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Spectroscopic studies of the color modulation mechanism of firefly (beetle) bioluminescence with amino-analogs of luciferin and oxyluciferin

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Abstract

Spectroscopic properties of amino-analogs of luciferin and oxyluciferin were investigated to confirm the color modulation mechanism of firefly (beetle) bioluminescence. Fluorescence solvatochromic character of aminooxyluciferin analogs indicates that the bioluminescence of aminoluciferin is useful for evaluating the polarity of a luciferase active site.

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Notes and references

  1. W. D. McElroy, and M. DeLuca, Chemistry of firefly luminescence, in Bioluminescence in Action, ed. P. J. Herring, Academic Press, London, 1978, pp. 109–127. Bioluminescence: Chemical Principles and Methods, ed. O. Shimomura, World Scientific Publishing, Singapore, 2006, pp. 1–29.

    Google Scholar 

  2. H. H. Seliger, W. D. McElroy, The colors of firefly bioluminescence: enzyme configuration and species specificity, Proc. Natl. Acad. Sci. U. S. A., 1964, 52, 75–81.

    Article  CAS  Google Scholar 

  3. K. V. Wood, Y. A. Lam, H. H. Seliger, W. D. McElroy, Complementary DNA coding click beetle luciferases can elicit bioluminescence of different colors, Science, 1989, 244, 700–703.

    Article  CAS  Google Scholar 

  4. K. V. Wood, Y. A. Lam, W. D. McElroy, Introduction to beetle luciferases and their applications, J. Biolumin. Chemilumin., 1989, 4, 289–301.

    Article  CAS  Google Scholar 

  5. V. R. Viviani, The origin, diversity, and structure function relationships of insect luciferases, Cell. Mol. Life Sci., 2002, 59, 1833–1850.

    Article  CAS  Google Scholar 

  6. B. R. Branchini, M. H. Murtiashaw, R. A. Magrar, N. C. Portier, M. C. Ruggiero, J. G. Stroh, Yellow-green and red firefly bioluminescence from 5,5-dimethyloxyluciferin, J. Am. Chem. Soc., 2002, 124, 2112–2113.

    Article  CAS  Google Scholar 

  7. B. R. Branchini, T. L. Southworth, M. H. Murtiashaw, R. A. Magrar, S. A. Gonzalez, M. C. Ruggiero, J. G. Stroh, An alternative mechanism of bioluminescence color determination in firefly luciferase, Biochemistry, 2004, 43, 7255–7262.

    Article  CAS  Google Scholar 

  8. P. Naumov, Y. Ozawa, K. Ohkubo, S. Fukuzumi, Structure and spectroscopy of oxyluciferin, the light emitter of the firefly bioluminescence, J. Am. Chem. Soc., 2009, 131, 11590–11605.

    Article  CAS  Google Scholar 

  9. T. Hirano, Y. Hasumi, K. Ohtsuka, S. Maki, H. Niwa, M. Yamaji, D. Hashizume, Spectroscopic studies of the light-color modulation mechanism of firefly (beetle) bioluminescence, J. Am. Chem. Soc., 2009, 131, 2385–2396.

    Article  CAS  Google Scholar 

  10. E. H. White, H. Wörther, H. H. Seliger, W. D. McElroy, Amino analogs of firefly luciferin and biological activity thereof, J. Am. Chem. Soc., 1966, 88, 2015–2019.

    Article  CAS  Google Scholar 

  11. R. Shinde, J. Perkins, C. H. Contag, Luciferin derivatives for enhanced in vitro and in vivo bioluminescence assays, Biochemistry, 2006, 45, 11103–11112.

    Article  CAS  Google Scholar 

  12. C. C. Woodroofe, J. W. Shultz, M. G. Wood, J. Osterman, J. J. Cali, W. J. Daily, P. L. Meisenheimer, D. H. Klaubert, N-Alkylated 6′-aminoluciferins are bioluminescent substrates for Ultra-Glo and QuantiLum luciferase: new potential scaffolds for bioluminescent assays, Biochemistry, 2008, 47, 10383–10393.

    Article  CAS  Google Scholar 

  13. G. R. Reddy, W. C. Thompson, S. C. Miller, Robust light emission from cyclic alkylaminoluciferin substrates for firefly luciferase, J. Am. Chem. Soc., 2010, 132, 13586–13587.

    Article  CAS  Google Scholar 

  14. H. Takakura, R. Kojima, Y. Urano, T. Terai, K. Hanaoka, T. Tsuboi, T. Nagano, Aminoluciferins as functional bioluminogenic substrates of firefly luciferase, Chem.-Asian J., 2011, 6, 1800–1810.

    Article  CAS  Google Scholar 

  15. C. Hansch, A. Leo, R. W. Taft, A survey of Hammett substituent constants and resonance and field parameters, Chem. Rev., 1991, 91, 165–195.

    Article  CAS  Google Scholar 

  16. Solvents and Solvent Effects in Organic Chemistry, ed. C. Reichardt, Wiley-VCH, Weinheim, 3rd edn, 2003.

    Google Scholar 

  17. Analysis of the Stokes shifts with the Lippert-Mataga equation did not give good correlations as reported in ref. 5.

  18. Details of DFT and TDDFT calculations are described in general methods of the ESI.

  19. G. Orlova, J. D. Goddard, L. Y. Brovko, Theoretical study of the amazing firefly bioluminescence: the formation and structures of the light emitters, J. Am. Chem. Soc., 2003, 125, 6962–6971.

    Article  CAS  Google Scholar 

  20. Modern Molecular Photochemistry of Organic Molecules, ed. N. J. Turro, V. Ramamurthy and J. C. Scaiano, University Science Books, Sausalito, 2010, pp. 169–264.

    Google Scholar 

  21. M. DeLuca, J. Wannlund, W. D. McElroy, Factors affecting the kinetics of light emission from crude and purified firefly luciferase, Anal. Biochem., 1979, 95, 194–198.

    Article  CAS  Google Scholar 

  22. R. A. Morton, T. A. Hopkins, H. H. Seliger, Spectroscopic properties of firefly luciferin and related compounds; an approach to product emission, Biochemistry, 1969, 8, 1598–1607.

    Article  CAS  Google Scholar 

  23. M. DeLuca, Hydrophobic nature of the active site of firefly luciferase, Biochemistry, 1969, 8, 160–166.

    Article  CAS  Google Scholar 

  24. V. R. Viviani, F. G. C. Arnoldi, B. Venkatesh, A. J. Silva Neto, F. G. T. Ogawa, T. L. Oehlmeyer, Y. Ohmiya, Active-site properties of Phrixothrix railroad worm green and red bioluminescence-eliciting luciferases, J. Biochem., 2006, 140, 467–474.

    Article  CAS  Google Scholar 

  25. N. N. Ugarova, L. Y. Brovko, Protein structure and bioluminescent spectra for firefly bioluminescence, Luminescence, 2002, 17, 321–330.

    Article  CAS  Google Scholar 

  26. H. H. Seliger, W. D. McElroy, Spectral emission and quantum yield of firefly bioluminescence, Arch. Biochem. Biophys., 1960, 88, 136–141.

    Article  CAS  Google Scholar 

  27. Y. Ando, K. Niwa, N. Yamada, T. Enomoto, T. Irie, H. Kubota, Y. Ohmiya, H. Akiyama, Firefly bioluminescence quantum yield and colour change by pH-sensitive green emission, Nat. Photonics, 2008, 2, 44–47.

    Article  CAS  Google Scholar 

  28. K. Niwa, Y. Ichino, Y. Ohmiya, Quantum yield measurements of firefly bioluminescence reactions using a commercial luminometer, Chem. Lett., 2010, 39, 291–293.

    Article  CAS  Google Scholar 

  29. K. Niwa, Y. Ichino, S. Kumata, Y. Nakajima, Y. Hiraishi, D. Kato, V. R. Viviani, Y. Ohmiya, Quantum yields and kinetics of the firefly bioluminescence reaction of beetle luciferases, Photochem. Photobiol., 2010, 86, 1046–1049.

    Article  CAS  Google Scholar 

  30. L. W. Chung, S. Hayashi, M. Lundberg, T. Nakatsu, H. Kato, K. Morokuma, Mechanism of efficient firefly bioluminescence via adiabatic transition state and seam of sloped conical intersection, J. Am. Chem. Soc., 2008, 130, 12880–12881.

    Article  CAS  Google Scholar 

  31. V. R. Viviani, Y. Ohmiya, Bovine serum albumin displays luciferase-like activity in presence of luciferyl adenylate: insights on the origin of protoluciferase activity and bioluminescence colours, Luminescence, 2006, 21, 262–267.

    Article  CAS  Google Scholar 

  32. V. R. Viviani, R. A. Prado, F. G. C. Arnoldi, F. C. Abdalla, An ancestral luciferase in the Malpighi tubules of a non-bioluminescent beetle, Photochem. Photobiol. Sci., 2009, 8, 57–61.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Engineering Science, Graduate School of Informatics and Engineering, The University of Electro-Communications, Chofu, Tokyo, 182-8585, Japan

    Takashi Hirano, Hiroyuki Nagai, Takuto Matsuhashi, Yosuke Hasumi, Satoshi Iwano, Kazuto Ito, Shojiro Maki & Haruki Niwa

  2. Laboratorio de Bioquimica e Biotecnologia de Sistemas Bioluminescentes, Universidade Federal de São Carlos, Campus de Sorocaba (UFSCAR), Sorocaba, São Paulo, Brazil

    Vadim R. Viviani

Authors
  1. Takashi Hirano
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  2. Hiroyuki Nagai
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  3. Takuto Matsuhashi
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  4. Yosuke Hasumi
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  5. Satoshi Iwano
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  7. Shojiro Maki
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  8. Haruki Niwa
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  9. Vadim R. Viviani
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Corresponding author

Correspondence to Takashi Hirano.

Additional information

Electronic supplementary information (ESI) available: General methods, synthesis and NMR spectra of luciferin and oxyluciferin analogs, measurements of bioluminescence activities and spectra, spectroscopic data of oxyluciferin analogs, and DFT and TDDFT calculation data. See DOI: 10.1039/c2pp25106j

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Hirano, T., Nagai, H., Matsuhashi, T. et al. Spectroscopic studies of the color modulation mechanism of firefly (beetle) bioluminescence with amino-analogs of luciferin and oxyluciferin. Photochem Photobiol Sci 11, 1281–1284 (2012). https://doi.org/10.1039/c2pp25106j

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  • DOI: https://doi.org/10.1039/c2pp25106j

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