Lelia E. Dicelio

N-Acetylcysteine Reduces Markers of Differentiation in 3T3-L1 Adipocytes

Oxidative stress plays a critical role in the pathogenesis of diabetes, hypertension and atherosclerosis. Some authors reported that fat accumulation correlates to systemic oxidative stress in humans and mice, but the relationship of lipid production and oxidative metabolism is still unclear. In our laboratory we used 3T3-L1 preadipocytes, which are able to differentiate into mature adipocytes and accumulate lipids, as obesity model. We showed that intracellular reactive oxygen species (ROS) and antioxidant enzymes superoxide dismutase (SOD) and glutathione peroxidase (GPx) activities increased in parallel with fat accumulation. Meanwhile N-acetylcysteine (NAC), a well known antioxidant and Glutathione (GSH) precursor, inhibited ROS levels as well as fat accumulation in a concentration-dependent manner. NAC also inhibited both adipogenic transcription factors CCAAT/enhancer binding protein beta (C/EBP β) and peroxisomal proliferator activated receptor gamma (PPAR γ) expression; we suggested that intracellular GSH content could be responsible for these effects.

About photo-damage of human hair.

This paper reviews the current knowledge about human hair photodamage and the photodegradation mechanisms proposed in the literature. It is shown that there are still a number of questions without answer regarding this issue. For example, a better understanding of the hair structural changes caused by different radiation wavelengths is still lacking. We also find controversies about the effects of sun exposure on different hair types. Explanations to these questions are frequently sustained on the amount and type of melanin of each hair, but factors such as the absence of knowledge of melanin structure and of established methodologies to use in human hair studies make it difficult to reach a general agreement on these issues.

Synthesis and photophysical properties of a new cationic water-soluble Zn phthalocyanine

The synthesis of tetrakis (1,1-dimethyl-2-trimethylammonium)ethylphthalocyaninato Zn(II) tetraiodide 2--a new cationic phthalocyanine--is reported as well as its photophysical properties in water, relevant for the use of this dye as photodynamic sensitizer. The hydrophobicity of the macrocycle leads to strong aggregation which lowers the fluorescence and singlet oxygen quantum yields of aqueous solutions of 2. Photophysical parameters agree with those of other Zn phthalocyanines when correction is performed for the fraction of light absorbed by the monomer.

Modeling of fluorescence quantum yields of supported dyes

Aggregation equilibrium and the fluorescence properties of hydroxoaluminium tricarboxymonoamidephthalocyanine adsorbed on microgranular cellulose have been studied at different dye loadings. Up to a concentration of nearly 3 × 10−6 mol phthalocyanine (g cellulose)−1 diffuse reflectance spectra may be interpreted on the basis of a simple monomer–dimer equilibrium. Monomer and dimer spectra are similar to the spectra of the monomeric dye in solution. The solid-state dimer spectrum is red-shifted with respect to that of the monomer and this is attributed to the coplanarity of dimers. Fluorescence spectra and quantum yields show typical effects of re-absorption and re-emission of light. In particular, the observed fluorescence quantum yields depend on concentration and span the range 0.29–0.07. To account for these effects as well as the effect of aggregation on fluorescence quantum yields and to obtain corrected fluorescence spectra a model based on the Kubelka–Munk theory of diffuse reflectance is developed. The application of this model to the case under study yields a true fluorescence quantum yield ϕ = 0.46 ± 0.02 in the whole range of concentrations, which is slightly higher than the value found for the same dye in dimethyl sulfoxide solution.

Quantum yield of singlet molecular oxygen sensitization by copper(II) tetracarboxyphthalocy anine

Abstract The quantum yield φ Δ for sensitization of singlet molecular oxygen, O 2 ( 1 Δ g ), by copper(II) tetracarboxyphthalocyanine (CuTCPc) in dimethyl sulphoxide was determined under stationary illumination, using diphenyl-isobenzofurane as chemical quencher. A constant value of φ Δ = 0.16 ± 0.03 was obtained, independent of sensitizer concentration in the range 2–26 μM even though dimers and possibly oligomers are present at the highest concentrations. The monomer and the aggregates of CuTCPc physically quench O 2 ( 1 Δ g ) with a nearly diffusional rate constant.

Photodynamic effects of isosteric water-soluble phthalocyanines on human nasopharynx KB carcinoma cells

The photodynamic activity of water-soluble cationic zinc(II) phthalocyanines using human nasopharynx carcinoma (KB cells) was investigated. A sulfur-linked cationic dye, named: 2,9(10),16(17),23(24)-tetrakis[(2-trimethylammonium)ethylsulfanyl]phthalocyaninatozinc(II) tetraioidide (13) is the most active of four sensitizer assays and shows a singlet oxygen quantum yield of 0.58 and a higher bathochromic shift of 10 nm for the Q-band as compared with the oxygen-linked cationic aliphatic phthalocyanine: 2,9(10),16(17),23(24)-tetrakis[(2-trimethylammonium)ethoxy]phthalocyaninatozinc(II) tetraioidide (11) and the best photo-stability in water in comparison with their tetra-alpha-substituted counterparts 1,8(11),15(18),22(25)-tetrakis[(2-trimethylammonium)ethoxy]phthalocyaninatozinc(II) tetraioidide (12) and 1,8(11),15(18),22(25)-tetrakis[(2-trimethylammonium)ethylsulfanyl]phthalocyaninatozinc(II) tetraioidide (14). Phthalocyanine 13, partially localized in lysosomes, led to cell photoinactivation in a concentration- and light dose-dependent manner. After photodynamic treatment, compound 13 induced an apoptotic response--as indicated by morphological cell changes--an increase in the activity of caspase-3 and the cleavage of poly-ADP-ribose-polymerase substrate (PARP).

Visible and near-IR spectroscopic and photochemical characterization of substituted metallophthalocyanines

Abstract The UV—visible spectra of copper(II) tetracarboxyphthalocyanine (CuTCPc), copper(II) tetrapentyloxycarbonyl- phthalocyanine (CuTPOCPc) and hydroxyaluminium tricarboxymonoamidephthalocyanine (AlTCPc) were studied as a function of concentration in various solvents. Dye aggregation equilibria were investigated and pure monomet and dimer spectra were obtained. Near-IR absorption maxima for the above compounds and for cobalt(II) dicarboxydiamidephthalocyanine (Co(II)TCPc) and dicyanocobalt(III) dicarboxydiamidephthalocyanine (Co(III)TCPc) were also obtained and their assignment to triplet—multiplet transitions is discussed. The analysis of the monomer and dimer spectra on the basis of exciton theory and results obtained from molecular mechanics computational calculations allows conclusions to be drawn on the monomer and dimer structures and observed differences in aggregation ability to be interpreted. Quantum yields of singlet molecular oxygen photoproduction by monomers and dimers were determined for aluminium and copper dyes by steady state irradiation using diphenylisobenzofuran as singlet oxygen quencher. The lack of activity in dimers, in accordance with the literature available, is interpreted in terms of the vibronic coupling between monomeric units in the dimer (exciton theory).

A comparative study of the photophysical and phototoxic properties of octakis(decyloxy)phthalocyaninato zinc(II), incorporated in a hydrophilic polymer, in liposomes and in non-ionic micelles

Factors such as charge, aggregation and lipophilicity influence photosensitiser localisation. The lipophilic octasubstituted sensitiser 2,3,9,10,16,17,23,24-octakis(decyloxy)phthalocyaninato zinc(II) was incorporated into liposomes of dimyristoyl-L-alpha-phosphatidylcholine (DMPC), non-ionic micelles of Tween 80 and the hydrosoluble polymer Solutol HS 15 in order to investigate how these different environments affect the photophysical properties and phototoxicity of the photosensitiser. Fluorescence quantum yields and singlet molecular oxygen generation are enhanced in the presence of Solutol HS 15. Phototoxicities were calculated by employing a concentration of 10(-7) M of the dye against the Hep-2 cell line, which showed a viability of 53 and 30% in DMPC and Solutol HS 15, respectively. After 24 h of photodynamic therapy with 15 min irradiation, apoptotic and necrotic cells were observed.

Dye-polyelectrolyte layer-by-layer self-assembled materials: molecular aggregation, structural stability, and singlet oxygen photogeneration.

The interaction of rose Bengal (RB) and fluorescein (FL) with poly[diallyldimethylammonium] chloride (PDDA) was studied in layer-by-layer self-assembled thin films and in solution. The spectroscopic behavior is explained in terms of dye-dye, dye-polyelectrolyte, and in solution, dye-solvent interactions. A correlation among dye hydrophobicity, aggregation tendency, polymer folding in solution, and the stability of self-assembled films is obtained. In spite of the very high dye concentration (approximately 1 M), RB-PDDA multilayer thin films are able to photogenerate singlet molecular oxygen, as demonstrated by chemical monitoring and IR phosphorescence detection.

Meso-substituted cationic porphyrins of biological interest. Photophysical and physicochemical properties in solution and bound to liposomes.

Abstract A series of cationic porphyrins with 1–4 positive charges are studied: mono(N-methyl-4-pyridyl)triphenylporphine chloride [Mono], cis(N-methyl-4-pyridyl)diphenylporphine chloride [Cis], tri(N-methyl-4-pyridyl)monophenylporphine chloride [Tri] and tetra(N-methyl-4-pyridyl)porphine chloride [Tetra]. Their photophysical properties are measured in small unilamellar vesicles and compared with those in homogeneous solution. Liposomes of l-α-dimyristoyl-phosphatidylcholine (100 nm diameter) and l-α-dipalmitoyl-phosphatidylcholine (50 nm diameter) in phosphate-buffered saline (pH = 7.4) or D2O 0.15 M NaCl were used. The effect of the medium microheterogeinity is discussed. The triplet quantum yields in liposomes for all the porphyrins are about 0.7, similar to the value obtained for Tetra in aqueous media. The singlet molecular oxygen quantum yields for the hydrophilic compounds Tri and Tetra are greater than those of the hydrophobic ones, Mono and Cis. Also, association constants (KL) of the dyes to liposomes and their localization within the membranes are determined from fluorescence and fluorescence polarization measurements, respectively. KL values are in the range of 104–105 M−1 for all the compounds, indicating that hydrophobic and coulombic interactions between porphyrins and liposomes are responsible for the dye association. Fluorescence polarization experiments indicate that Mono and Cis can penetrate into the lipidic phase, and that Tri and Tetra are located near the polar heads of the lipidic molecules.