Highly-active, surface-modified anatase TiO2 nanoparticles were successfully synthesized and characterized. The morphological and optical properties of the obtained (metallo)porphyrin@qTiO2 materials were evaluated using absorption and fluorescence spectroscopy, scanning electron microscopy (SEM) imaging, and dynamic light scattering (DLS). These hybrid nanoparticles efficiently generated reactive oxygen species (ROS) under blue-light irradiation (420 ± 20 nm) and possessed a unimodal size distribution of 20–70 nm in diameter. The antimicrobial performance of the synthetized agents was examined against Gram-negative and Gram-positive bacteria. After a short-term incubation of microorganisms with nanomaterials (at 1 g/L) and irradiation with blue-light at a dose of 10 J/cm2, 2–3 logs of Escherichia coli, and 3–4 logs of Staphylococcus aureus were inactivated. A further decrease in bacteria viability was observed after potentiation photodynamic inactivation (PDI), either by H2O2 or KI, resulting in complete microorganism eradication even when using low material concentration (from 0.1 g/L). SEM analysis of bacteria morphology after each mode of PDI suggested different mechanisms of cellular disruption depending on the type of generated oxygen and/or iodide species. These data suggest that TiO2-based materials modified with sulfonated porphyrins are efficient photocatalysts that could be successfully used in biomedical strategies, most notably, photodynamic inactivation of microorganisms.
22 October 2019 in Research on Chemical Intermediates
Interaction of amorphous and crystalline TiO2ultrafine particles (2–6 nm) with rutin results in the formation of colored nanomaterials of an excellent dispersity and enhanced colloidal stability in aqueous media. The FTIR and Raman spectra confirmed attachment of the rutin ligand via vicinal hydroxyl groups in a catechol-like fashion. The binding of rutin to amorphous TiO2gives rise to spontaneous crystallization of the parent nanoparticles into hydrogen titanates (H2Ti3O7and H2Ti12O25). Such structural transformations result in photosensitization toward visible light with enhanced efficiency of the charge separation and interfacial charge transfer processes, confirmed by detailed photoelectrochemical studies of the examined nanomaterials. The effectiveness of the photocatalytic ROS generation reactions was also strongly influenced by hydrogen peroxide, which plays a double role of a reactant prone to reduction and generation of hydroxyl radicals or a redox agent destroying the intra-band gap electronic states, suppressing thereby charge recombination. The photoinduced charge transfer processes lead to generation of various reactive oxygen species, which were detected by EPR using DMPO spin trap (HOO·detection) and in the reaction with terephthalic acid acting as a chemical scavenger (HO·detection). Complexation of TiO2particles with rutin shifts the photogeneration of hydroperoxyl (HOO·) and hydroxyl (HO·) radicals toward visible light (λ > 400 nm). A triple effect of rutin attachment to titania was established. It consists in pronounced photosensitization, promotion of crystallization and enhancement of the colloidal stability of ultrafine titania particles. Environmental implications of these assets on the photoinduced redox reactions with hydrogen peroxide in aqueous solutions upon UV or visible light irradiation were also discussed.
The core-shell NaYb0.99F4:Tm0.01@NaYF4 upconverting particles (UCPs) with a high UV emission to apply in NIR-driven photocatalysis were synthesized. The influence of the Yb3+ doping concentration in NaYxF4:Yb0.99−xTm0.01 core particles, and the role of the NaYF4 shell on the upconversion emission intensity of the UCPs were studied. The absorption of NIR light by the obtained UCPs was maximized by increasing the Yb3+ concentration in the core, reaching the maximum for Y3+-free particles (NaYb0.99F4:Tm0.01). Additionally, covering the NaYb0.99F4:Tm0.01 core with a protective layer of NaYF4 minimized the surface luminescence quenching, which significantly improved the efficiency of upconversion emission. The high intensity of the UV light emitted by the NaYb0.99F4:Tm0.01@NaYF4 under NIR irradiation resulted in a high photocatalytic activity of TiO2 (P25) mixed with the synthesized material.