Skip to main content
SpringerLink
Log in

A comparative study of water soluble 5,10,15,20-tetrakis(2,6-dichloro-3-sulfophenyl)porphyrin and its metal complexes as efficient sensitizers for photodegradation of phenols

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

Abstract

5,10,15,20-Tetrakis(2,6-dichloro-3-chlorosulfophenyl)porphyrin and its tin and zinc complexes were synthesized with high yields and fully characterized. The corresponding water-soluble 5,10,15,20-tetrakis(2,6-dichloro-3- sulfophenyl)porphyrins were obtained by hydrolysis with water. An extensive photophysical study of the new water soluble porphyrinic compounds was carried out including absorption and fluorescence spectra, fluorescence quantum yields, triplet absorption spectra, triplet lifetimes, triplet and singlet oxygen quantum yields. These sensitizers were successfully used in the photodegradation of 4-chlorophenol and 2,6-dimethylphenol. A comparison is made of their efficiencies, and some mechanistic considerations are highlighted.

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

Refences

  1. M. Sarakha, M. Bolte, H. D. Burrows Electron-transfer oxidation of chlorophenols by uranyl ion excited state in aqueous solution. Steady-state and nanosecond flash photolysis studies J. Phys. Chem. A 2000 104 3142–3149

    Article  CAS  Google Scholar 

  2. J. C. D’Oliveira, G. Al-Sayyed, P. Pichat Photodegradation of 2-chlorophenol and 3-chlorophenol in TiO2 aqueous suspensions Environ. Sci. Technol 1990 24 990–996

    Article  Google Scholar 

  3. M. J. Kochany, J. R. Bolton Mechanism of photodegradation of aqueous organic pollutants. 2. Measurement of the primary rate constants for reaction of OH radicals with benzene and some halobenzenes using and EPR spin-trapping method following the photolysis of H2O2Environ. Sci. Technol. 1992 26 262–265

    Article  CAS  Google Scholar 

  4. M. Sarakha, H. D. Burrows, M. Bolte Selective oxidation of meta- and para-phenylphenol photosensitized by [Co(NH35N3]2+ in aqueous solution J. Photochem. Photobiol., A 1996 97 81–86

    Article  CAS  Google Scholar 

  5. M. Sarakha, M. Bolte, H. D Burrows The photo-oxidation of 2,6-dimethylphenol and monophenylphenols by uranyl ion in aqueous solution J. Photochem. Photobiol., A 1997 107 101–106

    Article  CAS  Google Scholar 

  6. M. Nowakowska, M. Kepczynski Polymeric photosensitizers—2. Photosensitized oxidation of phenol in aqueous solution J. Photochem. Photobiol., A 1998 116 251–256

    Article  CAS  Google Scholar 

  7. O. Legrini, E. Oliveros, A. M. Braun Photochemical processes for water treatment Chem. Rev. 1993 93 671–698

    Article  CAS  Google Scholar 

  8. P. Boule, C. Richard, K. David-Oudjehani, G. Grabner Photochemical behaviour of halophenols in aqueous solution Proc. Indian Acad. Sci. Chem. Sci. 1997 109 509–519

    Article  CAS  Google Scholar 

  9. Y. I. Skurlatov, L. S. Ernestova, E. V. Vichutinskaya, D. P. Samsonov, I. V. Semenova, I. Y. Rodko, V. O. Shvidky, R. I. Pervunina, T. J Kemp Photochemical transformation of polychlorinated phenols J. Photochem. Photobiol., A 1997 107 207–213

    Article  CAS  Google Scholar 

  10. H. D. Burrows, L. S. Ernestov, T. J. Kemp, Y. I. Skurlatov, A. P. Purmal, A. N. Yermakov Kinetics and mechanism of photodegradation of chlorophenols Prog. React. Kinet. 1998 23 145–207

    Article  CAS  Google Scholar 

  11. P. G. Tratnyek, J. Hoigné Oxidation of substituted phenols in the environment—a QSAR analysis of rate constants for reaction with singlet oxygen Environ. Sci. Technol. 1991 25 1596–1604

    Article  CAS  Google Scholar 

  12. N. A. Garcia Singlet-molecular-oxygen mediated photodegradation of aquatic phenolic pollutants, A kinetic and mechanistic overview J. Photochem. Photobiol., B 1994 22 185–196

    Article  CAS  Google Scholar 

  13. J. A. Rosso, S. Criado, S. G. Bertolotti, P. E. Allegretti, J. Furlong, N. A. Garcia, M. C. Gonzalez, D. O. Mártire Photochem. Photobiol. Sci. 2003 2 882–887

    Article  CAS  PubMed  Google Scholar 

  14. M. Gouterman, Optical spectra and electronic structure of porphyrins and related rings, in The Porphyrins Vol. III Physical Chemistry, Part A, ed. D. Dolphin, Academic Press, New York, 1978, pp. 1–156

    Google Scholar 

  15. K. Ozoemena, N. Kuznetsova, T. Nyokong Photosensitized transformation of 4-chlorophenol in the presence of aggregated and non-aggregated metallophthalocyanines J. Photochem. Photobiol., A 2001 139 217–224

    Article  CAS  Google Scholar 

  16. G. Lente, J. H. Espenson Photoaccelerated oxidation of chlorinated phenols Chem. Commun. 2003 1162–1163

    Google Scholar 

  17. E. Silva, M. M. Pereira, H. D. Burrows, M. E. Azenha, M. Sarakha, M. Bolte Photooxidation of 4-chlorophenol sensitised by iron meso-tetrakis(2,6-dichloro-3-sulfophenyl)porphyrin in aqueous solution Photochem. Photobiol. Sci. 2004 3 200–204

    Article  CAS  PubMed  Google Scholar 

  18. C. Tanielian, R. Mechin, R. Seghrouchini, C. Schweitzer Mechanistic and kinetics aspects of photosensitization in the presence of oxygen Photochem. Photobiol. 2000 71 12–19

    Article  CAS  PubMed  Google Scholar 

  19. M. Pineiro, L. Carvalho, M. M. Pereira, A. M. D. R. Gonsalves, L. G. Arnaut, S. J. Formosinho Photoacoustic measurements of porphyrin triplet-state quantum yields and singlet-oxygen efficiencies Chem.–Eur. J. 1998 4 2299–2307

    Article  CAS  Google Scholar 

  20. E. G. Azenha, A. C. Serra, M. Pineiro, M. M. Pereira, J. S. de Melo, L. G. Arnaut, S. J. Formosinho, A. M. D. R. Gonsalves Heavy-atom effects on metalloporphyrins and polyhalogenated porphyrins Chem. Phys. 2002 280 177–190

    Article  CAS  Google Scholar 

  21. M. C. DeRosa, R. J. Crutchley Photosensitized singlet oxygen and its applications Coord. Chem. Rev. 2002 233 351–371

    Article  Google Scholar 

  22. D. Murtinho, M. Pineiro, M. M. Pereira, A. M. D. R. Gonsalves, L. G. Arnaut, M. G. Miguel, H. D. Burrows Novel porphyrins and a chlorin as efficient singlet oxygen sensitizers for photooxidation of naphthols and phenols to quinones J. Chem. Soc., Perkin Trans. 2 2000 2441–2447

    Google Scholar 

  23. A. M. D. R. Gonsalves, R. A. W. Johnstone, M. M. Pereira, A. M. P. deSantAna, A. C. Serra, A. J. F. N. Sobral, P. A. Stocks New procedures for the synthesis and analysis of 5,10,15,20-tetrakis(sulfophenyl)porphyrins and derivatives through chlorosulfonation Heterocycles 1996 43 829–838

    Article  Google Scholar 

  24. A. D. Adler, F. R. Longo, F. Kampas, J. Kim On preparation of metalloporphyrins J. Inorg. Nucl. Chem. 1970 32 2443–2445

    Article  CAS  Google Scholar 

  25. D. G. Whitten, J. C. Yau, F. A. Carroll Photochemistry and oxidation-reduction reactions of tin porphyrins J. Am. Chem. Soc. 1971 93 2291–2296

    Article  CAS  Google Scholar 

  26. W. A. Lee, M. Graetzel, K. Kalyanasundaram Anomalous ortho effects in sterically hindered porphyrins: tetrakis(2,6-dimethylphenyl)porphyrin and its sulfonate derivative Chem. Phys. Lett. 1984 107 308–313

    Article  CAS  Google Scholar 

  27. S. L. Murov, I. Carmichael, G. L. Hug, Handbook of Photochemistry, Marcel Dekker, New York, 1993

    Google Scholar 

  28. J. P. Keene, D. Kessel, E. J. Land, R. W. Redmond, T. G. Truscott Direct detection of singlet oxygen sensitized by hematoporphyrin and related compounds Photochem. Photobiol. 1986 43 117–120

    Article  CAS  PubMed  Google Scholar 

  29. S. Navaratnam, I. Hamblet, H. H. Tonnesen Photoreactivity of biologically active compounds. XVI. Formation and reactivity of free radicals in mefloquine J. Photochem. Photobiol., B 2000 56 25–38

    Article  CAS  Google Scholar 

  30. H. D. Burrows, J. S. de Melo, C. Serpa, L. G. Arnaut, A. P. Monkman, I. Hamblett, S. Navaratnam S1 to T1 intersystem crossing in p-conjugated organic polymers J. Chem. Phys. 2001 115 9601–9606

    Article  CAS  Google Scholar 

  31. J. Davila, A. Harriman Phototosensitized-oxidation of biomaterials and related model compounds Photochem. Photobiol. 1989 50 29–35

    Article  CAS  PubMed  Google Scholar 

  32. J. G. Calvert and J. M. Pitts, Photochemistry, John Wiley and Sons, New York, 1996, pp. 783–786

    Google Scholar 

  33. P. J. Gonçalves, L. De Boni, N. M. Barbosa Neto, J. J. Rodrigues, Jr., S. C. Zílio, I. E. Borissevitch Effect of protonation on the photophysical properties of meso-tetra(sulfonatophenyl)porphyrin Chem. Phys. Lett. 2005 407 236–241

    Article  CAS  Google Scholar 

  34. D. L. Akins, H. R. Zhu, C. Guo Aggregation of tetraaryl-substituted porphyrins in homogeneous solution J. Phys. Chem. 1996 100 5420–5425

    Article  CAS  Google Scholar 

  35. T. Gensch, C. Viappiani, S. E. Braslavsky Structural Volume Changes upon photoexcitation of porphyrins: role of the nitrogen–water interactions J. Am. Chem. Soc. 1999 121 10573–10582

    Article  CAS  Google Scholar 

  36. M. Gouterman Spectra of porphyrins J. Mol. Spectrosc. 1961 6 138–163

    Article  CAS  Google Scholar 

  37. P. G. Seybold, M. Gouterman Porphyrins, 13: Fluorescence spectra and quantum yields J. Mol. Spectrosc. 1969 31 1–13

    Article  CAS  Google Scholar 

  38. T. Gensch, S. E. Braslavsky Volume changes related to triplet formation of water-soluble porphyrins. A laser-induced optoacoustic spectroscopy (LIOAS) study J. Phys. Chem. B 1997 101 101–108

    Article  CAS  Google Scholar 

  39. O. L. Gijzema, F. Kaufman, G. Porter Oxygen quenching of aromatic triplet-states in solution. Part 1 J. Chem. Soc., Faraday Trans. 2 1973 69 708–720

    Article  Google Scholar 

  40. M. Pineiro, M. M. Pereira, A. M. D. R. Gonsalves, L. G. Arnaut, S. J. Formosinho Singlet oxygen quantum yields from halogenated chlorins: potential new photodynamic therapy agents J. Photochem. Photobiol., A 2001 138 147–157

    Article  CAS  Google Scholar 

  41. M. Pineiro, A. M. D. R. Gonsalves, M. M. Pereira, S. J. Formosinho, L. G. Arnaut New halogenated phenylbacteriochlorins and their efficiency in singlet-oxygen sensitization J. Phys. Chem. A 2002 106 3787–3795

    Article  CAS  Google Scholar 

  42. R. Schmidt, C. Tanielian, R. Dunsbach, C. Wolff Phenalenone, a universal reference compound for the determination of quantum yields of singlet oxygen O21Δg) sensitization J. Photochem. Photobiol., A 1994 79 11–17

    Article  CAS  Google Scholar 

  43. C. Tanielian, C. Wolff, M. Esch Singlet oxygen production in water: aggregation and charge-transfer effects J. Phys. Chem 1996 100 6555–6560

    Article  CAS  Google Scholar 

  44. J. Davila, A. Harriman Photoreactions of macrocyclic dyes bound to human-serum albumin Photochem. Photobiol. 1990 51 9

    Article  CAS  PubMed  Google Scholar 

  45. M. C. Aragoni, M. Arca, G. Crisponi, V. M. Nurchi Simultaneous decomposition of several spectra into the constituent Gaussian peaks Anal. Chim. Acta 1995 316 195–204

    Article  CAS  Google Scholar 

  46. H. Gorner Photoprocesses of p-benzoquinones in aqueous solution J. Phys. Chem. A 2003 107 11587–11595

    Article  CAS  Google Scholar 

  47. T. G. Gantchev, W. M. Sharman, J. E. van Lier Metallophthalocyanines photosensitize the breakdown of (hydro)peroxides in solution to yield hydroxyl or alkoxyl and peroxyl free radicals via different interaction pathways J. Photochem. Photobiol. 2003 77 469–479

    CAS  Google Scholar 

  48. R. V. Bensson, E. J. Land, T. G. Truscott, Excited states and free radicals in biology and medicine, Oxford University Press, Oxford, 1993, pp. 76–82

    Google Scholar 

  49. G. S. Nahor, J. Rabani, F. Grieser Properties of excited tetrakis(sulfonatophenyl)porphyrin in aqueous solution. Photoredox reactions with quenchers J. Phys. Chem. 1981 85 697–702

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Departamento de Química, Universidade de Coimbra, 3004-535, Coimbra, Portugal

    Carlos J. P. Monteiro, Mariette M. Pereira, M. Emilia Azenha, Hugh D. Burrows, Carlos Serpa & Luis G. Arnaut

  2. Departamento de Química, Universidad de Burgos, Plaza Misael Bañuelos, Burgos, 09001, Spain

    M. J. Tapia & Pascal Wong-Wah-Chung

  3. Laboratoire de Photochimie Moléculaire et Macromoléculaire, UMR CNRS 433, Université Blaise-Pascal, Clermont Ferrand, 63177, Aubière Cedex, France

    Mohamed Sarakha

  4. Free Radical Research Facility, Daresbury Laboratory, Warrington, UK, WA4 4AD

    Suppiah Navaratnam

  5. Biosciences Research Institute, University of Salford, UK, M4 4WT

    Suppiah Navaratnam

Authors
  1. Carlos J. P. Monteiro
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mariette M. Pereira
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. M. Emilia Azenha
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Hugh D. Burrows
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Carlos Serpa
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Luis G. Arnaut
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. M. J. Tapia
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Mohamed Sarakha
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Pascal Wong-Wah-Chung
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Suppiah Navaratnam
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mariette M. Pereira.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Monteiro, C.J.P., Pereira, M.M., Azenha, M.E. et al. A comparative study of water soluble 5,10,15,20-tetrakis(2,6-dichloro-3-sulfophenyl)porphyrin and its metal complexes as efficient sensitizers for photodegradation of phenols. Photochem Photobiol Sci 4, 617–624 (2005). https://doi.org/10.1039/b507597a

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/b507597a

Search

Navigation