg V. Maltsev, Cyril Ruckebusch, Lukas Hintermann, Pance Naumov, Michel Sliwa

    Research output: Contribution to journalArticle

    Abstract

    The mysterious flashes of light communicated by fireflies conceal a rich and exciting solution spectrochemistry that revolves around the chemiexcitation and photodecay of the fluorophore, oxyluciferin. A triple chemical equilibrium by double deprotonation and keto–enol tautomerism turns this simple molecule into an intricate case where the relative spectral contributions of six chemical species combine over a physiologically relevant pH range, rendering physical isolation and spectral characterization of most of the species unmanageable. To disentangle the individual spectral contributors, here we demonstrate the advantage of chemical oriented multivariate data analysis. We designed a set of specific oxyluciferin derivatives and applied a multivariate curve resolution-alternating least squares (MCR-ALS) procedure simultaneously to an extensive set of pH-dependent spectroscopic data for oxyluciferin and the target derivatives. The analysis provided, for the first time, the spectra of the pure individual components free of contributions from the other forms, their pH-dependent profiles and distributions, and the most accurate to date values for the three equilibrium constants.

    Original languageEnglish (US)
    Pages (from-to)3803-3809
    Number of pages7
    JournalChemical Science
    Volume4
    Issue number10
    DOIs
    StatePublished - Aug 26 2013

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    Protonation
    Derivatives
    Deprotonation
    Fluorophores
    Equilibrium constants
    Molecules
    oxyluciferin

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Rebarz, M., Kukovec, B. M., Maltsev, O. V., Ruckebusch, C., Hintermann, L., Naumov, P., & Sliwa, M. (2013). Deciphering the protonation and tautomeric equilibria of firefly oxyluciferin by molecular engineering and multivariate curve resolution. Chemical Science, 4(10), 3803-3809. https://doi.org/10.1039/c3sc50715g

    Deciphering the protonation and tautomeric equilibria of firefly oxyluciferin by molecular engineering and multivariate curve resolution. / Rebarz, Mateusz; Kukovec, Boris Marko; Maltsev, Oleg V.; Ruckebusch, Cyril; Hintermann, Lukas; Naumov, Pance; Sliwa, Michel.

    In: Chemical Science, Vol. 4, No. 10, 26.08.2013, p. 3803-3809.

    Research output: Contribution to journalArticle

    Rebarz, M, Kukovec, BM, Maltsev, OV, Ruckebusch, C, Hintermann, L, Naumov, P & Sliwa, M 2013, 'Deciphering the protonation and tautomeric equilibria of firefly oxyluciferin by molecular engineering and multivariate curve resolution', Chemical Science, vol. 4, no. 10, pp. 3803-3809. https://doi.org/10.1039/c3sc50715g
    Rebarz, Mateusz ; Kukovec, Boris Marko ; Maltsev, Oleg V. ; Ruckebusch, Cyril ; Hintermann, Lukas ; Naumov, Pance ; Sliwa, Michel. / Deciphering the protonation and tautomeric equilibria of firefly oxyluciferin by molecular engineering and multivariate curve resolution. In: Chemical Science. 2013 ; Vol. 4, No. 10. pp. 3803-3809.
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