Confocal Raman spectroscopy: In vivo biochemical changes in the human skin by topical formulations under UV radiation.

A new approach to the study of the effects on human skin of mycosporine-like amino acids (MAAs) and gadusol (Gad) incorporated in polymer gel is proposed in this work. The depth profile and photoprotector effects of Pluronic F127® gels containing each of the natural actives were evaluated by in vivo confocal Raman spectroscopy aiming at the analysis of the biochemical changes on human skin. Hierarchical cluster analysis (HCA) showed that the data corresponding to different depths of the skin, from surface to 4 µm, and from 6 to 16 µm, remained in the same cluster. In vivo Raman spectra, classified into five different layers of epidermis according to their similarities, indicated that the amount of Gad gel increased by about 26% in the outermost layer of the stratum corneum (SC) and that MAAs gel at 2 µm depth was 103.4% higher than in the outermost layer of the SC. Variations in the SC of urocanic acid at 1490-1515 cm(-1) and 1652 cm(-1) and histidine at 1318 cm(-1) were calculated, before and after UV exposure with or without gels. With the application of gels the vibrational modes that correspond to lipids in trans conformation (1063 and 1128 cm(-1)) increased with respect to normal skin, whereas gauche conformation (1085 cm(-1)) disappeared. Our studies suggest that gels protected the skin against the stress of the natural defense mechanism caused by high levels of UV exposure.

Interaction of cationic phthalocyanines with DNA. Importance of the structure of the substituents.

The interaction of novel zinc (II) cationic phthalocyanines with CT-DNA was studied using absorption and fluorescence spectroscopy, as well as thermal denaturation profiles. Results showed an electrostatic interaction between the phthalocyanines and CT-DNA. The properties of these phthalocyanines were compared taking the structure of the macrocycle peripheral substituents into account. 2,9(10),16(17),23(24)-tetrakis[(N-butyl-N-methylammonium)ethylsulfanyl]phthalocyaninatozinc(II) tetraiodide (Pc6) had a greater affinity for the CT-DNA helix than its bioisoster 2,9(10),16(17),23(24)-tetrakis[(N-dibutyl-N-methylammonium)ethoxy]phthalocyaninatozinc(II) tetraiodide (Pc7). 2,9(10),16(17),23(24)-tetrakis[(2-trimethylammonium)ethyl-sulfanyl]phthalocyaninatozinc(II) tetraiodide (Pc13) also carried a sulfur atom like Pc6, but linked to bulky substituents such as trimethylammonium groups. The planar aromatic region of the cationic phthalocyanines in this study appears to be unable to facilitate their intercalation with CT-DNA.

Photo yellowing of human hair.

In general, human hair is claimed to turn yellower after sun exposure. This is particularly affirmed for white hair. However, quantitative data relating yellowness to hair type and to the radiation wavelength are missing. This work shows results of the effect of full or UVB-filtered radiation of a mercury vapor or a xenon-arc lamp on the yellowness of virgin white, dark-brown, blond and red hair. All hair types showed a substantial change in yellowness after irradiation, which is dependent on the hair type and radiation wavelength. Surprisingly, white hair turns less yellow after both full and UVB-filtered radiation exposure. This effect is more pronounced when UVB is filtered from the radiation system. The only radiation that shows a photo-yellowing effect on white hair is infrared. As the yellowness of white hair is commonly related to tryptophan degradation, fluorescence experiments with hair solutions were performed to identify the natural degradation of tryptophan which occurs in hair after light irradiation. Pigmented hairs were also studied, as well as hair treated with a bleaching solution. Although we observe a decrease in tryptophan content of hair after lamp radiation, a direct correlation with hair yellowness was not achieved. Results are discussed in terms of hair type, composition and melanin content.

Photodynamic ultradeformable liposomes: Design and characterization.

Hydrophobic ([tetrakis(2,4-dimetil-3-pentyloxi)-phthalocyaninate]zinc(II)) (ZnPc) and hydrophilic ([tetrakis(N,N,N-trimethylammoniumetoxi)-phthalocyaninate]zinc(II) tetraiodide) (ZnPcMet) phthalocyanines were synthesized and loaded in ultradeformable liposomes (UDL) of soybean phosphatidylcholine and sodium cholate (6:1, w/w, ratio), resulting 100 nm mean size vesicles of negative Zeta potential, with encapsulation efficiencies of 85 and 53%, enthalpy of phase transition of 5.33 and 158 J/mmol for ZnPc and ZnPcMet, respectively, indicating their deep and moderate partition into UD matrices. Matrix elasticity of UDL-phthalocyanines resulted 28-fold greater than that of non-UDL, leaking only 25% of its inner aqueous content after passage through a nanoporous barrier versus 100% leakage for non-UDL. UDL-ZnPc made ZnPc soluble in aqueous buffer while kept the monomeric state, rendering singlet oxygen quantum yield (Phi(Delta)) similar to that obtained in ethanol (0.61), whereas UDL-ZnPcMet had a four-fold higher Phi(Delta) than that of free ZnPcMet (0.21). Free phthalocyanines were non-toxic at 1 and 10 microM, both in dark or upon irradiation at 15 J/cm2 on Vero and J-774 cells (MTT assay). Only liposomal ZnPc at 10 microM was toxic for J-774 cells under both conditions. Additionally, endo-lysosomal confinement of the HPTS dye was kept after irradiation at 15 J/cm2 in the presence of UDL-phtalocyanines. This could lead to improve effects of singlet oxygen against intra-vesicular pathogen targets inside the endo-lysosomal system.

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.

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

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-alpha-dimyristoyl-phosphatidylcholine (100 nm diameter) and L-alpha-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 10(4)-10(5) 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.

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.