Excited-State Dynamics of Oxyluciferin in Firefly Luciferase

Joris J. Snellenburg, Sergey P. Laptenok, Richard J. Desa, Pance Naumov, Kyril M. Solntsev

    Research output: Contribution to journalArticle

    Abstract

    The color variations of light emitted by some natural and mutant luciferases are normally attributed to collective factors referred to as microenvironment effects; however, the exact nature of these interactions between the emitting molecule (oxyluciferin) and the active site remains elusive. Although model studies of noncomplexed oxyluciferin and its variants have greatly advanced the understanding of its photochemistry, extrapolation of the conclusions to the real system requires assumptions about the polarity and proticity of the active site. To decipher the intricate excited-state dynamics, global and target analysis is performed here for the first time on the steady-state and time-resolved spectra of firefly oxyluciferin complexed with luciferase from the Japanese firefly (Luciola cruciata). The experimental steady-state and time-resolved luminescence spectra of the oxyluciferin/luciferase complex in solution are compared with the broadband time-resolved firefly bioluminescence recorded in vivo. The results demonstrate that de-excitation of the luminophore results in a complex cascade of photoinduced proton transfer processes and can be interpreted by the pH dependence of the emitted light. It is confirmed that proton transfer is the central event in the spectrochemistry of this system for which any assignment of the pH-dependent emission to a single chemical species would be an oversimplification.

    Original languageEnglish (US)
    Pages (from-to)16252-16258
    Number of pages7
    JournalJournal of the American Chemical Society
    Volume138
    Issue number50
    DOIs
    StatePublished - Dec 21 2016

    Fingerprint

    Firefly Luciferases
    Proton transfer
    Fireflies
    Excited states
    Luciferases
    Bioluminescence
    Photochemical reactions
    Extrapolation
    Protons
    Luminescence
    Catalytic Domain
    Color
    Photochemistry
    Light
    Rubiaceae
    Molecules
    oxyluciferin

    ASJC Scopus subject areas

    • Catalysis
    • Chemistry(all)
    • Biochemistry
    • Colloid and Surface Chemistry

    Cite this

    Snellenburg, J. J., Laptenok, S. P., Desa, R. J., Naumov, P., & Solntsev, K. M. (2016). Excited-State Dynamics of Oxyluciferin in Firefly Luciferase. Journal of the American Chemical Society, 138(50), 16252-16258. https://doi.org/10.1021/jacs.6b05078

    Excited-State Dynamics of Oxyluciferin in Firefly Luciferase. / Snellenburg, Joris J.; Laptenok, Sergey P.; Desa, Richard J.; Naumov, Pance; Solntsev, Kyril M.

    In: Journal of the American Chemical Society, Vol. 138, No. 50, 21.12.2016, p. 16252-16258.

    Research output: Contribution to journalArticle

    Snellenburg, JJ, Laptenok, SP, Desa, RJ, Naumov, P & Solntsev, KM 2016, 'Excited-State Dynamics of Oxyluciferin in Firefly Luciferase', Journal of the American Chemical Society, vol. 138, no. 50, pp. 16252-16258. https://doi.org/10.1021/jacs.6b05078
    Snellenburg JJ, Laptenok SP, Desa RJ, Naumov P, Solntsev KM. Excited-State Dynamics of Oxyluciferin in Firefly Luciferase. Journal of the American Chemical Society. 2016 Dec 21;138(50):16252-16258. https://doi.org/10.1021/jacs.6b05078
    Snellenburg, Joris J. ; Laptenok, Sergey P. ; Desa, Richard J. ; Naumov, Pance ; Solntsev, Kyril M. / Excited-State Dynamics of Oxyluciferin in Firefly Luciferase. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 50. pp. 16252-16258.
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