Theoretical study of the amazing firefly bioluminescence: the formation and structures of the light emitters

Journal of the American Chemical Society
Galina OrlovaLioubov Yu Brovko

Abstract

Reaction mechanisms for the formation of the keto-form of oxyluciferin (OxyLH(2)) from the luciferin of fireflies via a dioxetanone intermediate are predicted using the B3LYP/6-31G theoretical method. The ring opening of a model dioxetanone and the decarboxylation proceed in one step via a singlet diradical transition structure with an activation barrier of 18.1 and an exothermicity of 90.8 kcal/mol. The S(0) --> S(1) vertical excitation energies predicted with time dependent density functional theory, TDDFT B3LYP/6-31+G, for the anionic and neutral forms of OxyLH(2) are in the range of 60 to 80 kcal/mol. These energetic results support the generally accepted theory of chemically initiated electron exchange luminescence (CIEEL). The chemical origin of the multicolor bioluminescence from OxyLH(2) is examined theoretically using the TDDFT B3LYP/6-31+G, ZINDO//B3LYP/6-31+G, and CIS/6-31G methods. A change in color of the light emission upon rotation of the two rings in the S(1) excited state of OxyLH(2) is unlikely because both possible emitters, the planar keto- and enol-forms, are minima on the S(1) potential energy surface. The participation of the enol-forms of OxyLH(2) in bioluminescence is plausible but not required to expla...Continue Reading

References

Jan 1, 1978·Proceedings of the National Academy of Sciences of the United States of America·J A KooG B Schuster
Jul 1, 1989·Journal of Bioluminescence and Chemiluminescence·N N Ugarova
Feb 26, 1974·Biochemistry·M DeLuca, W D McElroy
May 1, 1996·BioTechniques·C H RoelantW Scheirer
Aug 1, 1997·The Journal of Biological Chemistry·B R BranchiniM H Murtiashaw
Jan 19, 1999·Annual Review of Cell and Developmental Biology·T Wilson, J W Hastings
Oct 26, 2000·Proceedings of the National Academy of Sciences of the United States of America·L A GrossR Y Tsien
Mar 7, 2002·Journal of the American Chemical Society·Bruce R BranchiniJustin G Stroh
Oct 31, 2002·Luminescence : the Journal of Biological and Chemical Luminescence·N N Ugarova, L Y Brovko
Jan 18, 2003·Cellular and Molecular Life Sciences : CMLS·V R Viviani

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Citations

Oct 28, 2009·Cellular and Molecular Life Sciences : CMLS·Satoshi Inouye
Dec 29, 2010·Cellular and Molecular Life Sciences : CMLS·Saman Hosseinkhani
Nov 25, 2005·Drug Development and Industrial Pharmacy·M L N DubuissonJ Marchand-Brynaert
Oct 13, 2012·Photochemistry and Photobiology·Isabelle NavizetRoland Lindh
Sep 20, 2005·Journal of Photochemistry and Photobiology. B, Biology·Ai-Min Ren, John D Goddard
Jul 22, 2016·The Journal of Physical Chemistry. B·Na'il SalehPanče Naumov
Jul 28, 2016·Biochemical and Biophysical Research Communications·Stephen C TrowellRodney W Rickards
Nov 1, 2016·Photochemistry and Photobiology·Michio KakiuchiTakashi Hirano
Nov 6, 2007·The Journal of Chemical Physics·Felipe CordovaAlberto Vela
Dec 18, 2009·Journal of the American Chemical Society·Isabelle NavizetRoland Lindh
May 2, 2018·Chemistry : a European Journal·Yuan-Yuan Cheng, Ya-Jun Liu
Nov 11, 2014·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Xue Qin RanJohn D Goddard
Sep 16, 2011·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Luís Pinto da Silva, Joaquim C G Esteves da Silva
Mar 2, 2005·Journal of Computational Chemistry·T K ManojkumarKwang S Kim
Feb 12, 2008·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·V R VivianiY Ohmiya
Feb 12, 2008·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Hugo Fraga
Nov 26, 2009·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Chun-Gang MinJi-Kang Feng
Dec 22, 2009·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·A J Silva NetoV R Viviani
Oct 30, 2009·Protein Science : a Publication of the Protein Society·Xueyan LiYoshihiro Ohmiya
Mar 12, 2010·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Parvaneh MaghamiPooria Gill
May 19, 2010·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Chun-Gang MinChia-Chung Sun
Oct 5, 2010·Physical Chemistry Chemical Physics : PCCP·Bruce F MilneFernando Nogueira
Jan 12, 2010·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Frederico G C ArnoldiVadim R Viviani
May 16, 2019·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Yuan-Yuan Cheng, Ya-Jun Liu
Sep 29, 2020·Physical Chemistry Chemical Physics : PCCP·Nuno Manuel de Almeida BarbosaNicolas Ferré
Jan 2, 2007·The Journal of Biological Chemistry·Narges Kh TafreshiHossein Naderi-Manesh
Jun 16, 2012·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Takashi HiranoVadim R Viviani
Jun 4, 2011·Journal of Computational Chemistry·Luís Pinto Da Silva, Joaquim C G Esteves Da Silva
Feb 23, 2011·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Luís Pinto da Silva, Joaquim C G Esteves da Silva
Jan 8, 2020·Photochemistry and Photobiology·Junko UsukuraNobuaki Koga
Nov 5, 2020·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·V R VivianiV R Bevilaqua
Nov 17, 2020·Frontiers in Bioengineering and Biotechnology·Nicholas Thomas BlumPeng Huang
Apr 21, 2020·The Journal of Physical Chemistry Letters·Pauline GossetPascal Didier
Apr 25, 2007·The Journal of Physical Chemistry. a·Tianxiao Yang, John D Goddard
Nov 13, 2007·Biochemistry·Bruce R BranchiniMarc Zimmer

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