Tetramethylalloxazines as efficient singlet oxygen photosensitizers and potential redox-sensitive agents.

Tetramethylalloxazines (TMeAll) have been found to have a high quantum yield of singlet oxygen generation when used as photosensitizers. Their electronic structure and transition energies (S0 → Si, S0 → Ti, T1 → Ti) were calculated using DFT and TD-DFT methods and compared to experimental absorption spectra. Generally, TMeAll display an energy diagram similar to other derivatives belonging to the alloxazine class of compounds, namely π,π* transitions are accompanied by closely located n,π* transitions. Photophysical data such as quantum yields of fluorescence, fluorescence lifetimes, and nonradiative rate constants were also studied in methanol (MeOH), acetonitrile (ACN), and 1,2-dichloroethane (DCE). The transient absorption spectra were also analyzed. To assess cytotoxicity of new compounds, a hemolytic assay was performed using human red blood cells (RBC) in vitro. Subsequently, fluorescence lifetime imaging experiments (FLIM) were performed on RBC under physiological and oxidative stress conditions alone or in the presence of TMeAll allowing for pinpointing changes caused by those compounds on the intracellular environment of these cells.

Tuning the Photophysical Properties of Flavins by Attaching an Aryl Moiety via Direct C-C Bond Coupling.

Palladium-catalyzed Suzuki reactions of brominated flavin derivatives (5-deazaflavins, alloxazines, and isoalloxazines) with boronic acids or boronic acid esters that occur readily under mild conditions were shown to be an effective tool for the synthesis of a broad range of 7/8-arylflavins. In general, the introduction of an aryl/heteroaryl group by means of a direct C-C bond has been shown to be a promising approach to tuning the photophysical properties of flavin derivatives. The aryl substituents caused a bathochromic shift in the absorption spectra of up to 52 nm and prolonged the fluorescence lifetime by up to 1 order of magnitude. Moreover, arylation of flavin derivatives decreased their ability to generate singlet oxygen.

Insight into the LED-assisted deposition of platinum nanoparticles on the titania surface: understanding the effect of LEDs.

This paper proposes a novel LED-assisted deposition of platinum nanoparticles on the titania surface. For the first time, this process was supported by a UV-LED solution. We used two light sources with different wavelengths (λmax = 365 and 395 nm), and power (P = 1, 5, and 10 W) because the photodeposition process based on LEDs has not been defined. The TiO2-Pt material was discovered to be nano-crystalline anatase particles with nano-platinum particles deposited on the surface of titanium dioxide. Furthermore, the luminescence intensity decreased when Pt was added to TiO2, indicating that charge carrier recombination was reduced. The spectra matching of the photocatalyst and LED reactor was performed for the first time in this work. We proposed a convenient LED reactor that focused light in the range of 350-450 nm, allowing us to effectively use photo-oxidative properties of TiO2-Pt materials in the process of removing 4-chlorophenol. In the presented work, the LED light source plays a dual role. They first induce the platinum photodeposition process, before becoming an important component of tailored photoreactors, which is an important innovative aspect of this research.