Spectral-structural effects of the keto-enol-enolate and phenol-phenolate equilibria of oxyluciferin

Panče Naumov, Manoj Kochunnoonny

Research output: Contribution to journalArticlepeer-review

Abstract

The effects of environmental polarity on the enolization of the keto form and the deprotonation of the enol, and the role of the neutral and ionized 6′-OH group in the fluorescence of the firefly emitter, oxyluciferin, were assessed through a detailed study of the structure and absorption and fluorescence spectra of its 6′-dehydroxylated analogue. It was found that the deprotonated 6′-O- group is a necessary, albeit insufficient, factor in accounting for the observed yellow-green and red emissions of oxyluciferin. Its negative charge is essential for effective excited-state charge transfer, which lowers the emission energy and broadens the emission spectrum. Deprotonation of the 6′-OH group changes its effect on the emission energy from blue- to red-shifting. Furthermore, the combination of these opposite effects and resonance stabilization of the phenolate-keto form causes switching of the order of maximum emission wavelengths of the three species involved in the keto-enol-enolate equilibrium from enol ≪ keto < enolate in absence of 6′-OH to keto < enol ≪ enolate with 6′-OH, to enol < enolate < keto with 6′-O-. If only the keto-enol-enolate equilibrium is considered, solvents of medium polarity are the most effective in decreasing the excited-state energy. Polar or very polar environments also stimulate shift of the ground-state equilibrium toward the enol form. Under such circumstances, the enol group can be partly or completely deprotonated in the ground state or from the excited state: a polar environment facilitates the ionization, while a less polar environment requires the presence of a stronger base. In the absence of bases, the ground-state keto form exists only in solvents of very weak to medium polarity, but with stronger bases, it can also exist in a nonpolar or very weakly polar environment, usually together with the enolate anion. The phenol-enolate form of oxyluciferin, a species that could not be experimentally detected prior to this study, was identified as a yellow-emitting species.

Original languageEnglish (US)
Pages (from-to)11566-11579
Number of pages14
JournalJournal of the American Chemical Society
Volume132
Issue number33
DOIs
StatePublished - Aug 25 2010

ASJC Scopus subject areas

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

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