A Multifrequency (X-, Q-, and W-band) EPR and DFT Study of a Photopolymerizable Dental Resin


The free radicals generated during the polymerization process of Z100 (3 M ESPE) dental resin were examined by electron paramagnetic resonance (EPR) in X-, Q- and W-bands. Experimental generation and spectra simulations were associated with density functional theory (DFT) calculations to determine the molecular structure and explain the EPR spectrum formation. It was assumed that the EPR spectrum was formed by the sum of two different types of radicals: “propagating” and allylic. The spectra simulations and DFT calculations showed good agreement, indicating that the proposed model fully explained the nine lines of the EPR spectrum in X-band and showed that the spectrum formation is the sum of “9 + 5” lines, rather than the “5 + 4” lines predicted early. Simulations in Q- and W-bands showed very close correlation and were essential to support the proposed model.

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7


  1. 1.

    H.R. Rawke, J. Escjuivel-Upshaw in Phillips Materiais Dentários, 10th edn., ed. by K.J. Anusavice, S.A. Guanabara Koogan (Rio de Janeiro, 1998), Chapter 15, p. 386

  2. 2.

    A.T. Bullock, L.H. Sutcliffe, Trans. Faraday Soc. 8, 625–633 (1964)

    Article  Google Scholar 

  3. 3.

    M.F. Ottaviani, A. Fiorini, P.N. Mason, C. Corvaja, Dent. Mater. 8, 118–124 (1992)

    Article  Google Scholar 

  4. 4.

    D. Cevc Sustercic, N.P. Funduk, M.M. Pintar, J. Mater. Sci. Mater. Med. 8, 507–510 (1997)

    Article  Google Scholar 

  5. 5.

    M.A. Menezes, A. Muench, Rev. Odontol. Univ. São Paulo 12, 281–285 (1998)

    Article  Google Scholar 

  6. 6.

    W. Sano, C.B.M. Mello, Rev. Bras. Eng. Biomed. 15, 17–20 (1999)

    Google Scholar 

  7. 7.

    L.G. Lovell, K.A. Berchtold, J.E. Elliott, H. Lu, C.N. Bowman, Polym. Adv. Technol. 12, 335–345 (2001)

    Article  Google Scholar 

  8. 8.

    L. Lapcik Jr, J. Jancar, A. Stasko, P. Saha, J. Mater. Sci. Mater. Med. 9, 257–262 (1998)

    Article  Google Scholar 

  9. 9.

    W. Teshima, Y. Nomura, N. Tanaka, H. Urabe, M. Okazaki, Y. Nahara, Biomaterials 24, 2097–2103 (2003)

    Article  Google Scholar 

  10. 10.

    W. Sano, C.B.M. Mello, SBPN Scientif. J. 5(1), 368–369 (2001)

    Google Scholar 

  11. 11.

    J. Leprince, G. Lamblin, D. Truffier-Boutry, S. Demoustier-Champagne, J. Devaux, M. Mestdagh, G. Leloup, Acta Biomate 5, 2518–2524 (2009)

    Article  Google Scholar 

  12. 12.

    D.C. Doetschman, R.C. Mehlenbacher, D. Cywar, Macromolecules 29(5), 1807–1816 (1996)

    ADS  Article  Google Scholar 

  13. 13.

    S.G. Pereira, J.P. Telo, T.G. Nunes, J. Mater. Sci. Mater. Med. 19(9), 3135–3144 (2008)

    Article  Google Scholar 

  14. 14.

    A.S. Fontes, E. Di Mauro, W. Sano, N.C.S. Lima, L.H. Dall’Antonia, Polímeros 19(4), 285–291 (2009)

    Article  Google Scholar 

  15. 15.

    J. Leprince, P. Leveque, B. Nysten, B. Gallez, J. Devaux, G. Leloup, Dent. Mater. 28, 512–520 (2012)

    Article  Google Scholar 

  16. 16.

    A.S. Fontes, W. Sano, L.H. Dall’Antonia, E. Di Mauro, Appl. Magn. Reson. 39(4), 381–390 (2010)

    Article  Google Scholar 

  17. 17.

    H. Fischer, J. Polym. Sci. B Polym. Lett. 2(5), 529–532 (1964)

    Article  Google Scholar 

  18. 18.

    M. Iwasaki, Y. Sakai, J. Polym. Sci. A1 Polym. Chem. 7(6), 1537–1547 (1969)

    ADS  Article  Google Scholar 

  19. 19.

    M. Langel, S.R.W. Louro, Nucl. Instrum. Methods Phys. Res. B 16(4–5), 419–423 (1986)

    ADS  Article  Google Scholar 

  20. 20.

    L. Hermosilla, C. Sieiro, P. Calle, M. Zerbetto, A. Polimeno, J. Phys. Chem. B 112, 11202–11208 (2008)

    Article  Google Scholar 

  21. 21.

    A.T. Bullock, L.H. Sutcliffe, Trans. Faraday Soc. 60, 2112–2124 (1964)

    Article  Google Scholar 

  22. 22.

    D. Truffier-Boutry, X.A. Gallez, S. Demoustier-Champagne, J. Devaux, M. Mestdagh, B. Champagne, G. Leloup, J. Polym. Sci. A Polym. Chem. 41(11), 1691–1699 (2003)

    ADS  Article  Google Scholar 

  23. 23.

    T.F. Scott, W.D. Cook, J.S. Forsythe, C.N. Bowman, K.A. Berchtold, Macromolecules 36, 6066–6074 (2003)

    ADS  Article  Google Scholar 

  24. 24.

    M. Valiev, E.J. Bylaska, N. Govind, K. Kowalski, T.P. Straatsma, H.J.J. van Dam, D. Wang, J. Nieplocha, E. Apra, T.L. Windus, W.A. de Jong, Comput. Phys. Commun. 181, 147–1489 (2010)

    Article  Google Scholar 

  25. 25.

    K.A. Berchtold, T.W. Randolph, C.N. Bowman, Macromolecules 38, 6954–6964 (2005)

    ADS  Article  Google Scholar 

  26. 26.

    J.G. Leprince, G. Lamblin, J. Devaux, M. Dewaele, M. Mestdagh, W.M. Palin, B. Gallez, G. Leloup, J. Dent. Res. 89(12), 1494–1498 (2010)

    Article  Google Scholar 

  27. 27.

    J.W. Orton, Electron Paramagnetic Resonance, 2nd edn. (ILIFFE Books, London, 1968), p. 24

    Google Scholar 

  28. 28.

    P. Levêque, J. Leprince, S. Bebelman, J. Devaux, G. Leloup, B. Gallez, J. Magn. Reson. 220, 45–53 (2012)

    ADS  Article  Google Scholar 

  29. 29.

    J. Vaara, J. Jokisaari, R.E. Wasylishen, D.L. Bryce, Prog. Nucl. Magn. Reson. Spectrosc. 41(3–4), 233–304 (2002)

    Article  Google Scholar 

Download references


We thank the EPR Division of Bruker-BioSpin GmbH (Germany) for recording the spectra in W-band, Dr. Otaciro Rangel Nascimento and José Fernando Lima (of the “Sergio Mascarenhas” Molecular Biophysics Group, USP, São Carlos, Brazil) for EPR spectra in Q-band, and Dr. Julian G. Leprince (Université Catholique de Louvain, Belgium), for his valuable insights/assistance in discussions concerning this research.

Author information



Corresponding author

Correspondence to Bruno Luiz Santana Vicentin.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

da Silva Fontes, A., Vicentin, B.L.S., Valezi, D.F. et al. A Multifrequency (X-, Q-, and W-band) EPR and DFT Study of a Photopolymerizable Dental Resin. Appl Magn Reson 45, 681–692 (2014). https://doi.org/10.1007/s00723-014-0546-2

Download citation


  • Electron Paramagnetic Resonance
  • Electron Paramagnetic Resonance Spectrum
  • Density Functional Theory Calculation
  • Hyperfine Interaction
  • Spectrum Simulation