Synthesis, Characterization, and Antiproliferative Properties of New Bio-Inspired Xanthylium Derivatives.

Xanthylium derivatives are curcumin analogs showing photochromic properties. Similarly, to anthocyanins, they follow the same multistate network of chemical species that are reversibly interconverted by external stimuli. In the present work, two new asymmetric monocarbonyl analogues of curcumin, 4-(4-hydroxy-3-metoxybenzylidene)-1,2,3,4-tetrahydroxanthylium chloride (compound 3) and 4-(4-hydroxybenzylidene)-6-methoxy-1,2,3,4-tetrahydroxanthylium chloride (compound 4) were synthesized, and their photochromic and biological properties were investigated. The UV-Vis spectroscopy and the direct and reverse pH-jumps studies confirmed the halochromic properties and the existence of different molecular species. A network of chemical reactions of these species was proposed. Furthermore, the antiproliferative properties of both compounds were evaluated using P19 murine embryocarcinoma cells and compared with each other. The results demonstrate that both new xanthylium derivatives modify the progression through the cell cycle of P19 cells, which translates into a significant antiproliferative effect. The effect of the methoxy group position is discussed and several checkpoint proteins are advanced as putative targets.

Experimental and Computational Studies on Bio-Inspired Flavylium Salts as Sensitizers for Dye-Sensitized Solar Cells.

Six new bio-inspired flavylium salts were synthesized and investigated by a combined computational and experimental study for dye-sensitized solar cell applications. The compounds were characterized by FT-IR, UV-Vis, NMR spectroscopy, and LC-MS spectrometry techniques. The pH-dependent photochromic properties of the flavylium dyes were investigated through a UV-Vis spectroscopy study and revealed that they follow the same network of chemical reactions as anthocyanins upon pH changes. The structural and electronic properties of the dyes were investigated using density functional theory (DFT) and time-dependent density functional theory (TD-DFT). Geometry optimization calculation revealed that all dyes, regardless of the specie, flavylium cations or quinoidal bases, present a planar geometry. The photovoltaic performances of the dyes, in both flavylium and quinoidal base forms, were evaluated by the HOMO and LUMO energies and by calculating the light-harvesting efficiencies, the free energy change of electron injection, and the free energy change regeneration. The MO analysis showed that all dyes can inject electrons into the conduction band of the TiO2 upon excitation and that the redox couple can regenerate the oxidized dyes. The results obtained for the free energy change of electron injection suggest that the quinoidal bases should inject electrons into the semiconductor more efficiently than the flavylium cations. The values for the free energy change regeneration showed that the redox electrolyte can easily regenerate all dyes. Dipole moment analysis was also performed. DSSCs based on the dyes, in both flavylium and quinoidal base forms, were assembled, and their photovoltaic performances were evaluated by measuring the open-circuit voltage, the short circuit current density, the fill factor, and the energy conversion efficiency. Results obtained by both experimental and computational studies showed that the overall performances of the DSSCs with the quinoidal forms were better than those obtained with the flavylium cations dyes.

Bio-Based pH Indicator Films for Intelligent Food Packaging Applications.

The widespread concerns about the environmental problems caused by conventional plastic food packaging and food waste led to a growing effort to develop active and intelligent systems produced from renewable biodegradable polymers for food packaging applications. Among intelligent systems, the most widely used are pH indicators, which are generally based on a pH-sensitive dye incorporated into a solid support. The objective of this study was to develop new intelligent systems based on renewable biodegradable polymers and a new bio-inspired pH-sensitive dye. The structure of the dye was elucidated through FT-IR and 1D and 2D NMR spectroscopic analyses. UV-VIS measurements of the dye solutions at various pH values proved their halochromic properties. Their toxicity was evaluated through theoretical calculations, and no toxicity risks were found. The new anthocyanidin was used for the development of biodegradable intelligent systems based on chitosan blends. The obtained polymeric films were characterized through UV-VIS and FT-IR spectroscopy. Their thermal properties were assessed through a thermogravimetric analysis, which showed a better stability of chitosan-PVA-dye and chitosan-starch-dye films compared to those of chitosan-cellulose-dye films and the dye itself. The films' sensitivity to pH variations was evaluated through immersion in buffer solutions with pH values ranging from 2 to 12, and visible color changes were observed.