The synthesis of a new 15-membered polyaza-macrocyclic ligand L3H3, which is based on a 2,2'-bipyridine moiety and a diethylenetriaminetriacetic acid core, is reported. The lanthanide chelates of this octadentate ligand were programmed for bimodal probes, luminescent agents (Sm, Eu, Tb, Dy), and magnetic resonance imaging agents (Gd3+). The neutral 1:1 complexes with these Ln3+ ions were prepared and studied in aqueous solution by luminescence and NMR techniques. The main photophysical characteristics of these complexes (i.e., the absorption and luminescence spectra, the metal-centered lifetimes, and the overall luminescence yields, Phi) were measured. In addition, the role played by nonradiative pathways (vibrational energy transfer involving coordinated water molecules, involvement of ligand-to-metal charge-transfer excited states, or metal --> ligand back transfer) is discussed. The L3.Eu and L3.Tb complexes show very bright luminescence when photoexcited from the lowest-energy absorption band of the bipyridine chromophore. The luminescence quantum yields in an air-equilibrated water solution at room temperature are 0.10 and 0.21, respectively, despite the presence of one water molecule in the first coordination sphere of the metal ion. NMR data show that L3.Gd contains also one H2O molecule in the inner sphere. The proton longitudinal relaxivity, r1, of this complex is 3.4 s(-1) mM(-1) (0.47 T, 310 K) and the rotational correlation time, tau(R), is 57 ps (310 K). These values are comparable to those of the clinically used Gd-DTPA. Interestingly, the water exchange rate between the coordination site and the bulk solvent is slow (tau(M) = 3.5 micros at 310 K). The presence of water molecules in the second sphere and in rapid exchange with the solvent is discussed. Finally, it was found by luminescence and NMR experiments that these lanthanide complexes are stable versus transmetalation by several cations (especially Ca2+ and Zn2+) at physiological pH and have no interaction with blood proteins.
The colorless carotenoids phytoene and phytofluene are comparatively understudied compounds found in common foods (e.g., tomatoes) and in human plasma, internal tissues, and skin. Being naturally present in common foods, their intake at dietary levels is not expected to present a safety concern. However, since the interest in these compounds in the context of many applications is expanding, it is important to conduct studies aimed at assessing their safety. We present here results of in vitro cytotoxicity and genotoxicity studies, revealing no significant cytotoxic or genotoxic potential and of short- and long-term human in vivo skin compatibility studies with phytoene- and phytofluene-rich tomato and Dunaliella salina alga extracts, showing a lack of irritancy or sensitization reactions. These results support the safe use of phytoene- and phytofluene-rich products in human topical applications.
Glycation, and the resulting buildup of advanced glycation end products (AGEs), is recognized as a key driver of cumulative skin damage and skin aging. Dunaliella salina is a halophile microalga adapted to intense solar radiation through the production of carotenoids. We present a natural supercritical CO2 extract of Dunaliella salina rich in the colorless carotenoids phytoene and phytofluene. The extract exhibited antiglycation and anti-inflammatory activities in ex vivo testing, showing strongly reduced formation of N-ε-carboxy-methyl-lysine with exposure to methylglyoxal, reduced AGE receptor levels, and significantly reduced interleukins 6 and 8. In a placebo-controlled clinical study under intense solar exposure, the extract significantly reduced the skin’s glycation scores and its sensitivity to histamine; key skin aging parameters were also significantly improved vs. placebo, including wrinkle counts and spots. These results demonstrate the value of this Dunaliella salina extract, rich in colorless carotenoids, as an antiglycative, anti-inflammatory, and antiaging active ingredient, including in high-irradiation contexts.
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