Mechanistic investigations of the 2-coumaranone chemiluminescence

Stefan Schramm, Isabelle Navizet, Durga Prasad Karothu, Pascal Oesau, Veronika Bensmann, Dieter Weiss, Rainer Beckert, Pance Naumov

    Research output: Contribution to journalArticle

    Abstract

    2-Coumaranones are evolving as a new, efficient, versatile, and synthetically accessible platform for the next generation chemiluminescent probes. Despite the favorable quantum yields, the exact mechanism of their chemiluminescence remains elusive. Here, we analyze the details of the mechanism of the 2-coumaranone chemiluminescence using a combination of experimental and computational methods. By using EPR spectroscopy we show that superoxide radical anions are involved in the reactions, in support of the hypothesis that the mechanism includes a single electron transfer step. The decomposition of the high-energy intermediate, 1,2-dioxetanone, is described in the ground state and in the first three excited singlet states, and indicates that there is at least one conical intersection, which is crucial for generation of excited-state molecules. A peroxy anion that is generated was found to be able to undergo a side reaction that leads to the same (isolated) product as in the light-generating reaction. These results demonstrate the applicability of 2-coumaranones as a model system for several bioluminescence reactions and may lead to the design of new 2-coumaranone derivatives with superior emission characteristics for bioanalytical applications.

    Original languageEnglish (US)
    Pages (from-to)22852-22859
    Number of pages8
    JournalPhysical Chemistry Chemical Physics
    Volume19
    Issue number34
    DOIs
    StatePublished - Jan 1 2017

    Fingerprint

    Chemiluminescence
    chemiluminescence
    Excited states
    Anions
    Bioluminescence
    anions
    bioluminescence
    inorganic peroxides
    Quantum yield
    Computational methods
    Superoxides
    intersections
    Ground state
    excitation
    Paramagnetic resonance
    electron transfer
    platforms
    Spectroscopy
    Derivatives
    Decomposition

    ASJC Scopus subject areas

    • Physics and Astronomy(all)
    • Physical and Theoretical Chemistry

    Cite this

    Schramm, S., Navizet, I., Prasad Karothu, D., Oesau, P., Bensmann, V., Weiss, D., ... Naumov, P. (2017). Mechanistic investigations of the 2-coumaranone chemiluminescence. Physical Chemistry Chemical Physics, 19(34), 22852-22859. https://doi.org/10.1039/c7cp03425c

    Mechanistic investigations of the 2-coumaranone chemiluminescence. / Schramm, Stefan; Navizet, Isabelle; Prasad Karothu, Durga; Oesau, Pascal; Bensmann, Veronika; Weiss, Dieter; Beckert, Rainer; Naumov, Pance.

    In: Physical Chemistry Chemical Physics, Vol. 19, No. 34, 01.01.2017, p. 22852-22859.

    Research output: Contribution to journalArticle

    Schramm, S, Navizet, I, Prasad Karothu, D, Oesau, P, Bensmann, V, Weiss, D, Beckert, R & Naumov, P 2017, 'Mechanistic investigations of the 2-coumaranone chemiluminescence', Physical Chemistry Chemical Physics, vol. 19, no. 34, pp. 22852-22859. https://doi.org/10.1039/c7cp03425c
    Schramm S, Navizet I, Prasad Karothu D, Oesau P, Bensmann V, Weiss D et al. Mechanistic investigations of the 2-coumaranone chemiluminescence. Physical Chemistry Chemical Physics. 2017 Jan 1;19(34):22852-22859. https://doi.org/10.1039/c7cp03425c
    Schramm, Stefan ; Navizet, Isabelle ; Prasad Karothu, Durga ; Oesau, Pascal ; Bensmann, Veronika ; Weiss, Dieter ; Beckert, Rainer ; Naumov, Pance. / Mechanistic investigations of the 2-coumaranone chemiluminescence. In: Physical Chemistry Chemical Physics. 2017 ; Vol. 19, No. 34. pp. 22852-22859.
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