Abstract
The protonation constants of 5,10,15,20-tetrakis(4-trimethyl-ammonio-phenyl)-porphine tetratosylate (TTMAPP) were determined in water–methanol mixed solvents, using a combination of spectrophotometric and potentiometric methods at 25 °C in 0.1 mol·dm−3 sodium perchlorate. Two protonation constants, K 1 and K 2, were characterized and analyzed in various media in terms of the normalized polarity parameter (\( E_{\text{T}}^{\text{N}} \)). A linear correlation is observed when the experimental log10 K 1 and log10 K 2 values are plotted versus the calculated ones over the range of 40–90 % (v/v) methanol. The self aggregation of TTMAPP was observed from acidic media (pH ≅ 3) to alkaline pH, where it reached its highest intensity, when methanol is lower than 40 % in solution. The formation of aggregate species prevents a quantitative analysis of titration curves and thus, the determination of the protonation constants of TTMAPP. Therefore, to evaluate the protonation constants of TTMAPP in low or zero percent of methanol, the Yasuda–Shedlovsky extrapolation approach has been used.
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Kadish, K., Smith, K.M., Guillard, R.: The Porphyrin Handbook. Academic Press, New York (1999)
Aveline, B., Hasan, T., Redmond, R.: Photophysical and photosensitizing properties of benzoporphyrin derivative monoacid ring A (BPD-MA). Photochem. Photobiol. 59, 328–335 (1994)
Lui, H., Anderson, R.R.: Photodynamic therapy in dermatology: recent developments. Dermatol. Clin. 11, 1–13 (1993)
Mosinger, J., Deumie, M., Lang, K., Kubat, P., Wagnerova, D.M.: Supramolecular sensitizer: complexation of meso-tetrakis(4-sulfonatophenyl)porphyrin with 2-hydroxypropyl-cyclodextrins. J. Photochem. Photobiol. A Chem. 130, 13–20 (2000)
Cunderlikova, B., Gangeskar, L., Moan, J.: Acid–base properties of chlorin e6: relation to cellular uptake. J. Photochem. Photobiol. B Biol. 53, 81–90 (1999)
Tannock, I.F., Rotin, D.: Acid pH in tumors and its potential for therapeutic exploitation. Cancer Res. 49, 4373–4384 (1989)
Brunner, H., Arndt, M.R., Treittinger, B.: Porphyrin platinum conjugates—new aims. Inorg. Chim. Acta 357, 1649–1669 (2004)
Delmarre, D., Hioka, N., Boch, R., Sternberg, E., Dolphin, D.: Aggregation studies of benzoporphyrin derivative. Can. J. Chem. 79, 1068–1074 (2001)
Kano, K., Nakajima, T., Takei, M., Hashimoto, S.: Self aggregation of cationic porphyrin in water. Bull. Chem. Soc. Jpn. 60, 1281–1287 (1987)
Ribo, J.M., Bofill, J.M., Crusats, J., Rubires, R.: Point-dipole approximation of the exciton coupling model versus type of bonding and of excitons in porphyrin supramolecular structures. Chem. Eur. J. 7, 2733–2737 (2001)
Kubat, P., Lang, K., Janda, P., Anzenbacher Jr, P.: Interaction of porphyrins with a dendrimer template: self aggregation controlled by pH. Langmuir 21, 9714–9720 (2005)
Pehrsson, L., Ingman, F., Johansson, A.: Acid–base titration by stepwise additions of equal volumes of titrant with special reference to automatic titration—I. Talanta 23, 769–780 (1976)
Gameiro, P., Reis, S., Lima, J.F.L.C., de Castro, B.: Calibration of pH glass electrodes by direct strong acid/strong base titrations under dilute conditions. Anal. Chim. Acta 405, 167–172 (2000)
Jaime Ferrer, J.S., Couallier, E., Rakib, M., Durand, G.: Electrochemical determination of acidity level and dissociation of formic acid/water mixtures as solvent. Electrochim. Acta 52, 5773–5780 (2007)
Gharib, F., Farajtabar, A., Masteri Farahani, A., Bahmani, F.: Solvent effects on protonation constants of tryptophan in some aqueous aliphatic alcohol solutions. J. Chem. Eng. Data 55, 327–332 (2010)
Andrade, S.M., Teixeira, R., Costa, S.M.B., Sobral, A.J.F.N.: Self aggregation of free base porphyrins in aqueous solution and in DMPC vesicles. Biophys. Chem. 133, 1–10 (2008)
Beck, M.T., Nagypal, I.: Chemistry of Complex Equilibria. Ellis Harwood, New York (1990)
Beltran, J.L., Codony, R., Prat, M.D.: Evaluation of stability constants from multi-wavelength absorbance data: program STAR. Anal. Chim. Acta 276, 441–454 (1993)
Shamim, A., Hambright, P.: An equilibrium and kinetic study of water-soluble cadmium porphyrins. Inorg. Chem. 19, 564–566 (1980)
Turay, J., Hambright, P.: Kinetics of copper incorporation into a meso-substituted trimethylanilinium water soluble porphyrin. Inorg. Chim. Acta 35, L319–L320 (1979)
Krishnamurthy, M.: Synthesis and characterization of a new water-soluble porphyrin. Ind. J. Chem. 15B, 964–966 (1977)
Gensch, T., Viappiani, C., Braslavsky, S.E.: Structural volume changes upon photoexcitation of porphyrins: role of the nitrogen–water interactions. J. Am. Chem. Soc. 121, 10573–10582 (1999)
Mohajer, D., Rayati, S.: Novel 1:2 molecular complexation of free base meso-tetraphenylporphyrins with σ-acceptor trialkylsilyl chlorides. New J. Chem. 27, 242–244 (2003)
Khavasi, H.R., Zahedi, M., Shahbazian, S., Safari, N., Ng, S.W., Mohajer, D.: Prediction of novel complexation of porphine and BF3: is it a 1:1 or 1:2 species? Chem. Phys. 301, 1–7 (2004)
Mohajer, D., Zakavi, S., Rayati, S., Zahedi, M., Safari, N., Khavasi, H.R., Shahbazian, S.: Unique 1:2 adduct formation of meso-tetraarylporphyrins and meso-tetraalkylporphyrins with BF3: a spectroscopic and ab initio study. New J. Chem. 28, 1600–1607 (2004)
Baker, H., Wagner, L., Hambright, P.: Metal ion porphyrin interactions. Evidence for nonexistence of sitting atop complexes in aqueous solution. J. Am. Chem. Soc. 95, 5942–5946 (1973)
Yasuda, M.: Dissociation constants of some carboxylic acids in mixed aqueous solvents. Bull. Chem. Soc. Jpn. 32, 429–432 (1959)
Shedlovsky, T.: The behavior of carboxylic acids in mixed solvents. In: Peasce, B. (ed.) Electrolytes. Pergamon, New York (1962)
Ruiz, R., Rafols, C., Roses, M., Bosch, B.: A potentially simpler approach to measure aqueous pKa of insoluble basic drugs containing amino groups. J. Pharm. Sci. 92, 1473–1481 (2003)
Avdeef, A., Box, K.J., Comer, J.E.A., Gilges, M., Hadley, M., Hibbert, C., Patterson, W., Tam, K.Y.: pH-metric log P 11. pK(a) determination of water-insoluble drugs in organic solvent–water mixtures. J. Pharm. Biomed. Anal. 20, 631–641 (1999)
Puranik, S.M., Kumbharkhane, A.C., Mehrotra, S.C.: The static permittivity of binary mixtures using an improved Bruggeman model. J. Mol. Liq. 59, 173–177 (1994)
Pasternack, R.F., Huber, P.R., Boyd, P., Engasser, G., Francesconi, L., Gibbs, E., Fasella, P., Venturo, G.C., Hinds, L.: On the aggregation of meso-substituted water-soluble porphyrins. J. Am. Chem. Soc. 94, 4511–4517 (1972)
Kano, K., Takei, M., Hashimoto, S.: Cationic porphyrins in water: proton NMR and fluorescence studies on dimer and molecular complex formation. J. Phys. Chem. 94, 2181–2187 (1990)
Pasternack, R.F., Bustmante, C., Collings, P.J., Giannetto, A., Gibbs, E.J.: Porphyrin assemblieson DNA as studied by a resonance light-scattering technique. J. Am. Chem. Soc. 115, 5393–5399 (1993)
Kano, K., Fukuda, K., Wakami, H., Nishiyabu, R., Pasternack, R.F.: Factors influencing self aggregation tendencies of cationic porphyrins in aqueous solution. J. Am. Chem. Soc. 122, 7494–7502 (2000)
Kamlet, M.J., Abboud, J.L.M., Abraham, M.H., Taft, R.W.: Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters, π*, α, and β, and some methods for simplifying the generalized solvatochromic equation. J. Org. Chem. 48, 2877–2887 (1983)
Blokzijl, W., Engberts, B.F.N.: Opinions and facts. Angew. Chem. Int. Edn. Engl. 32, 1545–1579 (1993)
Gharib, F., Zare, K., Mohammadi, B.: Solvent effects on complexation of molybdenum(VI) with nitrilotriacetic acid in different aqueous solutions of methanol. J. Mol. Liq. 124, 63–67 (2006)
Reichardt, C.: Solvents and Solvent Effects in Organic Chemistry, 3rd edn. VCH, New York (2004)
Maleki, N., Haghighi, B., Safavi, A.: Evaluation of formation constants, molar absorptivities of metal complexes and protonation constants of acids by nonlinear curve fitting using Microsoft Excel Solver. Microchem. J. 62, 229–236 (1999)
Marcus, Y.: The use of chemical probes for the characterization of solvent mixtures. Part 2. Aqueous mixtures. J. Chem. Soc. Perkin Trans. 2, 1751–1758 (1994)
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Jaberi, F., Gharib, F. & Farajtabar, A. Solute–Solvent Interaction Effects on Protonation and Aggregation Constants of TTMAPP in Different Aqueous Solutions of Methanol. J Solution Chem 42, 1559–1571 (2013). https://doi.org/10.1007/s10953-013-0057-z
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DOI: https://doi.org/10.1007/s10953-013-0057-z