Photoinduced dynamics of oxyluciferin analogues

Unusual enol "super"photoacidity and evidence for keto-enol isomerization

Kyril M. Solntsev, Sergey P. Laptenok, Pance Naumov

Research output: Contribution to journalArticle

Abstract

The first systematic pico-nanosecond time-resolved spectroscopic study of the firefly emitter oxyluciferin and two of its chemically modified analogues revealed that in the excited state the enol group is more acidic than the phenol group. The 6′-dehydroxylated derivative, in which only the 4-enolic hydroxyl proton is acidic, has an experimentally determined pK a* of 0.9 in dimethyl sulfoxide and an estimated pK a* of -0.3 in water. Moreover, this compound provided direct evidence that in a nonpolar, basic environment the keto form in the excited state can tautomerize into the enol, which subsequently undergoes excited-state proton transfer (ESPT) to produce enolate ion. This observation presents the first experimental evidence of excited-state keto-enol tautomerization of a firefly fluorophore, and it could be important in resolving the enol-keto conundrum related to the color-tuning mechanism of firefly bioluminescence. The 6′-dehydroxylated form of oxyluciferin adds a very rare case of a stable enol to the family of "super"photoacids.

Original languageEnglish (US)
Pages (from-to)16452-16455
Number of pages4
JournalJournal of the American Chemical Society
Volume134
Issue number40
DOIs
StatePublished - Oct 10 2012

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Fireflies
Isomerization
Excited states
Protons
Bioluminescence
Dimethyl Sulfoxide
Phenol
Hydroxyl Radical
Proton transfer
Dimethyl sulfoxide
Fluorophores
Color
Ions
Phenols
Water
Tuning
Derivatives
oxyluciferin

ASJC Scopus subject areas

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

Cite this

Photoinduced dynamics of oxyluciferin analogues : Unusual enol "super"photoacidity and evidence for keto-enol isomerization. / Solntsev, Kyril M.; Laptenok, Sergey P.; Naumov, Pance.

In: Journal of the American Chemical Society, Vol. 134, No. 40, 10.10.2012, p. 16452-16455.

Research output: Contribution to journalArticle

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abstract = "The first systematic pico-nanosecond time-resolved spectroscopic study of the firefly emitter oxyluciferin and two of its chemically modified analogues revealed that in the excited state the enol group is more acidic than the phenol group. The 6′-dehydroxylated derivative, in which only the 4-enolic hydroxyl proton is acidic, has an experimentally determined pK a* of 0.9 in dimethyl sulfoxide and an estimated pK a* of -0.3 in water. Moreover, this compound provided direct evidence that in a nonpolar, basic environment the keto form in the excited state can tautomerize into the enol, which subsequently undergoes excited-state proton transfer (ESPT) to produce enolate ion. This observation presents the first experimental evidence of excited-state keto-enol tautomerization of a firefly fluorophore, and it could be important in resolving the enol-keto conundrum related to the color-tuning mechanism of firefly bioluminescence. The 6′-dehydroxylated form of oxyluciferin adds a very rare case of a stable enol to the family of {"}super{"}photoacids.",
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