Vibrational spectra of chemical and isotopic variants of oxyluciferin, the light emitter of firefly bioluminescence

Oleg V. Maltsev, Ling Yue, Mateusz Rebarz, Lukas Hintermann, Michel Sliwa, Cyril Ruckebusch, Ljupčo Pejov, Ya Jun Liu, Pance Naumov

    Research output: Contribution to journalArticle

    Abstract

    The chemical complexity of oxyluciferin (OxyLH2), the light-emitting molecule in the bioluminescence of fireflies, originates from the possibility of keto/enol tautomerism and single or double deprotonation. Herein, we present detailed infrared spectroscopic analysis of OxyLH2 and several of its chemical isomers and isotopomers. To facilitate the future characterization of its biogenic forms, we provide accurate assignments of the solid-state and solution FTIR spectra of OxyLH2 based on comparison to six isotopically labeled variants ([2-13C]-OxyLH2, [3-15N]-OxyLH2, [4-13C]-OxyLH2, [5-13C]-OxyLH2, [2′-13C]-OxyLH 2, [3′-15N]-OxyLH2), five closely related structural analogues, and theoretically computed spectra. The computed DFT harmonic vibrational force fields (B3LYP and M06 functionals with basis sets of varying flexibility up to 6-311++G) reproduce well the observed shifts in the IR spectra of both isotopically labeled and structurally related analogues. Illuminating IR spectra: A detailed IR spectroscopic study of oxyluciferin, the light emitter of firefly bioluminescence, has been performed, which reveals the most accurate vibrational assignments to date (see figure). To that end, a set of oxyluciferin analogues and isotopomers were prepared, and their spectra were recorded in the solid state and in acetonitrile solution.

    Original languageEnglish (US)
    Pages (from-to)10782-10790
    Number of pages9
    JournalChemistry - A European Journal
    Volume20
    Issue number34
    DOIs
    StatePublished - Aug 18 2014

    Fingerprint

    Bioluminescence
    Vibrational spectra
    Deprotonation
    Spectroscopic analysis
    Acetonitrile
    Discrete Fourier transforms
    Isomers
    Infrared radiation
    Molecules
    oxyluciferin

    Keywords

    • bioluminescence
    • DFT calculations
    • IR spectroscopy
    • isotope labeling
    • oxyluciferin

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Maltsev, O. V., Yue, L., Rebarz, M., Hintermann, L., Sliwa, M., Ruckebusch, C., ... Naumov, P. (2014). Vibrational spectra of chemical and isotopic variants of oxyluciferin, the light emitter of firefly bioluminescence. Chemistry - A European Journal, 20(34), 10782-10790. https://doi.org/10.1002/chem.201400210

    Vibrational spectra of chemical and isotopic variants of oxyluciferin, the light emitter of firefly bioluminescence. / Maltsev, Oleg V.; Yue, Ling; Rebarz, Mateusz; Hintermann, Lukas; Sliwa, Michel; Ruckebusch, Cyril; Pejov, Ljupčo; Liu, Ya Jun; Naumov, Pance.

    In: Chemistry - A European Journal, Vol. 20, No. 34, 18.08.2014, p. 10782-10790.

    Research output: Contribution to journalArticle

    Maltsev, OV, Yue, L, Rebarz, M, Hintermann, L, Sliwa, M, Ruckebusch, C, Pejov, L, Liu, YJ & Naumov, P 2014, 'Vibrational spectra of chemical and isotopic variants of oxyluciferin, the light emitter of firefly bioluminescence', Chemistry - A European Journal, vol. 20, no. 34, pp. 10782-10790. https://doi.org/10.1002/chem.201400210
    Maltsev, Oleg V. ; Yue, Ling ; Rebarz, Mateusz ; Hintermann, Lukas ; Sliwa, Michel ; Ruckebusch, Cyril ; Pejov, Ljupčo ; Liu, Ya Jun ; Naumov, Pance. / Vibrational spectra of chemical and isotopic variants of oxyluciferin, the light emitter of firefly bioluminescence. In: Chemistry - A European Journal. 2014 ; Vol. 20, No. 34. pp. 10782-10790.
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    AU - Hintermann, Lukas

    AU - Sliwa, Michel

    AU - Ruckebusch, Cyril

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    AU - Liu, Ya Jun

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    AB - The chemical complexity of oxyluciferin (OxyLH2), the light-emitting molecule in the bioluminescence of fireflies, originates from the possibility of keto/enol tautomerism and single or double deprotonation. Herein, we present detailed infrared spectroscopic analysis of OxyLH2 and several of its chemical isomers and isotopomers. To facilitate the future characterization of its biogenic forms, we provide accurate assignments of the solid-state and solution FTIR spectra of OxyLH2 based on comparison to six isotopically labeled variants ([2-13C]-OxyLH2, [3-15N]-OxyLH2, [4-13C]-OxyLH2, [5-13C]-OxyLH2, [2′-13C]-OxyLH 2, [3′-15N]-OxyLH2), five closely related structural analogues, and theoretically computed spectra. The computed DFT harmonic vibrational force fields (B3LYP and M06 functionals with basis sets of varying flexibility up to 6-311++G) reproduce well the observed shifts in the IR spectra of both isotopically labeled and structurally related analogues. Illuminating IR spectra: A detailed IR spectroscopic study of oxyluciferin, the light emitter of firefly bioluminescence, has been performed, which reveals the most accurate vibrational assignments to date (see figure). To that end, a set of oxyluciferin analogues and isotopomers were prepared, and their spectra were recorded in the solid state and in acetonitrile solution.

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