Experimental Support for a Single Electron-Transfer Oxidation Mechanism in Firefly Bioluminescence

Bruce R. Branchini, Curran E. Behney, Tara L. Southworth, Danielle M. Fontaine, Andrew M. Gulick, David J. Vinyard, Gary W Brudvig

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

Firefly luciferase produces light by converting substrate beetle luciferin into the corresponding adenylate that it subsequently oxidizes to oxyluciferin, the emitter of bioluminescence. We have confirmed the generally held notions that the oxidation step is initiated by formation of a carbanion intermediate and that a hydroperoxide (anion) is involved. Additionally, structural evidence is presented that accounts for the delivery of oxygen to the substrate reaction site. Herein, we report key convincing spectroscopic evidence of the participation of superoxide anion in a related chemical model reaction that supports a single electron-transfer pathway for the critical oxidative process. This mechanism may be a common feature of bioluminescence processes in which light is produced by an enzyme in the absence of cofactors.

Original languageEnglish
Pages (from-to)7592-7595
Number of pages4
JournalJournal of the American Chemical Society
Volume137
Issue number24
DOIs
Publication statusPublished - Jun 24 2015

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Fireflies
Bioluminescence
Negative ions
Electrons
Chemical Models
Firefly Luciferases
Light
Oxidation
Critical Pathways
Beetles
Substrates
Superoxides
Hydrogen Peroxide
Anions
Enzymes
Oxygen

ASJC Scopus subject areas

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

Cite this

Branchini, B. R., Behney, C. E., Southworth, T. L., Fontaine, D. M., Gulick, A. M., Vinyard, D. J., & Brudvig, G. W. (2015). Experimental Support for a Single Electron-Transfer Oxidation Mechanism in Firefly Bioluminescence. Journal of the American Chemical Society, 137(24), 7592-7595. https://doi.org/10.1021/jacs.5b03820

Experimental Support for a Single Electron-Transfer Oxidation Mechanism in Firefly Bioluminescence. / Branchini, Bruce R.; Behney, Curran E.; Southworth, Tara L.; Fontaine, Danielle M.; Gulick, Andrew M.; Vinyard, David J.; Brudvig, Gary W.

In: Journal of the American Chemical Society, Vol. 137, No. 24, 24.06.2015, p. 7592-7595.

Research output: Contribution to journalArticle

Branchini, BR, Behney, CE, Southworth, TL, Fontaine, DM, Gulick, AM, Vinyard, DJ & Brudvig, GW 2015, 'Experimental Support for a Single Electron-Transfer Oxidation Mechanism in Firefly Bioluminescence', Journal of the American Chemical Society, vol. 137, no. 24, pp. 7592-7595. https://doi.org/10.1021/jacs.5b03820
Branchini BR, Behney CE, Southworth TL, Fontaine DM, Gulick AM, Vinyard DJ et al. Experimental Support for a Single Electron-Transfer Oxidation Mechanism in Firefly Bioluminescence. Journal of the American Chemical Society. 2015 Jun 24;137(24):7592-7595. https://doi.org/10.1021/jacs.5b03820
Branchini, Bruce R. ; Behney, Curran E. ; Southworth, Tara L. ; Fontaine, Danielle M. ; Gulick, Andrew M. ; Vinyard, David J. ; Brudvig, Gary W. / Experimental Support for a Single Electron-Transfer Oxidation Mechanism in Firefly Bioluminescence. In: Journal of the American Chemical Society. 2015 ; Vol. 137, No. 24. pp. 7592-7595.
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