Photosensitization Ability of a Water Soluble Zinc(II)tetramethyltetrapyridinoporphyrazinium Salt in Aqueous Solution and Biomimetic Reverse Micelles Medium

TOMAS C. TEMPESTI; JUAN C. STOCKERT; EDGARDO N. DURANTINI

The Journal of Physical Chemistry B

American Chemical Society

Lugar: Washington, DC 200361, 155 Sixteenth Street N.W.; Año: 2008 vol. 112 p. 15701 - 15707

The spectroscopic properties and the photodynamic activity of a highly water soluble zinc(II)tetramethyltetrapyridino[2,3-b:2¡Ç,3¡Ç-g:2¡Ç¡Ç,3¡Ç¡Ç-l:2¡Ç¡Ç¡Ç,3¡Ç¡Ç¡Ç-q]porphyrazinium salt (ZnTM2,3PyPz) were investigated in aqueous homogeneous solution and in biomimetic reverse micelles medium bearing photooxidizable biological substrates. Absorption and fluorescence spectroscopic studies indicate that ZnTM2,3PyPz is dissolved as monomer in water and in n-heptane/sodium bis(2-ethylhexyl)sulfosuccinate (AOT, 0.1 M)/water (W0 = 30) micellar system. Fluorescence quantum yields (¥ÕF) of 0.29 and 0.27 were calculated for ZnTM2,3PyPz in water and in AOT micelles, respectively. Spectroscopic analysis at different AOT concentrations showed interaction between ZnTM2,3PyPz and AOT reverse micelles with a binding constant (Kb) of 1.7 ¡¿ 103 M−1. The photosensitization ability of ZnTM2,3PyPz was evaluated using 9,10-dimethylanthracene (DMA). Singlet molecular oxygen, O2(1¥Äg), production yielded values of ¥Õ¥Ä = 0.65 for ZnTM2,3PyPz in AOT micelles. Also, ZnTM2,3PyPz induced efficiently the decomposition of the amino acid l-tryptophan (Trp) and the nucleotide guanosine 5¡Ç-monophosphate (GMP) in both media. A value of ¡­3.6 ¡¿ 107 s−1 M−1 was found for the second order rate constant of Trp (krTrp) decomposition in the AOT system, which is near to that found in pure water. Moreover, ZnTM2,3PyPz formed stable complexes with GMP with a binding constant of KGMP = 1.0 ¡¿ 103 M−1. 1H NMR studies indicated that ZnTM2,3PyPz interacts mainly with the guanine moiety more than the sugar part of GMP. On the other hand, the photodynamic activity of ZnTM2,3PyPz produced decomposition of GMP. Quantification of GMP by HPLC indicates that the nucleotide is photooxidized with a kobsGMP = 2.6 ¡¿ 10−4 s−1 in water. Photooxidation of GMP considerably increases in deuteriated water indicating that ZnTM2,3PyPz appears to perform its photosensitizing action via the intermediacy of O2(1¥Äg). Also, efficient sensitized decomposition was observed in micellar media resembling that in pure water. These results provide a better understanding of the effective photodynamic action produced by ZnTM2,3PyPz like a potential phototherapeutic agent for the treatment of neoplastic diseases by photodynamic therapy.