Photodynamic studies of metallo 5,10,15,20-tetrakis(4-methoxyphenyl) porphyrin: photochemical characterization and biological consequences in a human carcinoma cell line.

The photodynamic activities of the free-base 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin (TMP) and their metal complexes with zinc(II) (ZnTMP), copper(II) (CuTMP) and cadmium(II) (CdTMP) have been compared in two systems: reverse micelle of n-heptane/sodium bis(2-ethylhexyl)sulfosuccinate/water bearing photooxidizable substrates and Hep-2 human larynx carcinoma cell line. The quantum yields of singlet molecular oxygen, O2(1 delta g), production (phi delta) of TMP, ZnTMP and CdTMP in tetrahydrofuran, were determined yielding values of 0.65, 0.73 and 0.73, respectively, while O2(1 delta g) formation was not detected for CuTMP. In the reverse micellar system, the amino acid L-tryptophan (Trp) was used as biological substrate to analyze the O2(1 delta g)-mediated photooxidation. The observed rate constants for Trp photooxidation (kobsTrp) were proportional to the sensitizer quantum yield of O2(1 delta g). A value of approximately 2 x 10(7) s-1 M-1 was found for the second-order rate constant of Trp (krTry) in this system. The response of Hep-2 cells to cytotoxicity photoinduced by these agents in a biological medium was studied. The Hep-2 cultures were treated with 1 microM of porphyrin for 24 h at 37 degrees C and the cells exposed to visible light. The cell survival at different light exposure levels was dependent on phi delta. Under these conditions, the cytotoxic effect increases in the order: Cu-TMP << TMP < ZnTMP approximately CdTMP, correlating with the production of O2(1 delta g). A similar behavior was observed in both the chemical and biological media indicating that the O2(1 delta g) mediation appears to be mainly responsible for the cell inactivation.

Exciplex-type behavior and partition of 3-substituted indole derivatives in reverse micelles made with benzylhexadecyldimethylammonium chloride, water and benzene.

The fluorescence properties of 3-methylindole (MI), 3-indoleacetic acid (IAA), 3-indoleethyltrimethylammonium bromide (IETA), L-tryptophan (Trp) and tryptamine hydrochloride (TA) were studied in reverse micelles solutions made with the cationic surfactant benzylhexadecyldimethylammonium chloride (BHDC) in benzene as a function of the molar ratio water/surfactant R (= [H2O]/[BHDC]). The fluorescence quenching of the model compound MI by benzene in cyclohexane solutions and by BHDC in benzene solutions were also studied in detail. The fluorescence of MI in benzene is characteristic of a charge-transfer exciplex. The exciplex is quenched by the presence of BHDC, due to the interactions of the surfactant ion pairs with the polar exciplex. In reverse micelle solutions at low R values, all the indoles show exciplex-type fluorescence. As R increases, the fluorescence behavior strongly depends on the nature of the indole derivative. The anionic IAA remains anchored to the cationic interface and its fluorescence is quenched upon water addition due to the increases of interface's micropolarity. For IETA, TA and Trp an initial fluorescence quenching is observed at increasing R, but a fluorescence recovery is observed at R > 5, indicating a probe partition between the micellar interface and the water pool. For the neutral MI, the fluorescence changes with R indicate the partition of the probe between the micellar interface and the bulk benzene pseudophase. A simple two-site model is proposed for the calculation of the partition constants K as a function of R. In all cases, the calculation showed that even at the highest R value, about 90% of the indole molecules remain associated at the micellar interface.

Photodecarboxylation of ketoprofen in aqueous solution. A time-resolved laser-induced optoacoustic study.

The photodecarboxylation reaction of 2-(3-benzoylphenyl)propionate (ketoprofen anion, KP-) was studied in water and in 0.1 M phosphate buffer solutions in the pH range 5.7-11.0 by laser-induced optoacoustic spectroscopy (LIOAS, T range 9.5-31.6 degrees C). Upon exciting KP- with 355 nm laser pulses under anaerobic conditions, two components in the LIOAS signals with well-separated lifetimes were found (tau 1 < 20 ns; 250 < tau 2 < 500 ns) in the whole pH range, whereas a long-lived third component (4 < tau 3 < 10 microseconds) was only detected at pH < or = 6.1. The heat and structural volume changes accompanying the first step did not depend on pH or on the presence of buffer. The carbanion resulting from prompt decarboxylation within the nanosecond pulse (< 10 ns) drastically reduces its molar volume ([-18.9 +/- 2.0] cm3/mol) with respect to KP- and its enthalpy content is (256 +/- 10) kJ/mol. At acid pH (ca 6), a species is formed with a lifetime in the hundreds of ns. The enthalpy and structural volume change for this species with respect to KP- are (181 +/- 15) kJ/mol and (+0.6 +/- 2.0) cm3/mol, respectively. This species is most likely a neutral biradical formed by protonation of the decarboxylated carbanion, and decays to the final product 3-ethylbenzophenone in several microsecond. At basic pH (ca 11), direct formation of 3-ethylbenzophenone occurs in hundreds of ns involving a reaction with the solvent. The global decarboxylation reaction is endothermic ([45 +/- 15] kJ/mol) and shows an expansion of (+14.5 +/- 0.5) cm3/mol with respect to KP-. At low pH, the presence of buffer strongly affects the magnitude of the structural volume changes associated with intermolecular proton-transfer processes of the long-lived species due to reactions of the buffer anion with the decarboxylated ketoprofen anion.