Morphological and elemental tuning of BiOCl/BiVO4 heterostructure for uric acid electrochemical sensor and antibiotic photocatalytic degradation.

Deep eutectic solvents (DES) consisting of EG-(ChCl: C2H6O2) and TU-(ChCl: CH4N2S) assisted synthesized BiOCl/BiVO4 heterostructured catalyst studied for electrochemical uric acid (UA) sensor and tetracycline photocatalytic degradation. The chemical composition of the BiOCl/BiVO4 catalyst was analyzed by X-ray photoelectron spectroscopy (XPS). UV-vis spectroscopy reveals increased absorption of visible light till the near-infrared region, which results in a narrowing of band gap energy from 2.3 eV to 2.2 eV for BiOCl/BiVO4-TU. Morphology of catalyst analyzed using field-emission scanning electron microscope (FE-SEM) and Transmission electron microscope (TEM) technique. Time-Resolved photoluminescence (TRPL) confirms an increased lifetime of e-/h+ pair after heterostructure formation. The catalyst-modified glassy carbon electrode shows selectivity toward the detection of uric acid (UA). The limit of detection (LOD) is estimated to be 0.04688 µM for UA; also, interference and stability of catalyst were studied. Photocatalytic activity of the synthesized catalyst was investigated by degrading tetracycline (TC) antibiotic pollutants, and their intermediate product was analyzed by ion trap mass spectrometry (MS).

Visible Light-Responsive Platinum-Containing Titania Nanoparticle-Mediated Photocatalysis Induces Nucleotide Insertion, Deletion and Substitution Mutations.

Conventional photocatalysts are primarily stimulated using ultraviolet (UV) light to elicit reactive oxygen species and have wide applications in environmental and energy fields, including self-cleaning surfaces and sterilization. Because UV illumination is hazardous to humans, visible light-responsive photocatalysts (VLRPs) were discovered and are now applied to increase photocatalysis. However, fundamental questions regarding the ability of VLRPs to trigger DNA mutations and the mutation types it elicits remain elusive. Here, through plasmid transformation and ß-galactosidase α-complementation analyses, we observed that visible light-responsive platinum-containing titania (TiO2) nanoparticle (NP)-mediated photocatalysis considerably reduces the number of Escherichia coli transformants. This suggests that such photocatalytic reactions cause DNA damage. DNA sequencing results demonstrated that the DNA damage comprises three mutation types, namely nucleotide insertion, deletion and substitution; this is the first study to report the types of mutations occurring after photocatalysis by TiO2-VLRPs. Our results may facilitate the development and appropriate use of new-generation TiO2 NPs for biomedical applications.

Antibacterial property of Ag nanoparticle-impregnated N-doped titania films under visible light.

Photocatalysts produce free radicals upon receiving light energy; thus, they possess antibacterial properties. Silver (Ag) is an antibacterial material that disrupts bacterial physiology. Our previous study reported that the high antibacterial property of silver nanoparticles on the surfaces of visible light-responsive nitrogen-doped TiO2 photocatalysts [TiO2(N)] could be further enhanced by visible light illumination. However, the major limitation of this Ag-TiO2 composite material is its durability; the antibacterial property decreased markedly after repeated use. To overcome this limitation, we developed TiO2(N)/Ag/TiO2(N) sandwich films in which the silver is embedded between two TiO2(N) layers. Various characteristics, including silver and nitrogen amounts, were examined in the composite materials. Various analyses, including electron microscopy, energy dispersive spectroscopy, X-ray diffraction, and ultraviolet-visible absorption spectrum and methylene blue degradation rate analyses, were performed. The antibacterial properties of the composite materials were investigated. Here we revealed that the antibacterial durability of these thin films is substantially improved in both the dark and visible light, by which bacteria, such as Escherichia coli, Streptococcus pyogenes, Staphylococcus aureus, and Acinetobacter baumannii, could be efficiently eliminated. This study demonstrated a feasible approach to improve the visible-light responsiveness and durability of antibacterial materials that contain silver nanoparticles impregnated in TiO2(N) films.

Bactericidal performance of visible-light responsive titania photocatalyst with silver nanostructures.

BACKGROUND: Titania dioxide (TiO(2)) photocatalyst is primarily induced by ultraviolet light irradiation. Visible-light responsive anion-doped TiO(2) photocatalysts contain higher quantum efficiency under sunlight and can be used safely in indoor settings without exposing to biohazardous ultraviolet light. The antibacterial efficiency, however, remains to be further improved. METHODOLOGY/PRINCIPAL FINDINGS: Using thermal reduction method, here we synthesized silver-nanostructures coated TiO(2) thin films that contain a high visible-light responsive antibacterial property. Among our tested titania substrates including TiO(2), carbon-doped TiO(2) [TiO(2) (C)] and nitrogen-doped TiO(2) [TiO(2) (N)], TiO(2) (N) showed the best performance after silver coating. The synergistic antibacterial effect results approximately 5 log reductions of surviving bacteria of Escherichia coli, Streptococcus pyogenes, Staphylococcus aureus and Acinetobacter baumannii. Scanning electron microscope analysis indicated that crystalline silver formed unique wire-like nanostructures on TiO(2) (N) substrates, while formed relatively straight and thicker rod-shaped precipitates on the other two titania materials. CONCLUSION/SIGNIFICANCE: Our results suggested that proper forms of silver on various titania materials could further influence the bactericidal property.

Role of visible light-activated photocatalyst on the reduction of anthrax spore-induced mortality in mice.

BACKGROUND: Photocatalysis of titanium dioxide (TiO(2)) substrates is primarily induced by ultraviolet light irradiation. Anion-doped TiO(2) substrates were shown to exhibit photocatalytic activities under visible-light illumination, relative environmentally-friendly materials. Their anti-spore activity against Bacillus anthracis, however, remains to be investigated. We evaluated these visible-light activated photocatalysts on the reduction of anthrax spore-induced pathogenesis. METHODOLOGY/PRINCIPAL FINDINGS: Standard plating method was used to determine the inactivation of anthrax spore by visible light-induced photocatalysis. Mouse models were further employed to investigate the suppressive effects of the photocatalysis on anthrax toxin- and spore-mediated mortality. We found that anti-spore activities of visible light illuminated nitrogen- or carbon-doped titania thin films significantly reduced viability of anthrax spores. Even though the spore-killing efficiency is only approximately 25%, our data indicate that spores from photocatalyzed groups but not untreated groups have a less survival rate after macrophage clearance. In addition, the photocatalysis could directly inactivate lethal toxin, the major virulence factor of B. anthracis. In agreement with these results, we found that the photocatalyzed spores have tenfold less potency to induce mortality in mice. These data suggest that the photocatalysis might injury the spores through inactivating spore components. CONCLUSION/SIGNIFICANCE: Photocatalysis induced injuries of the spores might be more important than direct killing of spores to reduce pathogenicity in the host.

Visible-light-induced bactericidal activity of a nitrogen-doped titanium photocatalyst against human pathogens.

The antibacterial activity of photocatalytic titanium dioxide (TiO(2)) substrates is induced primarily by UV light irradiation. Recently, nitrogen- and carbon-doped TiO(2) substrates were shown to exhibit photocatalytic activities under visible-light illumination. Their antibacterial activity, however, remains to be quantified. In this study, we demonstrated that nitrogen-doped TiO(2) substrates have superior visible-light-induced bactericidal activity against Escherichia coli compared to pure TiO(2) and carbon-doped TiO(2) substrates. We also found that protein- and light-absorbing contaminants partially reduce the bactericidal activity of nitrogen-doped TiO(2) substrates due to their light-shielding effects. In the pathogen-killing experiment, a significantly higher proportion of all tested pathogens, including Shigella flexneri, Listeria monocytogenes, Vibrio parahaemolyticus, Staphylococcus aureus, Streptococcus pyogenes, and Acinetobacter baumannii, were killed by visible-light-illuminated nitrogen-doped TiO(2) substrates than by pure TiO(2) substrates. These findings suggest that nitrogen-doped TiO(2) has potential application in the development of alternative disinfectants for environmental and medical usages.

Low temperature kinetics and energetics of the electron and hole traps in irradiated TiO2 nanoparticles as revealed by EPR spectroscopy.

We have monitored exclusively the dynamics of photogenerated charge carriers trapping in deep traps and trapped electron-hole recombination in UV irradiated anatase TiO2 powders by electron paramagnetic resonance (EPR) spectroscopy at 10 K. The results reveal that the strategy of using low temperatures contributes to the stabilization of the charged pair states for hours by reducing the rate of electron-hole recombination processes. Since only the localized states such as holes trapped at oxygen anions and electrons trapped at coordinatively unsaturated cations are accessible to EPR spectroscopy, the time-dependent population and depopulation of these EPR signals reflect the kinetics and energetics of these trap states. The data support a model of sequential accumulation of deep trap site populations in which the initial fast direct trapping into a deep trap site is followed by slower carrier trap-to-trap hopping until a deep trap is encountered for both photogenerated electrons and holes. Effective modeling of the subsequent decay of trapped-holes is achieved by employing a first-order kinetics, whereas the decay of either surface- or inner-trapped electrons has both a fast and a slow component. The fast component is attributed to a trapped-electron and a free-hole recombination, and the slow component is attributed to trapped electron-hole recombination. The activation energies for the process of diffusion of trapped electrons from their Ti3+ trapping sites are estimated.

EPR investigation of TiO2 nanoparticles with temperature-dependent properties.

An in situ electron paramagnetic resonance (EPR) study has been carried out for anatase (Hombikat UV100) and rutile TiO(2) nanoparticles at liquid helium (He) temperature (4.2 K) under UV irradiation. Rutile titania was synthesized by ultrasonic irradiation with titanium tetrachloride (TiCl(4)) as the precursor. XRD and Raman results evidence the crystallinity of titania phases. The nature of trapped electrons and holes has been investigated by EPR spectroscopy under air and vacuum conditions. Illumination of TiO(2) powder (anatase and rutile) at 4.2 K resulted in the detection of electrons being trapped at Ti(4+) sites within the bulk and holes trapped at lattice oxide ions at the surface. The stability of electron traps was very sensitive to temperature in both phases of TiO(2). The annealing kinetics of the EPR detected radicals has been studied from 4.2 K to ambient temperature and also for calcined titania particles from 523 to 1273 K.

Visible-light-responsive nano-TiO(2) with mixed crystal lattice and its photocatalytic activity.

Ultraviolet- and visible-light-responsive titania-based photocatalysts were synthesized and employed in the photocatalytic oxidation of NO(x). Sol-gel processes using tetrabutyl orthotitanate and ethanol under acid catalyzed condition and controlled calcination were performed to synthesize titanium dioxide with a mixed crystal lattice of anatase, brookite and rutile phases. The TiO(2) prepared under calcination at 200 °C exhibited high photocatalytic activity for degradation of NO(x) under both ultraviolet (UV) and visible-light illumination. The experimental results showed that up to 70% removal of NO(x) could be obtained in a continuous flow type reaction system under irradiation with visible light. The calcination temperature has an important influence on the particle size and lattice structure of TiO(2). It is also found that the peculiar mixed-phase structure of TiO(2), evidenced from Raman, x-ray diffractometry (XRD), and UV-vis spectroscopy, was inferred to be an important factor for visible-light absorption and NO(x) removal activity under a wide range of visible-light illumination.