Effect of Nitrogen Doping on the Photocatalytic Properties and Antibiofilm Efficacy of Reduced TiO2 Nanoparticles.

Nanomaterial-mediated antibacterial photodynamic therapy (aPDT) emerges as a promising treatment against antibiotic-resistant bacterial biofilms. Specifically, titanium dioxide nanoparticles (TiO2 NPs) are being investigated as photosensitizers in aPDT to address biofilm related diseases. To enhance their photocatalytic performance in the visible spectral range for biomedical applications, various strategies have been adopted, including reduction of TiO2 NPs. However, despite improvements in visible-light photoactivity, reduced TiO2 NPs have yet to reach their expected performance primarily due to the instability of oxygen vacancies and their tendency to reoxidize easily. To address this, we present a two-step approach to fabricate highly visible-light active and stable TiO2 NP photocatalysts, involving nitrogen doping followed by a magnesium-assisted reductive annealing process. X-ray photoelectron spectroscopy analysis of the synthesized reduced nitrogen-doped TiO2 NPs (H:Mg-N-TiO2 NPs) reveals that the presence of nitrogen stabilizes oxygen vacancies and reduced Ti species, leading to increased production of reactive oxygen species under visible-light excitation. The improved aPDT efficiency translates to a 3-fold enhancement in the antibiofilm activity of nitrogen-doped compared to undoped reduced TiO2 NPs against both Gram-positive (Streptococcus mutans) and Gram-negative (Porphyromonas gingivalis, Fusobacterium nucleatum) oral pathogens. These results underscore the potential of H:Mg-N-TiO2 NPs in aPDT for combating bacterial biofilms effectively.

Unusual Hydration Properties of Choline Fluoride-Based Deep Eutectic Solvents.

The hydration properties of the fluoride-based deep eutectic solvent ethalineF [a solution of choline fluoride in ethylene glycol (EG) at a 1:2 molar ratio] are studied and compared to the most common deep eutectic solvent ethaline (the solution of choline chloride in EG at 1:2 molar ratio). The densities of the deep eutectic solvent (DES) based on choline fluoride in EG (ethalineF) and its mixtures with water as cosolvent are measured over the temperature range of 298-323 K. The excess properties, including excess molar volumes, excess partial molar volumes, and viscosity deviations from ideal behavior, are calculated for ethalineF/water and ethaline/water mixtures and compared. The experimental excess molar volumes and viscosity deviations of the studied pseudobinary mixtures are fitted using the Redlich-Kister (R-K) equation. The results of the R-K model successfully reproduced the experimentally calculated values with minimal standard deviations. All excess molar volumes and viscosity deviations had negative values, indicating stronger solvation interactions between the mixture components than between each pure DES or water. The excess partial molar volumes show that water molecules are preferentially solvated by the DES environment. We show that the disruption of the DES interactions (primarily OH...halide interactions) by high mole fractions of water is related to the peak ionic conductivity. The stark differences in hydration behavior between fluoride- and chloride-based ethaline are analyzed and discussed.