The influence of pH on charged porphyrins studied by fluorescence and photoacoustic spectroscopy.

We have studied the influence of solvent acidity on the aggregation/protonation behaviour of two charged tetraphenylporphyrins: positively charged tetrakis(N,N,N-trimethylanilinium-4-yl)porphyrin (TAP) and negatively charged tetrakis(4-sulfonatophenyl)porphyrin (TPPS4). Spectroscopic measurements (absorption, fluorescence, excitation and photoacoustic) have been made to follow the radiative and nonradiative relaxation processes of excited dye molecules at various pH values. The ability of these porphyrins to exist in aggregated and protonated forms was also investigated. It has been shown that TPPS4 exists in at least three spectroscopic forms: monomer (M1), dication (D1) and aggregated dication (AD), whereas TAP exists in two forms: monomer (M2) and dication (D2). These forms are characterised by different absorption and fluorescence properties. The short wavelength forms of the dyes (M1 and M2) were assigned to the monomeric forms and D1 and D2 were assigned to the protonated forms of TPPS4 and TAP, respectively; AD was identified as the aggregate of the protonated form of TPPS4. Each form shows deactivation of its excited state by nonradiative pathways-particularly high thermal deactivation was observed for the aggregates of the protonated form. Energy transfer between the monomeric form and the dication form has been demonstrated and Förster radii have been estimated (R0 = 31 and 44 A for TAP and TPPS4, respectively). Since protonation and aggregation of photoreceptors can strongly affect their photosensitizing effects (e.g. cellular uptake, singlet oxygen production) the results presented here may be important in the study of the function of photosensitizers in tumour tissues because, as is already known, the microenvironment in cancerous tissue is more acidic than in healthy cells.