Skip to main content
SpringerLink
Log in

Experimental and theoretical studies on the photodegradation of 2-ethylhexyl 4-methoxycinnamate in the presence of reactive oxygen and chlorine species

  • Research Article
  • Published:
Central European Journal of Chemistry

Abstract

2-Ethylhexyl 4-methoxycinnamate (EHMC) is one of the most commonly used sunscreen ingredient. In this study we investigated photodegradation of EHMC in the presence of such common oxidizing and chlorinating systems as H2O2, H2O2/HCl, H2O2/UV, and H2O2/HCl/UV. Reaction products were detected by gas chromatography with a mass spectrometric detector (GC-MS). As a result of experimental studies chloro-substituted 4-methoxycinnamic acid (4-MCA), 4-methoxybenzaldehyde (4-MBA) and 4-methoxyphenol (4-MP) were identified. Experimental studies were enriched with DFT and MP2 calculations. We found that reactions of 4-MCA, 4-MBA and 4-MP with Cl2 and HOCl were in all cases thermodynamically favorable. However, reactivity indices provide a better explanation of the formation of particular chloroorganic compounds. Generally, those isomeric forms of mono- and dichlorinated compounds which exhibits the highest hardness were identified. Nucleophilicity of the chloroorganic compounds precursors were examined by means of the Fukui function.

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. Y. Dobashi, T. Yuyama, Y. Ohkatsu, Polym. Degrad. Stab. 92, 1227 (2007)

    Article  CAS  Google Scholar 

  2. V. S. Sivokhin, Polym. Sci. USSR 21, 1207 (1980)

    Article  Google Scholar 

  3. A. Kikuchi, H. Saito, M. Mori, M. Yagi, Photochem. Photobiol. Sci. 10, 1902 (2011)

    Article  CAS  Google Scholar 

  4. A. J.M. Santos, M.S. Miranda, J.C.G. Esteves da Silva, Water Res. 46, 3167 (2012)

    Article  CAS  Google Scholar 

  5. A. J.M. Santos, D.M.A. Crista, M.S. Miranda, I.F. Almeida, J.P. Sousa e Silva, P.C. Costa, M.H. Amaral, P.A.L. Lobão, J.M. Sousa Lobo, J.C.G. Esteves da Silva, Environ. Chem. 10, 127 (2013)

    Article  CAS  Google Scholar 

  6. M. S. Miranda, L. Pinto da Silva, J.C.G. Esteves da Silva, J. Phys. Org. Chem. 27, 47 (2014)

    Article  CAS  Google Scholar 

  7. Y. T. Chen, Y.T. Lin, C.C. Li, S.F. Sie, Y.W. Chen-Yang, Colloids Surf. B 115, 191 (2014)

    Article  Google Scholar 

  8. Z. A. Lewicka, W.W. Yu, B.L. Oliva, E.Q. Contreras, V.L. Colvin, J. Photochem. Photobiol. A, 263, 24 (2013)

    Article  CAS  Google Scholar 

  9. L. Zhou, Y. Ji, C. Zeng, Y. Zhang, Z. Wang, X. Yang, Water Res., 47, 153 (2013)

    Article  CAS  Google Scholar 

  10. Y. Ji, L. Zhou, Y. Zhang, C. Ferronato, M. Brigante, G. Mailhot, X. Yang, J.-M. Chovelon, Water Res. 47, 5865 (2013)

    Article  CAS  Google Scholar 

  11. A. Christiansson, J. Eriksson, D. Teclechiel, Å. Bergman, Environ. Sci. Pollut. Res. 16, 312 (2009)

    Article  CAS  Google Scholar 

  12. L. A. MacManus-Spencer, M.L. Tse, J.L. Klein, A.E. Kracunas, Environ. Sci. Technol. 45, 3931 (2011)

    Article  CAS  Google Scholar 

  13. C. Ferrari, H. Chen, R. Lavezza, C. Santinelli, I. Longo, E. Bramanti, Int. J. Photoenergy 2013, 1 (2013)

    Article  Google Scholar 

  14. V. Nikolić, D. Ilić, L. Nikolić, M. Stanković, M. Cakić, L. Stanojević, A. Kapor, M. Popsavin, Cent. Eur. J. Chem. 8, 744 (2010)

    Article  Google Scholar 

  15. A. Y.C. Tong, R. Braund, D.S. Warren, B.M. Peake, Cent. Eur. J. Chem. 10, 989 (2012)

    Article  CAS  Google Scholar 

  16. S. Pattanaargson, P. Limphong, Int. J. Cosmetic. Sci. 23, 153 (2001)

    Article  CAS  Google Scholar 

  17. N. Tarras-Wahlberg, G. Stenhagen, O. Larkö, A. Rosén, A.-M. Wennberg, O. Wennerström, J. Invest. Dermatol. 113, 547 (1999)

    Article  CAS  Google Scholar 

  18. J. Gaca, S. Żak Hydrogen peroxide and chlorides, examples of application and theoretical aspects (University of Technology and Agriculture in Bydgoszcz Publishers, Poland, 2004) (in Polish)

    Google Scholar 

  19. M. Nakajima, T. Kawakami, T. Niino, Y. Takahashi, S. Onodera, J. Health. Sci. 55, 363 (2009)

    Article  CAS  Google Scholar 

  20. A. Gackowska, J. Gaca, Chemik 4, 301 (2011)

    Google Scholar 

  21. N. Higashi, A. Ikehata, N. Kariyama, Y. Ozaki, Appl. Spectrosc. 62, 1022 (2008)

    Article  CAS  Google Scholar 

  22. P. Cysewski, A. Gackowska, J. Gaca, Chemosphere 63, 165 (2006)

    Article  CAS  Google Scholar 

  23. C. W. Jones, Applications of hydrogen peroxide and derivatives (Royal Society of Chemistry, Cambridge 1999)

    Google Scholar 

  24. A. D. Becke, Phys. Rev. A 38, 3098 (1988)

    Article  CAS  Google Scholar 

  25. A. D. Becke, J. Chem. Phys. 98, 5648 (1993)

    Article  CAS  Google Scholar 

  26. B. Miehlich, A. Savin, H. Stoll, H. Preuss, Chem. Phys. Lett. 157, 200 (1989)

    Article  CAS  Google Scholar 

  27. C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37, 785 (1988)

    Article  CAS  Google Scholar 

  28. S. Miertuš, E. Scrocco, J. Tomasi, Chem. Phys. 55, 117 (1981)

    Article  Google Scholar 

  29. S. Miertuš, J. Tomasi, Chem. Phys. 65, 239 (1982)

    Article  Google Scholar 

  30. M. J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery, Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03, Revision E. 01 (Gaussian, Inc., Pittsburgh PA, 2004)

    Google Scholar 

  31. R. G. Pearson, Proc. Natl. Acad. Sci. USA 83, 8440 (1986)

    Article  CAS  Google Scholar 

  32. R. G. Parr, L. von Szentpály, S. Liu, J. Am. Chem. Soc. 121, 1922 (1999)

    Article  CAS  Google Scholar 

  33. C. Møller, M.S. Plesset, Phys. Rev. 46, 0618 (1934)

    Article  Google Scholar 

  34. M. Head-Gordon, J.A. Pople, M.J. Frisch, Chem. Phys. Lett. 153, 503 (1988)

    Article  CAS  Google Scholar 

  35. S. Saebø, J. Almlöf, Chem. Phys. Lett. 154, 83 (1989)

    Article  Google Scholar 

  36. M. J. Frisch, M. Head-Gordon, J.A. Pople, Chem. Phys. Lett. 166, 275 (1990)

    Article  CAS  Google Scholar 

  37. M. J. Frisch, M. Head-Gordon, J.A. Pople, Chem. Phys. Lett. 166, 281 (1990)

    Article  CAS  Google Scholar 

  38. M. Head-Gordon, T. Head-Gordon, Chem. Phys. Lett. 220, 122 (1994)

    Article  CAS  Google Scholar 

  39. J. Kruszewski, T.M. Krygowski, Tetrahedron Lett. 13, 3839 (1972)

    Article  Google Scholar 

  40. T. M. Krygowski, M.K. Cyrański, Z. Czarnocki, G. Haäfelinger, A.R. Katritzky, Tetrahedron 56, 1783 (2000)

    Article  CAS  Google Scholar 

  41. W. Yang, W.J. Mortier, J. Am. Chem. Soc. 108, 5708 (1986)

    Article  CAS  Google Scholar 

  42. S. Pattanaargson, T. Munhapol, P. Hirumsupachot, P. Luangthongaram, J. Photochem. Photobiol. A 161, 269 (2004)

    Google Scholar 

  43. S. P. Huong, V. Andrieu, J.-P. Reynier, E. Rocher, J.-D. Fourneron, J. Photochem. Photobiol. A 186, 65 (2007)

    Article  CAS  Google Scholar 

  44. P. Renard, F. Siekmann, A. Gandolfo, J. Socorro, G. Salque, S. Ravier, E. Quivet, J.-L. Clément, M. Traikia, A.-M. Delort, D. Voisin, V. Vuitton, R. Thissen, A. Monod, Atmos. Chem. Phys. 13, 6473 (2013)

    Article  CAS  Google Scholar 

  45. N. De la Cruz, J. Giménez, S. Esplugas, D. Grandjean, L.F. de Alencastro, C. Pulgarín Water Res. 46, 1947 (2012)

    Article  Google Scholar 

  46. M. Czaplicka, J. Hazard. Mater. 134, 45 (2006)

    Article  CAS  Google Scholar 

  47. X. -W. Li, E. Shibata, T. Nakamura, Mater. Trans. 44, 2441 (2003)

    Article  CAS  Google Scholar 

  48. M. V. Roux, M. Temprado, J.S. Chickos, Y. Nagano, J. Phys. Chem. Ref. Data 37, 1855 (2008)

    Article  CAS  Google Scholar 

  49. V. A. Platonov, Yu.N. Simulin Russ. J. Phys. Chem. 59, 179 (1985)

    Google Scholar 

  50. J. D. Cox, D.D. Wagman, V.A. Medvedev, CODATA Key Values for Thermodynamics (Hemisphere Publishing Corp, New York, 1984)

    Google Scholar 

  51. M. W. Chase, NIST-JANAF Thermochemical Tables, J. Phys. Chem. Ref. Data, Monograph 9, 4th edition (American Chemical Society, American Institute of Physics, Washington, DC, 1998)

    Google Scholar 

  52. M. Bekbolet, Z. Çınar, M. Kılıç, C.S. Uyguner, C. Minero, E. Pelizzetti, Chemosphere 75, 1008 (2009)

    Article  CAS  Google Scholar 

  53. E. Zahedi, S. Ali-Asgari, V. Keley, Cent. Eur. J. Chem. 8, 1097 (2010)

    Article  Google Scholar 

  54. R. Taylor, in: C.H. Bamford, C.F.H. Tipper (Eds.), Comprehensive chemical kinetics, (Elsevier Publishing Co, Amsterdam/New York, 1972) Volume 13: Reactions of aromatic compounds, 1

  55. G. S. Hammond, J. Am. Chem. Soc. 77, 334 (1955)

    Article  CAS  Google Scholar 

  56. T. E. Jones, J. Phys. Chem. A 116, 4233 (2012)

    Article  CAS  Google Scholar 

  57. Md. E.U. Hoque, H.W. Lee, Bull. Korean. Chem. Soc. 32, 2109 (2011)

    Article  CAS  Google Scholar 

  58. M. Przybyłek, J. Gaca, Chem. Pap. 66, 699 (2012)

    Article  Google Scholar 

  59. V. Benin, J. Mol. Struc. (Theochem) 764, 21 (2006)

    Article  CAS  Google Scholar 

  60. H. D. Banks, J. Org. Chem. 68, 2639 (2003)

    Article  CAS  Google Scholar 

  61. C. Hansch, A. Leo, R.W. Taft, Chem. Rev. 91, 165 (1991)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Faculty of Chemical Technology and Engineering, University of Technology and Life Science, 85-326, Bydgoszcz, Poland

    Alicja Gackowska, Waldemar Studziński & Jerzy Gaca

  2. Department of Physical Chemistry, Collegium Medicum, Nicolaus Copernicus University, 85-950, Bydgoszcz, Poland

    Maciej Przybyłek

Authors
  1. Alicja Gackowska
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Maciej Przybyłek
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Waldemar Studziński
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jerzy Gaca
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Maciej Przybyłek.

About this article

Cite this article

Gackowska, A., Przybyłek, M., Studziński, W. et al. Experimental and theoretical studies on the photodegradation of 2-ethylhexyl 4-methoxycinnamate in the presence of reactive oxygen and chlorine species. cent.eur.j.chem. 12, 612–623 (2014). https://doi.org/10.2478/s11532-014-0522-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.2478/s11532-014-0522-6

Keywords

Search

Navigation