Skip to main content
SpringerLink
Log in

Lophine derivatives as activators in peroxyoxalate chemiluminescence

  • Paper
  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

Lophine and four of its derivatives were used as activators (ACTs) of the chemiluminescent peroxyoxalate (PO) reaction of bis(2,4,6-trichlorophenyl)oxalate with H2O2, catalysed by imidazole. Kinetic emission assays have shown that with the tested compounds the reaction mechanism, regarding the formation of the high energy intermediate (HEI) of the PO reaction, occurs as previously seen for commonly used ACTs. A bimolecular interaction of the compounds with the HEI leads to chemiexcitation through the chemically initiated electron exchange luminescence (CIEEL) mechanism, as confirmed by a linear free-energy correlation between the relative catalytic rate constants and the oxidation potentials of the compounds. The yields of excited state formation and light emission, in the range of 10−2–10−3 E mol−1, are comparable to the ones seen with commonly used ACTs. A Hammett plot with ρ = −0.90 indicates the buildup of a partial positive charge on the transition step of the catalytic process, consistent with the formation of a radical cation of the ACT, being an additional validation of the CIEEL mechanism in this system.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. B. Radziszewski, Ueber die Constitution des Lophins und verwandter Verbindungen Ber. Dtsch. Chem. Ges. 1877 10 70.

    Article  Google Scholar 

  2. G. Lu, J. Wada, T. Kimoto, H. Iga, H. Nishigawa, M. Kimura and Z. Z. Hu, The Chemiexcitation of the Chemiluminescence of Lophine Peroxide Anions via a Partially Cyclic Transition State Eur. J. Org. Chem. 2014 1212.

    Google Scholar 

  3. M. Kimura, G. H. Lu, H. Nishigawa, Z. Q. Zhang and Z. Z. Hu, Singlet oxygen generation from lophine hydroperoxides Luminescence 2007 22 72.

    Article  CAS  PubMed  Google Scholar 

  4. M. Tsunenaga, H. Iga and M. Kimura, Location effect of an OH group on the chemiluminescence efficiency of 4-hydroperoxy-2-(o-, m-, or p-hydroxyphenyl)-4,5-diphenyl-4H-isoimidazoles Tetrahedron Lett. 2005 46 1877.

    Article  CAS  Google Scholar 

  5. M. Kimura, H. Nishikawa, H. Kura, H. Lim and E. H. White, Maximization of the Chemiluminescence Efficiency of 1,4,5-Triarylhydroperoxy-4H-isoimidazoles Chem. Lett. 1993 505.

    Google Scholar 

  6. E. H. White and M. J. C. Harding, Chemiluminescence in liquid solutions: the chemiluminescence of lophine and its derivatives Photochem. Photobiol. Sci. 1965 4 1129.

    Article  CAS  Google Scholar 

  7. E. H. White and M. J. C. Harding, The chemiluminescence of lophine and its derivatives J. Am. Chem. Soc. 1964 86 5686.

    Article  CAS  Google Scholar 

  8. T. Hayashi and K. Maeda, Mechanism of chemiluminescence of 2,4,5-triphenylimidazole Bull. Chem. Soc. Jpn 1962 35 2057.

    Article  CAS  Google Scholar 

  9. K. Nakashima, Lophine derivatives as versatile analytical tools Biomed. Chromatogr. 2003 17 83.

    Article  CAS  PubMed  Google Scholar 

  10. N. Kuroda, R. Shimoda, M. Wada and K. Nakashi, Lophine derivatives and analogues as new phenolic enhancers for the luminol–hydrogen peroxide–horseradish peroxidase chemiluminescence system Anal. Chim. Acta 2000 403 131.

    Article  CAS  Google Scholar 

  11. L. F. M. L. Ciscato, F. A. Augusto, D. Weiss, F. H. Bartoloni, S. Albrecht, H. Brandl, T. Zimmermann and W. J. Baader, The chemiluminescent peroxyoxalate system: state of the art almost 50 years from its discovery ARKIVOC 2012 iii, 391.

    Article  Google Scholar 

  12. F. H. Bartoloni, L. F. M. L. Ciscato, M. M. M. Peixoto, A. P. F. Santos, C. S. Santos, S. Oliveira, F. A. Augusto, A. P. E. Pagano and W. J. Baader, Light: a rare reaction product Quim. Nova 2011 34 544.

    Article  CAS  Google Scholar 

  13. W. J. Baader, C. V. Stevani, and E. L. Bastos, Chemilumine-scence of Organic Peroxides, in The Chemistry of Peroxides, ed. Z. Rappoport, John Wiley & Sons, Chichester, 2006, vol. 2, pp. 1211.

    Article  CAS  Google Scholar 

  14. F. A. Augusto, G. A. de Souza, S. P. de Souza Jr., M. Khalid and W. J. Baader, Efficiency of Electron Transfer Initiated Chemiluminescence Photochem. Photobiol. 2013 89 1299.

    Article  CAS  PubMed  Google Scholar 

  15. C. V. Stevani, S. M. da Silva and W. J. Baader, Studies on the mechanism of the excitation step in peroxyoxalate chemiluminescence Eur. J. Org. Chem. 2000 4037.

    Google Scholar 

  16. F. H. Bartoloni, L. F. M. L. Ciscato, F. A. Augusto and W. J. Baader, Inverse electron transfer in peroxyoxalate chemiexcitation using easily reducible activators Quim. Nova 2010 33 2055

    CAS  Google Scholar 

  17. L. F. M. L. Ciscato, F. H. Bartoloni, E. L. Bastos and W. J. Baader, Direct Kinetic Observation of the Chemiexcitation Step in Peroxyoxalate Chemiluminescence J. Org. Chem. 2009 74 8974.

    Article  CAS  PubMed  Google Scholar 

  18. S. M. Silva, K. Wagner, D. Weiss, R. Beckert and W. J. Baader, Studies on the chemiexcitation step in peroxyoxalate chemiluminescence using steroid-substituted activators Luminescence 2002 17 362.

    Article  CAS  PubMed  Google Scholar 

  19. C. L. R. Catherall, T. F. Palmer and R. B. Cundall, Chemiluminescence from reactions of bis(pentachlorophenyl)oxalate, hydrogen peroxide and fluorescent compounds. Kinetics and mechanism J. Chem. Soc., Faraday Trans. 2 1984 80 823.

    Article  CAS  Google Scholar 

  20. S. M. da Silva, F. Casallanovo, K. Oyamaguchi, L. F. M. L. Ciscato, C. V. Stevani and W. J. Baader, Kinetic studies on the peroxyoxalate chemiluminescence reaction: determination of the cyclization rate constant Luminescence 2002 17 313.

    Article  CAS  PubMed  Google Scholar 

  21. C. V. Stevani, D. F. Lima, V. G. Toscano and W. J. Baader, Kinetic studies on the peroxyoxalate chemiluminescent reaction: imidazole as a nucleophilic catalyst J. Chem. Soc., Perkin Trans. 2 1996 989.

    Google Scholar 

  22. G. B. Schuster, Chemiluminescence of organic peroxides. Conversion of ground-state reactants to excited-state products by the chemically initiated electron-exchange luminescence mechanism Acc. Chem. Res. 1979 12 366.

    Article  CAS  Google Scholar 

  23. G. B. Schuster and S. P. Schmidt, Chemiluminescence of organic compounds Adv. Phys. Org. Chem. 1982 18 187.

    CAS  Google Scholar 

  24. M. L. Cotton and H. B. Dunford, Studies on horseradish peroxidase. XI. On the nature of compounds I and II as determined from the kinetics of the oxidation of ferrocyanide Can. J. Chem. 1973 5 582.

    Article  Google Scholar 

  25. L. Benisvy, A. J. Blake, D. Collison, E. S. Davies, C. D. Garner, E. J. L. McInnes, J. McMaster, G. Whittaker and C. Wilson, A phenol-imidazole pro-ligand that can exist as a phenoxyl radical, alone and when complexed to copper (II) and zinc (II) Dalton Trans. 2003 1975.

    Google Scholar 

  26. S. L. Murov, I. Carmichael, and G. L. Hug, Handbook of Photochemistry, Marcel Decker Inc. New York, 2nd edn, 1993.

    Google Scholar 

  27. J. Lee, A. S. Wesley, J. F. Ferguson III, and H. H. Seliger, The use of luminol as a standard of photon emission, in Bioluminescence in Progress, ed. F. H. Johnson and Y. Haneda, Princeton University Press, Princeton, 1965, p. 35.

    Google Scholar 

  28. A. MacDonald, K. W. Chan and T. A. Nieman, Lophine chemiluminescence for metal ion determinations Anal. Chem. 1979 51 2077.

    Article  CAS  Google Scholar 

  29. C. V. Stevani, Ph.D. Thesis, Universidade de São Paulo, 1997.

    Google Scholar 

  30. M. A. de Oliveira, F. H. Bartoloni, F. A. Augusto, L. F. M. L. Ciscato, E. L. Bastos and W. J. Baader, Revision of Singlet Quantum Yields in the Catalyzed Decomposition of Cyclic Peroxides J. Org. Chem. 2012 77 10537.

    Article  CAS  Google Scholar 

  31. L. F. M. L. Ciscato, F. H. Bartoloni, A. S. Colavite, D. Weiss, R. Beckert and S. Schramm, Evidence supporting a 1,2-dioxetanone as an intermediate in the benzofuran-2(3H)-one chemiluminescence Photochem. Photobiol. Sci. 2014 13 32.

    Article  CAS  PubMed  Google Scholar 

  32. R. A. Marcus, Chemical and electrochemical electron-transfer theory Annu. Rev. Phys. Chem. 1964 15 155.

    Article  CAS  Google Scholar 

  33. F. Scandola, V. Balzani and G. B. Schuster, Free-energy relationships for reversible and irreversible electron-transfer processes J. Am. Chem. Soc. 1981 103 2519.

    Article  CAS  Google Scholar 

  34. Chemical and Biological Generation of Excited States, ed. W. Adam and G. Cilento, Academic Press, New York, 1982.

    Google Scholar 

  35. J. P. Smith, A. K. Shrock and G. B. Schuster, Chemiluminescence of organic peroxides. Thermal generation of an o-xylylene peroxide J. Am. Chem. Soc. 1982 104 1041.

    Article  CAS  Google Scholar 

  36. M. J. Darmon and G. B. Schuster, Thermal chemistry of cyclopropyl-substituted malonyl peroxides. A new chemiluminescent reaction J. Org. Chem. 1982 47 4658.

    Article  CAS  Google Scholar 

  37. S. P. Schmidt and G. B. Schuster, Chemiluminescence of dimethyldioxetanone. Unimolecular generation of excited singlet and triplet acetone. Chemically initiated electron-exchange luminescence, the primary light generating reaction J. Am. Chem. Soc. 1980 102 306.

    Article  CAS  Google Scholar 

  38. B. G. Dixon and G. B. Schuster, Investigation of the mechanism of the unimolecular and the electron-donor-catalyzed thermal fragmentation of secondary peroxy esters. Chemiluminescence of 1-phenylethyl peroxyacetate by the chemically initiated electron-exchange luminescence mechanism J. Am. Chem. Soc. 1979 101 3116.

    Article  CAS  Google Scholar 

  39. J.-Y. Koo and G. B. Schuster, Chemiluminescence of diphenoyl peroxide–chemically-initiated electron exchange luminescence–new general mechanism for chemical production of electronically excited-states J. Am. Chem. Soc. 1978 100 4496.

    Article  CAS  Google Scholar 

  40. W. Adam, Determination of chemiexcitation yields in the thermal generation of electronic excitation from 1,2-dioxetanes, in Chemical and Biological Generation of Excited States, ed. W. Adam and G. Cilento, Academic Press, New York, 1982, p. 115.

    Chapter  Google Scholar 

  41. T. Wilson, Int. Rev. Sci.: Phys. Chem. Ser. Two 1976 9 266.

    Google Scholar 

  42. L. F. M. L. Ciscato, F. H. Bartoloni, D. Weiss, R. Beckert and W. J. Baader, Experimental Evidence of the Occurrence of Intramolecular Electron Transfer in Catalyzed 1,2-Dioxetane Decomposition J. Org. Chem. 2010 75 6574.

    Article  CAS  PubMed  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, SP, Brazil

    J. Alves, A. Boaro, V. B. Keslarek, C. A. Cabral, R. B. Orfão Jr., L. F. M. L. Ciscato & F. H. Bartoloni

  2. Instituto de Ciências Ambientais, Químicas e Farmacêuticas, Universidade Federal de São Paulo, Diadema, SP, Brazil

    J. S. da Silva & T. L. Ferreira

Authors
  1. J. Alves
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. Boaro
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. J. S. da Silva
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. T. L. Ferreira
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. V. B. Keslarek
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. C. A. Cabral
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. R. B. Orfão Jr.
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. L. F. M. L. Ciscato
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. F. H. Bartoloni
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to F. H. Bartoloni.

Additional information

Electronic supplementary information (ESI) available: Spectrophotometric data (Fig. S1 and S2), chemiluminescence emission time-profiles (Fig. S3) and the spectrum (Fig. S4), and emission kinetics data (Tables S1–S3). See DOI: 10.1039/c4pp00311j

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Alves, J., Boaro, A., da Silva, J.S. et al. Lophine derivatives as activators in peroxyoxalate chemiluminescence. Photochem Photobiol Sci 14, 320–328 (2015). https://doi.org/10.1039/c4pp00311j

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/c4pp00311j

Search

Navigation