Computational exploration of the photoprotective potential of gadusol.

Gadusol shows one of the simplest structures among a series of natural UV-absorbing compounds that have been related to the photoprotective and antioxidant functions in aquatic organisms. CASPT2//CASSCF methodology was used to carry out a theoretical study on this basic structure in order to describe the underlying features responsible for the photoprotective capacity of the molecule. The influence of the enol-enolate equilibrium on the photophysical properties was explored. The results confirm that both forms undergo a rapid deactivation, which very efficiently dissipates light energy as heat. This work highlights the potential of molecular-level studies to provide an understanding of natural photoprotective mechanisms and gives support to the future design of structurally related new synthetic sunscreens.

Influence of mycosporine-like amino acids and gadusol on the rheology and Raman spectroscopy of polymer gels.

BACKGROUND: The amphiphilic nature of polymers allows them to be widely incorporated as carriers in different pharmaceutical applications since they are able to work as vehicles for hydro- or lipo-soluble actives. OBJECTIVE: The aim of this study was to determine the rheological behavior and vibrational spectral variations of two hydrophilic gels prepared with Poloxamer 407 (PO) or Pluronic F-127 (PL) with the addition of the actives mycosporine-like amino acids and gadusol. METHODS: The structures of these polymers in two different concentrations (20% w/w and 27% w/w) were characterized by rheological studies and Raman spectroscopy. RESULTS: Gels prepared with higher polymer concentration showed larger G' (storage modulus) values. The C-C stretch and the CH2 rocking predominated in the gels containing PL (20% w/w) and this correlated with a less viscous behavior. The mixture of the actives induced higher contributions of Raman peaks related to trans conformation of the C-C bonds located in hydrophilic polymer blocks, whereas the same peaks decreased in the sample containing only gadusol. CONCLUSIONS: Larger tensile strength and elastic component were observed upon increasing polymer concentration, thus evidencing polymer-polymer and/or polymer-polymer-actives interactions. The presence of the actives affected the mechanical properties of the polymer gels. Gadusol particularly seems to alter the conformation of the polymer chains by favoring gauche orientations, in parallel with rising viscoelastic parameters. More stretched arrangements of the polymer are probably induced in the presence of larger concentration of actives, due to specific interactions with their hydrophilic groups.

The deactivation pathways of the excited-states of the mycosporine-like amino acids shinorine and porphyra-334 in aqueous solution.

In vitro studies on the structurally related mycosporine-like amino acids (MAAs) porphyra-334 and shinorine in aqueous solutions were carried out aiming at their full photochemical and photophysical characterization and expanding the evidence on the assigned UV-photoprotective role of the molecules in vivo. The experiments on shinorine confirmed a high photostability and a poor fluorescence quantum yield, in concordance with previous results on porphyra-334. The estimation of triplet production quantum yields for both MAAs was achieved by laser-flash photolysis measurements. In particular, photosensitization experiments on porphyra-334 support the participation of the triplet state in the photodecomposition mechanism yielding a more precise value of [capital Phi](T). As well, photoacoustic calorimetry experiments allowed the first direct quantification of the nonradiative relaxation pathways of the excited MAAs in solution, corroborating that the vast majority (ca. 97%) of the absorbed energy is promptly delivered to the surroundings as heat, consistently with the low photodecomposition and emission yields observed.

In vitro cis-trans photoisomerization of palythene and usujirene. Implications on the in vivo transformation of mycosporine-like amino acids.

The in vitro photoinduced reactions of the mycosporine-like amino acids (MAA) usujirene and palythene were studied by monochromatic stationary irradiation at 366 nm. High-performance liquid chromatography analysis of the irradiated aqueous solution of usujirene indicated a low photoreactivity on the basis of the observed photodecomposition quantum yield of phi(-U) = (2.86 +/- 0.80) x 10(-5), which can be partially accounted for by the cis-trans photoisomerization of usujirene to palythene (phi(U-->P) = [1.71 +/- 0.13] x 10(-5)). However, palythene in aqueous solution showed a higher photostability than did usujirene under equivalent conditions, establishing a photostationary mixture of cis-trans isomers with a relative composition of palythene-usujirene (11:1). These results may explain the preferential in vivo accumulation of palythene relative to that of usujirene observed in several dinoflagellate species.