Abstract
The kinetics of photobleaching and formation of photoproducts upon irradiation (735 nm) of 5,10,15,20-tetrakis(m-hydroxyphenyl)bacteriochlorin (m-THPBC) in phosphate buffer saline (PBS) supplemented with human serum albumin (HSA) were studied by means of absorption and steady-state fluorescence spectroscopy. Measurements were performed either immediately after the dye was dissolved in the HSA solution (0 h) or after six hours incubation in the HSA solution (6 h). Spectroscopic studies indicated that the dye was mainly present as aggregates in freshly prepared solutions, whereas incubation favored monomerisation. Irrespective to incubation time, the rates of photobleaching obtained by fluorescence measurements were higher than those obtained from absorbance measurements. Photobleaching of freshly prepared m-THPBC can be described by a single exponential decay, while the absorbance and fluorescence decays of the incubated dye solutions better fit a bi-exponential decay. Two photobleaching rates probably reflect differences in the photosensitivity of monomer (bound to proteins) and aggregated (non-bound) forms. Irradiation of the freshly prepared m-THPBC solution led to phototransformation of 50% of the bleached m-THPBC into 5,10,15,20-tetrakis(m-hydroxyphenyl)chlorin (m-THPC), a clinically used second generation photosensitizer. For irradiation 6 h after dissolving m-THPBC, different kinetics of m-THPC formation were found. A rapid decrease in concentration of m-THPBC was accompanied by a slow formation of m-THPC. The quantum yield of this process was small since only 5% of m-THPBC was transformed to m-THPC. The kinetics characteristics of m-THPBC photobleaching reported in the present study, together with the different kinetics of photoproduct formation during m-THPBC photobleaching, may provide important indications in the m-THPBC-based PDT dosimetry.
Similar content being viewed by others
References
J. D. Spikes, Quantum yields and kinetics of the photobleaching of hematoporphyrin, Photofrin II, tetra(4-sulfonatophenyl)-porphine and uroporphyrin Photochem. Photobiol. 1992 55 797–808.
R. Bonnett, G. Martínez, Photobleaching of sensitisers used in photodynamic therapy, report number 591 Tetrahedron 2001 57 9513–9547.
B. C. Wilson, M. S. Patterson and L. Lilge, Implicit and explicit dosimetry in photodynamic therapy: a new paradigm. Lasers Med. Sci. 1997 12 182–199.
H. Zeng, M. Korbelik, D. I. McLean, C. MacAulay and H. Lui, Monitoring photoproduct formation and photobleaching by fluorescence spectroscopy has the potential to improve PDT dosimetry with a verteporfin-like photosensitizer Photochem. Photobiol. 2002 75 398–405.
J. Moan, Effect of bleaching of porphyrin sensitizers during photodynamic therapy Cancer Lett. 1986 33 45–53.
R. Bonnett, R. D. White, U. J. Winfield and M. C. Berenbaum, Hydroporphyrins of the meso-tetra(hydroxyphenyl)porphyrin series as tumour photosensitizers Biochem. J. 1989 261 277–280.
R. Bonnett, P. Charlesworth, B. D. Djelal, S. Foley, D. J. McGarvey and T. G. Truscott, Photophysical properties of 5,10,15,20-tetrakis(m-hydroxyphenyl)porphyrin (m-THPP), 5,10,15,20-tetrakis(m-hydroxyphenyl)chlorin (m-THPC) and 5,10,15,20-tetrakis(m-hydroxyphenyl) bacteriochlorin (m-THPBC): a comparative study J. Chem. Soc., Perkin Trans. 2 1999 2 325–328.
J. P. Rovers, M. L. de Jode and M. F. Grahn, Significantly increased lesion size by using the near-infrared photosensitizer 5,10,15,20-tetrakis (m-hydroxyphenyl)bacteriochlorin in interstitial photodynamic therapy of normal rat liver tissue Lasers Surg. Med. 2000 27 235–240.
K. Engelmann, M. G. Mack, K. Eichler, R. Straub, S. Zangos and T. J. Vogl, Interstitial photodynamic laser therapy for liver metastases: first results of a clinical phase I study RoeFo, Fortschr. Geb. Rontgenstr. Neuen. Bildgeb. Verfahr. 2003 175 682–687.
R. Bonnett, B. D. Djelal, P. A. Hamilton, G. Martinez and F. Wierrani, Photobleaching of 5,10,15,20-tetrakis(m-hydroxyphenyl)porphyrin (m-THPP) and the corresponding chlorin (m-THPC) and bacteriochlorin(m-THPBC). A comparative study J. Photochem. Photobiol. B 1999 53 136–143.
J. P. Rovers, M. L. de Jode, H. Rezzoug and M. F. Grahn, In vivo photodynamic characteristics of the near-infrared photosensitizer 5,10,15,20-tetrakis(M-hydroxyphenyl) bacteriochlorin Photochem. Photobiol. 2000 72 358–364.
M. Angotti, B. Maunit, J. F. Muller, L. Bezdetnaya and F. Guillemin, Characterization by matrix-assisted laser desorption/ionizat ion Fourier transform ion cyclotron resonance mass spectrometry of the major photoproducts of temoporfin (m-THPC) and bacteriochlorin (m-THPBC) J. Mass. Spectrom. 2001 36 825–831.
R. Rotomskis, S. Bagdonas and G. Streckyte, Spectroscopic studies of photobleaching and photoproduct formation of porphyrins used in tumour therapy J. Photochem. Photobiol. B 1996 33 61–67.
M. B. Ericson, S. Grapengiesser, F. Gudmundson, A. M. Wennberg, O. Larko, J. Moan and A. Rosen, A spectroscopic study of the photobleaching of protoporphyrin IX in solution Lasers Med. Sci. 2003 18 56–62.
L. Bezdetnaya, N. Zeghari, I. Belitchenko, M. Barberi-Heyob, J. L. Merlin, A. Potapenko and F. Guillemin, Spectroscopic and biological testing of photobleaching of porphyrins in solutions Photochem. Photobiol. 1996 64 382–386.
I. Belitchenko, V. Melnikova, L. Bezdetnaya, H. Rezzoug, J. L. Merlin, A. Potapenko and F. Guillemin, Characterization of photodegradation of meta-tetra(hydroxyphenyl)chlorin (m-THPC) in solution: biological consequences in human tumor cells Photochem. Photobiol. 1998 67 584–590.
M. F. Grahn, A. McGuinness, R. Benzie, R. Boyle, M. L. de Jode, M. G. Dilkes, B. Abbas and N. S. Williams, Intracellular uptake, absorption spectrum and stability of the bacteriochlorin photosensitizer 5,10,15,20-tetrakis (m-hydroxyphenyl)bacteriochlorin (m-THPBC). Comparison with 5,10,15,20-tetrakis(m-hydroxyphenyl)chlorin (m-THPC) J. Photochem. Photobiol. B 1997 37 261–266.
B. M. Aveline, T. Hasan and R. W. Redmond, The effects of aggregation, protein binding and cellular incorporation on the photophysical properties of benzoporphyrin derivative monoacid ring A (BPDMA) J. Photochem. Photobiol. B 1995 30 161–169.
D. J. Ball, S. R. Wood, D. I. Vernon, J. Griffiths, T. M. Dubbelman and S. B. Brown, The characterisation of three substituted zinc phthalocyanines of differing charge for use in photodynamic therapy. A comparative study of their aggregation and photosensitising ability in relation to mTHPC and polyhaematoporphyrin J. Photochem. Photobiol. B 1998 45 28–35.
J. Moan, The photochemical yield of singlet oxygen from porphyrins in different states of aggregation. Photochem. Photobiol. 1984 39 445–449.
J. Moan, G. Streckyte, S. Bagdonas, O. Bech and K. Berg, Photobleaching of protoporphyrin IX in cells incubated with 5-aminolevulinic acid Int. J. Cancer 1997 70 90–97.
A. B. Uzdensky, V. Iani, L. W. Ma and J. Moan, Photobleaching of hypericin bound to human serum albumin, cultured adenocarcinoma cells and nude mice skin Photochem. Photobiol. 2002 76 320–328.
J. Moan, P. Juzenas and S. Bagdonas, Degradation and transformation of photosensitizers during light exposure Recent Res. Dev. Photochem. Photobiol. 2000 4 121–132.
R. Bonnett and G. Martinez, Photobleaching of compounds of the 5,10,15,20-tetrakis(m-hydroxyphenyl) porphyrin series (m-THPP, m-THPC and m-THPBC) Org. Lett. 2002 4 2013–2016.
L. W. Ma, J. Moan, M. F. Grahn and V. Iani, Comparison of meso-tetrahydroxyphenyl-chlorin and meso-tetrahydroxyphenyl-bacteriochlorin with respect to photobleaching and PCT efficiency in vivo Proc. SPIE 1996 2924 219–224.
I. Georgakoudi, M. G. Nichols and T. H. Foster, The mechanism of Photofrin photobleaching and its consequences for photodynamic dosimetry Photochem. Photobiol. 1997 65 135–144.
I. Georgakoudi and T. H. Foster, Singlet oxygen versus non-singlet oxygen-mediated mechanisms of sensitizer photobleaching and their effects on photodynamic dosimetry Photochem. Photobiol. 1998 67 612–625.
C. Hadjur, N. Lange, J. Rebstein, P. Monnier, H. van den Bergh and G. Wagnières, Spectroscopic studies of photobleaching and photoproduct formation of meta(tetrahydroxyphenyl) chlorin (m-THPC) used in photodynamic therapy. The production of singlet oxygen by m-THPC J. Photochem. Photobiol. B 1998 45 170–178.
S. Coutier, S. Mitra, L. N. Bezdetnaya, R. M. Parache, I. Georgakoudi, T. H. Foster and F. Guillemin, Effects of fluence rate on cell survival and photobleaching in meta-tetra-(hydroxyphenyl)chlorin-photosensitized Colo 26 multicell tumor spheroids Photochem. Photobiol. 2001 73 297–303.
C. R. Shea, Y. Hefetz, R. Gillies, J. Wimberly, G. Dalickas and T. Hasan, Mechanistic investigation of doxycycline photosensitization by picosecond-pulsed and continuous wave laser irradiation of cells in culture J. Biol. Chem. 1990 265 5977–5982.
B. W. Pogue, B. Ortel, N. Chen, R. W. Redmond and T. Hasan, A photobiological and photophysical-based study of phototoxicity of two chlorins Cancer Res. 2001 61 717–724.
Author information
Authors and Affiliations
Corresponding author
Additional information
Presented at the 10th Congress of the European Society for Photobiology, Vienna, Austria, 09 6th-11th, 2003.
Rights and permissions
About this article
Cite this article
Lassalle, HP., Bezdetnaya, L., Iani, V. et al. Photodegradation and phototransformation of 5,10,15,20-tetrakis(m-hydroxyphenyl)bacteriochlorin (m-THPBC) in solution. Photochem Photobiol Sci 3, 999–1005 (2004). https://doi.org/10.1039/b405138f
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1039/b405138f