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Article

Spectroscopic Behavior of Some A3B Type Tetrapyrrolic Complexes in Several Organic Solvents and Micellar Media

1
Faculty of Pharmacy, “Carol Davila” University of Medicine and Pharmacy, 6 Traian Vuia Street, Bucharest 020956, Romania
2
“Ilie Murgulescu” Institute of Physical Chemistry, Romanian Academy, 202 Splaiul Independenţei, Bucharest 060021, Romania
*
Author to whom correspondence should be addressed.
Int. J. Mol. Sci. 2011, 12(9), 5552-5564; https://doi.org/10.3390/ijms12095552
Submission received: 20 June 2011 / Revised: 19 August 2011 / Accepted: 26 August 2011 / Published: 30 August 2011
(This article belongs to the Section Physical Chemistry, Theoretical and Computational Chemistry)

Abstract

:
The paper presents spectral studies of some unsymmetrical A3B tetrapyrrolic, porphyrin-type complexes with Cu(II) and Zn(II) in different solvents and micellar media aimed at estimating their properties in connection with the living cell. The results indicate that the position of the absorption and emission peaks is mostly influenced by the central metal ion and less by the environmental polarity or the peripheric substituents of the porphyrinic core. The comparison between the overall absorption and emission spectra of the compounds in methanol or cyclohexane vs. direct and reverse Triton X micellar systems, respectively, suggests for all compounds the localization at the interface between the polyethylene oxide chains and the tert-octyl-phenyl etheric residue of the Triton X-100 molecules. These findings could be important when testing the compounds embedded in liposomes or other delivery systems to the targeted cell.

1. Introduction

Spectroscopic characterization of porphyrins in different media is an important step in assessing their application in the biomedical field, as the matrix in which they are supposed to act is a complex one, involving both hydrophilic and lipophilic characteristics [17].
The amphiphilic character of the porphyrins, given by the hydrophobic and hydrophilic groups placed in various proportions and positions of the substituted structure, generates an intramolecular axis of polarity. This specific structure is responsible for the biological properties of porphyrins related to the cell membranes penetration and/or cellular target binding. When used in therapy (e.g., photodynamic therapy—PDT) or as markers (molecular probes in photodynamic diagnosis—PDD), their spectral properties are important characteristics that often define their efficiency as photosensitizers [8,9]. Because the lifetime of oxygen singlet (1Δg) in organic solvents or micelles is higher than in water, the singlet-oxygen-mediated photodamage will increase when the porphyrins are located in hydrophobic regions [10]. Also, the incorporation of porphyrins in micelles dramatically influences the aggregation characteristics and location of these molecules within the cells [11]. These are the main reasons to study the particular case of the A3B unsymmetrically meso-substituted metalloporphyrins as amphiphilic structures in different polarity media and incorporated in nanostructures such as micelles [1214].
Solvatochromy studies can also provide valuable information to identify the potential molecular targets within the cell [10], to predict the cellular intake and subsequent porphyrin metabolism [15] and to obtain optimum conditions for the photosensitization, as spectral properties are often dramatically changed by the microenvironment [16,17].
The non-ionic surfactants exhibit an extended polar part, with variable dimensions given by the number of oxyethylene units, which is highly influenced by hydration. Among this kind of surfactants, tert-octylphenoxypolyethoxyethanol (Triton X-100) has a polyoxyethylene chain consisting of 9.5 ethylene oxide units on average, thus being a medium-chain length surfactant [18]. Literature data indicate a general good understanding of the rules governing self-assembly in direct (DM) and reverse micelles (RM) built with this surfactant [19,20]. Therefore, we chose to work with two well characterized TX-100 micelle systems, having well-defined dimensions, aggregation numbers and core polarities (Figure 1). Polyethylene glycol (PEG) has been widely used in pharmaceutical preparations [21]. The similarity of PEG chemical structure allowed us to compare the spectral changes observed for the porphyrins embedded in DM and RM and to suggest the possible localization of the compounds tested within the micelles.
The study presents a few of such spectral properties for some unsymmetrical porphyrinic complexes which have been previously synthesized [2224], and are presented in Figure 2: 5-[(3,4- methylendioxy)phenyl]-10,15,20-tris-(4-carboxymethylphenyl)-21,23-Zn(II)-porphine (Zn(II)TRMOPP), 5-[(3,4-methylendioxy)phenyl]-10,15,20-tris-(4-carboxymethylphenyl)-21,23-Cu(II)-porphine (Cu(II) TRMOPP), 5-(4-hydroxyphenyl)-10,15,20-tris-(4-carboxymethylphenyl)-21,23-Zn(II)-porphine (Zn(II)TCMPOHp), 5-(4-hydroxyphenyl)-10,15,20-tris-(4-carboxymethylphenyl)-21,23-Cu(II)-porphine (Cu(II)TCMPOHp), 5-(x-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-Cu(II)-porphine (Cu(II)TPPOHX), 5-(x-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-Zn(II)-porphine (Zn(II)TPPOHX) (x = 2, 3, 4).
The spectral characteristics defined as follows could predict the spectral characteristics of protein-bound mesoporphyrinic systems and also the properties of the studied compounds in pharmaceutical formulation.

2. Results and Discussion

2.1. UV-Vis Spectroscopy

Porphyrinic complexes display in their molecular absorption spectra, one Soret (B) band as a result of a1u (π) → eg (π*) transition, generally situated in the spectral range 400–440 nm, and one or two Q bands between 500–650 nm, corresponding to the a2u (π) → eg (π*) transition [25,26].
The unsymmetrical mesoporphyrinic complexes used in this study revealed a strong Soret band with maximum in the range 410–430 nm accompanied by Q bands situated in the range 540–600 nm (Figure 3, Tables 1, 2). Results are consistent with those obtained on similar compounds [27].
The main differences observed in the spectral band position are due to the type of metallic ion. That means that the influence of the central ion is higher in what concerns the displacement of the spectral bands position compared to that induced by the peripheral substituents of the porphyrinic macrocycle, which is of only 2–4 nm. Therefore, in the case of Cu(II) complexes, Soret bands are 10–12 nm hypsochromically shifted compared to the corresponding Zn(II) complex having the same ligand, in the same solvent. Similarly, the Q bands of the copper porphyrins show a blue shift of about 20 nm compared to the corresponding zinc porphyrins. Results confirm earlier results obtained with other metalloporphyrins [2224,26].
These spectral differences are the result of stronger conjugation effects that occur between the metallic ion orbitals and the π electrons of the tetrapyrrolic ring, effects that cause an energy decrease of the a1u (π) and a2u (π) orbitals relative to the eg (π*) orbitals, with increased energy available for copper porphyrins that generate the blue shift of the spectral bands compared to the zinc porphyrins [28].
From the experimental data we could observe that the influence of the non-symmetrical substituents versus spectral properties of the metalloporphyrins is insignificant. The hydrophilic groups placed in various positions of the porphyrinic structure did not significantly disturb the inner π electron ring of the macrocycle, which is responsible for the active electronic transitions in the above mentioned spectral range [29,30].
The change of the charge density and distribution on the periphery of the porphyrine macrocycle induced by the polar substituents supports the localization of the photosensitizer at the cellular level, without significant change of the spectral properties responsible to its photophysical activation.
The organic solvents were chosen for the study taking into account their relative polarity, as defined by Reichard [31]. Thus, cyclohexane, dimethysulfoxide and methanol, having relative polarity indices of 0.0006, 0.444 and 0.762, respectively, have been chosen. Only for comparison purposes, the ethylene glycol (relative polarity index 0.790) was also chosen.
The spectral data obtained indicate that the position of the absorption bands is less influenced by environmental polarity. However, a few observations can be made. For the same compound, the longest wavelengths maxima can be found in dimethylsulfoxide (generally, about 5 nm bathochromically shifted as compared to the other solvents), followed by cyclohexane and methanol (with 1 to 3 nm separate from each other). The observation is valid for both Soret and Q bands.
In case of direct micelles compared to PEG 300 (considered as reference), the shifts are too small (1–2 nm) or missing (in most cases in copper porphyrinic complexes). Meanwhile, the comparison of the wavelengths of the maxima with those belonging to the same compound dissolved in methanol (the most polar solvent) show that there is a slight bathochromic shift in case of the direct micelles vs. MeOH, suggesting the presumptive localization for the entire group of porphyrins as individual probe in direct micelles, as expected, in the polyethyleneoxide chain, at the interface with the tert-octyl-phenylether bulk of the TX-100 molecule, and not at the water-oxyethylene chain interface.
Similar results were obtained in the case of reverse micelles, i.e., the maxima of the Soret bands position are in the same region as the PEG 300 reference system, indicating the metalloporphyrins localization at the oxyethylene chains level. The results confirm those obtained earlier on similar mesoporphyrinic compounds [32].

2.2. Fluorescence Spectroscopy

The fluorescence measurements were performed on the studied complexes in the same solvents and micellar systems. Only the zinc porphyrinic compounds exhibit fluorescent properties strong enough to be taken into account.
In order to get a good comparison between the compounds, the excitation was set to 420 nm.
One can observe that the differences between the emission wavelengths are small, confirming the results already obtained for the absorption spectra. Therefore, the fluorescence spectral data shows for zinc porphyrinic complexes two bands located in the spectral region of 605–665 nm (Figure 4, Table 3) and reveal smaller shifts of the emission maxims when changing the environmental polarity. This smal bathocromic shift of the fluorescence maximum position indicates incorporation of the porphyrinic complex in the micellar media.
In Triton X-100/cyclohexane reverse micelles the fluorescence data of zinc complexes confirm their localization in the area of the polyethyleneoxidic chains, as the maximum wavelength is located in the same spectral range as in the PEG 300 reference system.
For the zinc tetrapyrollic complexes a smaller bathochromic shift in direct micelles was registered as compared to PEG 300 systems and methanolic solution, suggesting a localization of the complex in the polar area of the micelle.
The results indicate that the administration of the porphyrins to cells in view of photosensitization will probably not change the photophysical characteristics of the porphyrins even embedded in liposomes or other kind of delivery systems.
The Stokes shifts of the studied Zn(II) mesoporphyrins, computed as the difference between the maximum of emission and that one of absorption, as displayed in Table 4, show that the influence DMSO compared to the other two solvents used results in less change of the Stokes shift (of 1 to 3 nm).

3. Experimental Section

Porphyrinic complexes used in this study were synthesized as previously described [2224].
Poly (oxyethylene) tert-octylphenyl ether (Triton X-100–TX, purity > 99%), methanol (MeOH, HPLC gradient grade), dimethyl sulfoxide (DMSO, analytical grade) dichloromethane (analytical grade) and polyethylene glycol 300 (Carbowax 300) were bought from Sigma and used without supplementary preparation before. Water was double distilled and deionized before use.
Molecular absorption spectra were recorded on a Lambda 35 Perkin-Elmer UV-Vis spectrophotometer in 10 mm path length quartz cells, in single beam mode.
Fluorescence spectra were recorded on a steady-state Jasco FP 6500 spectrofluorimeter in 10 mm path length quartz cells.
The solutions used were prepared by repeated dilution to obtain a final 2.5 × 10−6 M concentration of each compound in the three solvents.
The 0.24 mM TX-100 in water (w/w) direct micelles (DM) and 0.66 M TX-100 in cyclohexane (w/w) reverse micelles (RM) loaded with 2.5 × 10−6 M metalloporphyrins were prepared according to the procedure described before [33]. Briefly, appropriate volumes of metalloporphyrins in dichloromethane solutions were evaporated to dryness at room temperature on the bottom of a test tube. Aliquots of 3mL of appropriate concentrations of Triton X-100 in water and cyclohexane were added, and then the tubes were mildly vortex mixed for 5 minutes, capped and then left still overnight to ensure the solubilization and diffusion of the metalloporphyrins into the micelles. The final concentration of each porphyrinic compound in micellar media was set at 2.5 × 10−6 M; the solutions were kept in dark to prevent photodegradation before the measurements, which were performed 24 h after preparation.

4. Conclusions

The paper presents the molecular spectral characteristics of certain A3B type meso-substituted metalloporphyrins in different polarity solvents and in micellar media. The studies revealed that the position of Soret and Q bands of the porphyrins is mainly influenced by the central metal ion and less by the peripheral substituents of the porphyrinic core or polarity of the solvent, thus confirming the results previously obtained on other metalloporphyrins.
The estimated localization of the porphyrinic in direct and reversed micelles compounds was possible by the evaluation of the spectral changes, for each compound, using PEG 300 as reference versus TX-100 (0, 66 M)/cyclohexane and TX-100 (5% g/g)/water, accounting simultaneously for the micropolarity of the oxyethylenic chains and of the hydrophilic and hydrophobic parts of micellar systems. For all compounds, the localization at the interface between the polyethylene oxide chains and the tert-octyl-phenyl etheric residue of the Triton X-100 molecules was considered most probable. The steady-state fluorescence emission studies confirm the results obtained by UV-Vis absorption in what concerns the small differences between the maximum emission peak in correlation to the chemical structure of the porphyrin and in the lack of correlation between the position of the bands and the solvent polarity as defined by Reichard. All these findings suggest that the photophysical properties of the compounds will not be dramatically changed if the compounds are embedded in liposomes to obtain a better delivery to the cellular target.

Acknowledgments

This research was supported by CNMP project No. 41–047/2007 and ERA NET project No. 7–030/2010 the Romanian Ministry of Education and Research

References

  1. Santiago, PS; Netoa, DS; Gandini, SCM; Tabak, M. On the localization of water-soluble porphyrins in micellar systems evaluated by static and time-resolved frequency-domain fluorescence techniques. Colloid Surface B 2008, 65, 247–256. [Google Scholar]
  2. Gandini, SCM; Yushmanov, VE; Tabak, M. Interaction of Fe(III)- and Zn(II)-tetra(4-sulfonatophenyl) porphyrins with ionic and nonionic surfactants: Aggregation and binding. J Inorg Biochem 2001, 85, 263–277. [Google Scholar]
  3. Scolaro, LM; Donato, C; Castriciano, M; Romeo, A; Romeo, R. Micellar aggregates of platinum(II) complexes containing porphyrins. Inorg Chim Acta 2000, 300, 978–986. [Google Scholar]
  4. Berg, K; Selbo, PK; Weyergang, A; Dietze, A; Prasmickaite, L; Bonsted, A. Porphyrin related photosensitizers for cancer imaging and therapeutic. J Microsc 2005, 218, 133–147. [Google Scholar]
  5. Chatterjee, DK; Yong, Z. Nanoparticles in photodynamic therapy: An emerging paradigm. Adv Drug Deliv Rev 2008, 60, 1627–1637. [Google Scholar]
  6. Bonneau, S; Bizet, CV; Mojzisova, H; Brault, D. Tetrapyrrole-photosensitizers vectorization and plasma LDL: A physic-chemical approach. Int J Pharm 2007, 344, 78–87. [Google Scholar]
  7. Boyle, RW; Dolphin, D. Structure and biodistribution relationships of photodynamic sensitizers. Photochem Photobiol 1996, 64, 469–485. [Google Scholar]
  8. Weitemeyer, A; Kliesch, H; Michelsen, U; Hirth, A; Wöhrle, D. Unsymmetrically Substituted Porphyrazines. In Photodynamic Tumor Therapy: Second and Third Generation Photosensitizers; Moser, JG, Ed.; Harwood: New Delhi, India, 1998; pp. 87–99. [Google Scholar]
  9. Sandberg, S; Romslo, I. Porphyrin-induced photodamage at the cellular and the subcellular level as related to the solubility of the porphyrin. Clin Chim Acta 1981, 109, 193–201. [Google Scholar]
  10. Ricchelli, F. Photophysical properties of porphyrins in biological membranes. J Photochem Photobiol B 1995, 29, 109–118. [Google Scholar]
  11. Gandini, SCM; Yushmanov, VE; Borissevitch, IE; Tabak, M. Interaction of the tetra (4-sulfonatophenyl)porphyrin with ionic surfactants: Aggregation and location in micelles. Langmuir 1999, 15, 6233–6243. [Google Scholar]
  12. Correa, NM; Durantini, EN; Silber, JJ. substituent effects on binding constants of carotenoids to n-heptane/AOT reverse micelles. J Colloid Interface Sci 2001, 240, 573–580. [Google Scholar]
  13. Suchetti, CA; Durantini, EN. Monomerization and photodynamic activity of Zn(II) tetraalkyltetrapyridinoporphyrazinium derivatives in AOT reverse micelles. Dye Pigment 2007, 74, 630–635. [Google Scholar]
  14. Correa, NM; Durantini, EN; Silber, JJ. Binding of nitrodiphenylamines to reverse micelles of AOT in n-hexane and carbon tetrachloride: Solvent and substituent effects. J Colloid Interface Sci 1998, 208, 96–103. [Google Scholar]
  15. Battah, S; O’Neill, S; Edwards, C; Balaratnam, S; Dobbin, P; MacRobert, AJ. Enhanced porphyrin accumulation using dendritic derivatives of 5-aminolaevulinic acid for photodynamic therapy: An in vitro study. Int J Biochem Cell Biol 2006, 38, 1382–1392. [Google Scholar]
  16. Medhage, B; Almgren, M. Diffusion-influenced fluorescence quenching dynamics in one to three dimensions. J Fluoresc 1992, 2, 7–21. [Google Scholar]
  17. Barghouthi, SA; Perrault, J; Holmes, LH. Effect of solvents on the fluorescence emission spectra of 1-anilino-8-naphthalene sulfonic acid: A physical chemistry experiment. Chem Educ 1998, 3, 1–5. [Google Scholar]
  18. Shen, D; Zhang, R; Han, B; Dong, Y; Wu, W; Zhang, J; Li, J; Jiang, T; Liu, Z. Enhancement of the solubilization capacity of water in triton X-100/cyclohexane/water system by compressed gases. Chemistry 2004, 10, 5123–5128. [Google Scholar]
  19. Medhage, B; Almgren, M; Alsins, J. Phase structure of poly(oxyethylene) surfactants in water studied by fluorescence quenching. J Phys Chem 1993, 97, 7753–7762. [Google Scholar]
  20. Zhu, DM; Wu, X; Schelly, ZA. Reverse micelles and water in oil microemulsions of Triton X 100 in mixed solvents of benzene and n-hexane. Dynamic light scattering and turbidity studies. Langmuir 1992, 8, 1538–1540. [Google Scholar]
  21. Harris, JM; Chess, RB. Effect of pegylation on pharmaceuticals. Nat Rev Drug Discov 2003, 2, 214–221. [Google Scholar]
  22. Boscencu, R. Asymmetrical mesoporphyrinic complexes of Copper (II) and Zinc (II). Microwave-assisted synthesis, spectral and cytotoxicity evaluation. Molecules 2011, 16, 5604–5617. [Google Scholar]
  23. Boscencu, R; Socoteanu, R; Oliveira, AS; Vieira Ferreira, LF; Nacea, V; Patrinoiu, G. Synthesis and characterization of some unsymmetrically-substituted mesoporphyrinic monohydroxyphenyl complexes of Copper(II). Pol J Chem 2008, 82, 509–522. [Google Scholar]
  24. Boscencu, R; Socoteanu, R; Oliveira, AS; Ferreira, LFV. Studies on Zn(II) monohydroxyphenyl mesoporphyrinic complexes. Synthesis and characterization. J Serb Chem Soc 2008, 73, 713–726. [Google Scholar]
  25. Mack, J; Stilman, MJ. Electronic Structure of Metal Phtalocyanine and Porphyrin Complexes from Analysys of UV-Visible Absorption and Magnetic Circular Dichroism Spectra and Molecular Orbital Calculations. In The Porphyrin Handbook; Kadish, KM, Smith, KM, Guilard, R, Eds.; Academic Press: San Diego, CA, USA, 2003; Volume 16, pp. 43–52. [Google Scholar]
  26. Gouterman, M. Optical Spectra and Electronic Structure of Porphyrins and Related Rings. In The Porphyrins; Dolphin, D, Ed.; Academic Press: New York, NY, USA, 1978; Volume III, pp. 1–165. [Google Scholar]
  27. Boscencu, R; Ilie, M; Socoteanu, R; Oliveira, AS; Constantin, C; Neagu, M; Manda, G; Vieira Ferreira, LF. Microwave synthesis, basic spectral and biological evaluation of some Copper (II) mesoporphyrinic complexes. Molecules 2010, 15, 3731–3743. [Google Scholar]
  28. Gouterman, M; Wagniere, GH; Snyder, LC. Spectra of porphyrins: Part II. Four orbital model. J Mol Spectrosc 1963, 11, 108–127. [Google Scholar]
  29. Harriman, A. Luminescence of porphyrins and metalloporphyrins. J Chem Soc Faraday Trans 1981, 77, 369–377. [Google Scholar]
  30. Quimby, DJ; Longo, FR. Luminiscence studies on several tetraarylporphins and their Zinc derivatives. J Am Chem Soc 1975, 97, 5111–5117. [Google Scholar]
  31. Reichard, C; Welton, T. Solvents and Solvent Effects in Organic Chemistry, 4th ed; Wiley-VCH: Hoboken, NJ, USA, 2010. [Google Scholar]
  32. Boscencu, R; Socoteanu, R; Ilie, M; Bandula, R; Sousa, OA; Vieira Ferreira, LF. Spectral propreties of Copper (II) and Zinc(II) complexes with mesoporphyrinic ligands in micellar media. Rev Chim 2010, 61, 135–139. [Google Scholar]
  33. Caragheorgheopol, A; Bandula, R; Caldararu, H; Joela, H. Polarity profiles in reverse micelles of Triton X-100, as studied by spin probe and absorption probe techniques. J Mol Liq 1997, 72, 105–119. [Google Scholar]
Figure 1. General scheme of the porphyrinoid systems studied.
Figure 1. General scheme of the porphyrinoid systems studied.
Ijms 12 05552f1
Figure 2. General structures of the unsymmetrical mesoporphyrinic complexes used in this study.
Figure 2. General structures of the unsymmetrical mesoporphyrinic complexes used in this study.
Ijms 12 05552f2
Figure 3. Absorption spectra of 2.5 × 106 M Cu(II)TPPOHm in different solvents and micellar solutions: (a) Soret band; and (b) Q band.
Figure 3. Absorption spectra of 2.5 × 106 M Cu(II)TPPOHm in different solvents and micellar solutions: (a) Soret band; and (b) Q band.
Ijms 12 05552f3
Figure 4. Fluorescence emission of 5-(4-hydroxyphenyl)-10,15,20-tris-phenyl-21, 23-Zn(II)-porphine in different solvents and micellar solutions (c = 2.5 × 10−6 M, λex = 420 nm).
Figure 4. Fluorescence emission of 5-(4-hydroxyphenyl)-10,15,20-tris-phenyl-21, 23-Zn(II)-porphine in different solvents and micellar solutions (c = 2.5 × 10−6 M, λex = 420 nm).
Ijms 12 05552f4
Table 1. Wavelengths maxima (λmax) and molar extinction coefficient values (lg ɛ) for the zinc porphyrinic complexes in different solvents and micellar media (c = 2.5 × 10−6 M).
Table 1. Wavelengths maxima (λmax) and molar extinction coefficient values (lg ɛ) for the zinc porphyrinic complexes in different solvents and micellar media (c = 2.5 × 10−6 M).
Solventλmax (nm) [lg ɛ (L mol−1 cm−1)]
Soret B (0,0)Q (1,0)Q (0,0)

5-(2-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-Zn(II)-porphine
MeOH421 [5.726]556 [4.342]595 [4.033]
DMSO428 [5.695]560 [4.326]560 [4.121]
Chx425 [5.570]557 [4.191]597 [3.741]
PEG300426 [5.659]558 [4.310]597 [4.000]
TX/water427 [5.674]559 [4.357]598 [4.342]
TX/Chx427 [5.674]559 [4.356]598 [4.334]

5-(3-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-Zn(II)-porphine
MeOH421 [5.867]556 [4.394]595 [3.982]
DMSO428 [5.867]559 [4.408]600 [4.146]
Chx425 [5.778]557 [4.254]596 [3.702]
PEG300426 [5.820]558 [4.358]598 [4.000]
TX/water426 [5.817]559 [4.471]599 [4.342]
TX/Chx427 [5.991]558 [4.408]598 [4.017]

5-(4-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-Zn(II)-porphine
MeOH422 [5.718]557 [4.246]596 [3.924]
DMSO429 [5.702]561 [4.246]602 [4.017]
Chx425 [5.729]558 [4.292]598 [3.903]
PEG300427 [5.713]559 [4.350]599 [4.121]
TX/water428 [5.709]560 [4.255]601 [3.982]
TX/Chx427 [5.713]560 [4.265]600 [3.964]

5-[(3,4-methylendioxy)phenyl]-10,15,20-tris-(4-carboxymethylphenyl)-21,23-Zn(II)-porphine
MeOH424 [5.686]557 [4.255]598 [3.880]
DMSO431 [5.632]562 [4.246]603 [3.964]
Chx425 [5.554]558 [4.218]599 [3.941]
PEG300427 [5.577]559 [4.221]599 [3.940]
TX/water428 [5.584]559 [4.224]602 [3.962]
TX/Chx427 [5.579]559 [4.226]602 [3.963]

5-(4-hydroxyphenyl)-10,15,20-tris-(4-carboxymethylphenyl)-21,23-Zn(II)-porphine
MeOH1425 [5.732]558 [4.342]599 [4.049]
DMSO1431 [5.800]563 [4.246]604 [4.028]
Chx427 [5.571]561 [4.255]601 [3.826]
PEG300426 [5.640]558 [4.272]599 [3.956]
TX/water427 [5.570]559 [4.232]600 [3.980]
TX/Chx426 [5.616]558 [4.265]598 [3.856]
MeOH = methanol; DMSO = dimethylsulfoxide; Chx = cyclohexane; PEG300 = polyethylenegliycol 300; TX = Triton X-100;
1Data were taken from [22].
Table 2. Wavelengths maxima (λmax) and molar extinction coefficient values (lg ɛ) for the copper porphyrinic complexes in different solvents and micellar media (c = 2.5 × 10−6 M).
Table 2. Wavelengths maxima (λmax) and molar extinction coefficient values (lg ɛ) for the copper porphyrinic complexes in different solvents and micellar media (c = 2.5 × 10−6 M).
Solventλmax (nm) [lg ɛ (L mol−1 cm−1)]
Soret B (0,0)Q (1,0)

5-(2-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-Cu(II)-porphine
MeOH411 [5.820]537 [4.447]
DMSO417 [5.769]540 [4.505]
Chx413 [5.843]538 [4.447]
PEG300416 [5.763]539 [4.380]
TX/water415 [5.838]538 [4.505]
TX/Chx416 [5.867]539 [4.447]

5-(3-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-Cu(II)-porphine
MeOH411 [5.780]536 [4.422]
DMSO418 [5.757]542 [4.422]
Chx414 [5.782]538 [4.350]
PEG300416 [5.763]538 [4.350]
TX/water416 [5.784]539 [4.441]
TX/Chx415 [5.766]538 [4.415]

5-(4-hydroxyphenyl)-10,15,20- tris-phenyl - 21,23-Cu(II)-porphine
MeOH412 [5.701]538 [4.422]
DMSO420 [5.695]542 [4.428]
Chx414 [5.678]539 [4.394]
PEG300417 [5.684]540 [4.326]
TX/water416 [5.691]539 [4.441]
TX/Chx417 [5.701]539 [4.537]

5-[(3,4-methylendioxy)phenyl]-10,15,20-tris-(4-carboxymethylphenyl)-21,23-Cu(II)-porphine
MeOH414 [5.741]538 [4.394]
DMSO422 [5.652]544 [4.408]
Chx416 [5.770]540 [4.371]
PEG300417 [5.782]540 [4.803]
TX/water418 [5.792]539 [4.800]
TX/Chx418 [5.788]540 [4.807]

5-(4-hydroxyphenyl)-10,15,20-tris-(4-carboxymethylphenyl)-21,23-Cu(II)-porphine
MeOH 1414 [5.532]539 [4.260]
DMSO 1423 [5.507]545 [4.203]
Chx419 [5.661]540 [4.283]
PEG300416 [5.782]539 [4.150]
TX/water416 [5.507]539 [4.440]
TX/Chx416 [5.766]539 [4.415]
MeOH = methanol; DMSO = dimethylsulfoxide; Chx = cyclohexane; PEG300 = polyethylenegliycol 300; TX = Triton X-100;
1Data were taken from [22].
Table 3. Fluorescence emission peak wavelength of the zinc mesoporphyrinic complexes in solvents with different polarities and micellar media (c = 2.5 × 10−6 M, λex = 420 nm).
Table 3. Fluorescence emission peak wavelength of the zinc mesoporphyrinic complexes in solvents with different polarities and micellar media (c = 2.5 × 10−6 M, λex = 420 nm).
Solventλmax (nm)
5-(2-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-Zn(II)-porphine
MeOH600651
DMSO605654
Chx602651
PEG300602651
TX/water603652
TX/Chx602651
5-(3-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-Zn(II)-porphine
MeOH600650
DMSO605656
Chx605656
PEG300602652
TX/water603652
TX/Chx603651
5-(4-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-Zn(II)-porphine
MeOH602651
DMSO608655
Chx602652
PEG300605653
TX/water605653
TX/Chx605651
5-[(3,4-methylendioxy)phenyl]-10,15,20-tris-(4-carboxymethylphenyl)-21,23-Zn(II)-porphine
MeOH605652
DMSO610658
Chx604650
PEG300605662
TX/water606665
TX/Chx605665
5-(4-hydroxyphenyl)-10,15,20-tris-(4-carboxymethylphenyl)-21,23-Zn(II)-porphine
MeOH1605652
DMSO1611656
Chx604652
PEG300605663
TX/water606665
TX/Chx606665
MeOH = methanol, DMSO = dimethylsulfoxide, Chx = cyclohexane, PEG300 = polyethylene glycol 300, TX = Triton X-100;
1Data were taken from [22].
Table 4. Stokes shifts (λem – λabs) for the Zn(II) complexes [nm].
Table 4. Stokes shifts (λem – λabs) for the Zn(II) complexes [nm].
Porphyrinic complexesλem – λabs [nm]
MeOHDMSOChxPEG300TX-100/wTX-100/Chx
Zn(II)TPPOHo179177177177176175
Zn(II)TPPOHm179177176176177176
Zn(II)TPPOHp180179177178177178
Zn(II)TRMOPP181179179178178178
Zn(II)TCMPOHp180180177179179180

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Boscencu, R.; Ilie, M.; Socoteanu, R. Spectroscopic Behavior of Some A3B Type Tetrapyrrolic Complexes in Several Organic Solvents and Micellar Media. Int. J. Mol. Sci. 2011, 12, 5552-5564. https://doi.org/10.3390/ijms12095552

AMA Style

Boscencu R, Ilie M, Socoteanu R. Spectroscopic Behavior of Some A3B Type Tetrapyrrolic Complexes in Several Organic Solvents and Micellar Media. International Journal of Molecular Sciences. 2011; 12(9):5552-5564. https://doi.org/10.3390/ijms12095552

Chicago/Turabian Style

Boscencu, Rica, Mihaela Ilie, and Radu Socoteanu. 2011. "Spectroscopic Behavior of Some A3B Type Tetrapyrrolic Complexes in Several Organic Solvents and Micellar Media" International Journal of Molecular Sciences 12, no. 9: 5552-5564. https://doi.org/10.3390/ijms12095552

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