W-Doped TiO2 Nanorods for Multimode Tumor Eradication in Osteosarcoma Models under Single Ultrasound Irradiation.

Sonosensitizers play crucial roles in the controlled production of reactive oxygen species (ROS) under ultrasound (US) irradiation with high tissue-penetration depth for noninvasive solid tumor therapy. It is desirable to fabricate structurally simple yet multifunctional sonosensitizers from ultrafine nanoparticles for ROS-based multimode therapy to overcome monomode limitations such as low ROS production yields and endogenous reductive glutathione (GSH) to ROS-based treatment resistance. We report the facile high-temperature solution synthesis of ultrafine W-doped TiO2 (W-TiO2) nanorods for exploration of their sonodynamic, chemodynamic, and GSH-depleting activities in sonodynamic-chemodynamic combination tumor therapy. We found that W5+ and W6+ ions doped in W-TiO2 nanorods play multiple roles in enhancing their ROS production. First, W doping narrows the band gap from 3.2 to 2.3 eV and introduces oxygen and Ti vacancies for enhancing their sonodynamic performance. Second, W5+ doping endows W-TiO2 nanorods with Fenton-like reaction activity to produce •OH from endogenous H2O2 in the tumor. Third, W6+ ions reduce endogenous GSH to glutathione disulfide (GSSG) and, in turn, form W5+ ions that further enhance their chemodynamic activity, which greatly modifies thae oxidation-reduction tumor microenvironment in the tumor. In vivo experiments display the excellent ability of W-TiO2 nanorods for enhanced tumor eradication in human osteosarcoma models under single US irradiation. Importantly, the ultrafine nanorod morphology facilitates rapid excretion from the body, displaying no significant systemic toxicity. Our work suggests that multivalent metal doping in ultrafine nanomaterials is an effective and simple strategy for the introduction of new functions for ROS-based multimode therapy.

Mussel-Inspired Immobilization of Photocatalysts with Synergistic Photocatalytic-Photothermal Performance for Water Remediation.

The serious problem of pharmaceutical and personal care product pollution places great pressure on aquatic environments and human health. Herein, a novel coating photocatalyst was synthesized by adhering Ag-AgCl/WO3/g-C3N4 (AWC) nanoparticles on a polydopamine (PDA)-modified melamine sponge (MS) through a facile layer-by-layer assembly method to degrade trimethoprim (TMP). The formed PDA coating was used for the anchoring of nanoparticles, photothermal conversion, and hydrophilic modification. TMP (99.9%; 4 mg/L) was removed in 90 min by the photocatalyst coating (AWC/PDA/MS) under visible light via a synergistic photocatalytic-photothermal performance route. The stability and reusability of the AWC/PDA/MS have been proved by cyclic experiments, in which the removal efficiency of TMP was still more than 90% after five consecutive cycles with a very little mass loss. Quantitative structure-activity relationship analysis revealed that the ecotoxicities of the generated intermediates were lower than those of TMP. Furthermore, the solution matrix effects on the photocatalytic removal efficiency were investigated, and the results revealed that the AWC/PDA/MS still maintained excellent photocatalytic degradation efficiency in several actual water and simulated water matrices. This work develops recyclable photocatalysts for the potential application in the field of water remediation.

Anionic polyacrylamide-assisted construction of thin 2D-2D WO3/g-C3N4 Step-scheme heterojunction for enhanced tetracycline degradation under visible light irradiation.

Thin 2D/2D WO3/g-C3N4 Step-scheme (S-scheme) heterojunction with carbon doping and bridge (C-W/N) was constructed with anionic polyacrylamide (APAM), in which APAM functioned as an assistant templet and a carbon source. APAM and WO3 were inserted into g-C3N4 nanosheet. The carbon, thin planar structure and WO3 with oxygen vacancies result in fast charge transfer, high quantum efficiency and strong driving force for photocatalytic reaction. Consequently, as-prepared C-W/N ternary composite photocatalyst exhibited significantly enhanced photocatalytic performance for tetracycline (TC) degradation under visible light compared to pure g-C3N4, WO3 and other binary composites. Moreover, the material showed high stability and reusability in cyclic TC degradation. The principal intermediate products over C-W/N photocatalyst were revealed by HPLC-MS analysis. Corresponding degradation pathway of TC was also presented in this work. According to the trapping experiments, analysis of electron spin resource (ESR) and band gap, possible charge transfer pathways of C-W/N are proposed and discussed in detail. Based on the results, carbon derived from APAM works not only as electron mediator but also as acceptor for photocatalytic degradation reaction. It is a promising way to further modulate heterojunction for varies applications.

Sono-photocatalytic degradation of tetracycline and pharmaceutical wastewater using WO3/CNT heterojunction nanocomposite under US and visible light irradiations: A novel hybrid system.

In this paper, in-situ fabrication of tungsten oxide (WO3) on carbon nano-tube (CNT) was performed via sol-gel/hydrothermal method to prepare WO3/CNT nanocomposites and then coupled with visible light and ultrasound (US) irradiations for sono-photocatalytic removal of tetracycline (TTC) and pharmaceutical wastewater treatment. The as-prepared catalysts were characterized by FT-IR, XRD, TEM, UV-VIS DRS, FESEM, EDS, TGA, BET, BJH, EIS, and EDX techniques. The characterization tests, indicated successful incorporation of CTNs into the WO3 framework and efficient reduction of charge carries recombination rate after modifying with CNT. The investigation of experimental parameters verified that 60 mg/L TTC could be perfectly degraded at optimum operational parameters (WO3/CNT: 0.7 g/L, pH: 9.0, US power: 250 W/m2, and light intensity: 120 W/m2 over 60 min treatment. Trapping experiments results verified that HO radicals and h+ were the main oxidative species in degradation of TTC. The as-prepared photocatalysts could be reused after six successive cycles with an approximately 8.8 % reduction in removal efficiency. Investigation of the effect of real pharmaceutical wastewater revealed that this system is able to eliminate 83.7 and 90.6 % of TOC and COD, respectively after 220 min of reaction time. Some compounds with lower toxic impact and molecular weight, compared to raw pharmaceutical wastewater, were detected after treatment by sono-photocatalysis process. The biodegradability of real pharmaceutical wastewater was improved significantly after treatment by WO3/CNT sono-photocatalysis.

Ag Nanoparticles/α-Ag2WO4 Composite Formed by Electron Beam and Femtosecond Irradiation as Potent Antifungal and Antitumor Agents.

The ability to manipulate the structure and function of promising systems via external stimuli is emerging with the development of reconfigurable and programmable multifunctional materials. Increasing antifungal and antitumor activity requires novel, effective treatments to be diligently sought. In this work, the synthesis, characterization, and in vitro biological screening of pure α-Ag2WO4, irradiated with electrons and with non-focused and focused femtosecond laser beams are reported. We demonstrate, for the first time, that Ag nanoparticles/α-Ag2WO4 composite displays potent antifungal and antitumor activity. This composite had an extreme low inhibition concentration against Candida albicans, cause the modulation of α-Ag2WO4 perform the fungicidal activity more efficient. For tumor activity, it was found that the composite showed a high selectivity against the cancer cells (MB49), thus depleting the populations of cancer cells by necrosis and apoptosis, without the healthy cells (BALB/3T3) being affected.

The role of ozone and influence of band structure in WO3 photocatalysis and ozone integrated process for pharmaceutical wastewater treatment.

Photocatalytic ozonation has great potential in wastewater treatment. However, the role of ozone and the contribution of photogenerated hole in this process have not been fully understood. Here three WO3 materials are synthesized and used as model catalysts in visible-light photocatalytic ozonation for the mineralization of pharmaceutical pollutants. A dual role of ozone in this process has been confirmed: (i) direct oxidation of the pollutant till formation of refractory intermediates, (ii) efficient trapping of photoelectron that cannot be captured by O2. The latter is crucial because it not only induces the O3--mediated pathway for hydroxyl radical (OH) formation but also separates the hole which has proven to be capable of oxidizing water into OH. Evidenced by photoluminescence results, the intrinsic charge separation ability of WO3 in photocatalytic ozonation is no more as important as that in photocatalysis with O2. Finally, this process is more applicable under acidic condition. This work contributes to a better understanding of the significance of ozone in WO3 photocatalytic ozonation and provides us an insight into the mechanism of photocatalytic ozonation.

Cell Fragmentation and Permeabilization by a 1 ns Pulse Driven Triple-Point Electrode.

Ultrashort electric pulses (ns-ps) are useful in gaining understanding as to how pulsed electric fields act upon biological cells, but the electric field intensity to induce biological responses is typically higher than longer pulses and therefore a high voltage ultrashort pulse generator is required. To deliver 1 ns pulses with sufficient electric field but at a relatively low voltage, we used a glass-encapsulated tungsten wire triple-point electrode (TPE) at the interface among glass, tungsten wire, and water when it is immersed in water. A high electric field (2 MV/cm) can be created when pulses are applied. However, such a high electric field was found to cause bubble emission and temperature rise in the water near the electrode. They can be attributed to Joule heating near the electrode. Adherent cells on a cover slip treated by the combination of these stimuli showed two major effects: (1) cells in a crater (<100 µm from electrode) were fragmented and the debris was blown away. The principal mechanism for the damage is presumed to be shear forces due to bubble collapse; and (2) cells in the periphery of the crater were permeabilized, which was due to the combination of bubble movement and microstreaming as well as pulsed electric fields. These results show that ultrashort electric fields assisted by microbubbles can cause significant cell response and therefore a triple-point electrode is a useful ablation tool for applications that require submillimeter precision.

Well-controlled in-situ growth of 2D WO3 rectangular sheets on reduced graphene oxide with strong photocatalytic and antibacterial properties.

Finding the materials, which help to control the water pollution caused by organic and bacterial pollutants is one of the challenging tasks for the scientific community. 2D sheets of WO3 and composite of WO3 and reduced graphene oxide (rGO) have been synthesized in a well-controlled way using a hydrothermal method. The as synthesized 2D sheet of WO3 and rGO-WO3 composite were characterized by various techniques. The 2D sheets of WO3 and rGO-WO3 composite are efficiently utilized for the photocatalytic degradation of methylene blue (MB) and Rhodamine B (RhB) dyes under sunlight. The rGO-WO3 composite reveals excellent photocatalytic degradation of RhB dye by degrading it upto 85% under sunlight. However, the MB dye was degraded by 32%. The greater degradation of RhB dye was explained in terms of the molecular electrostatic potential. We found that RhB has a more positive potential compared to MB dye where O2- and OH̊ radicals interact more strongly, resulting in a greater degradation of the RhB dye. The antibacterial activity of the 2D sheets of WO3 and rGO-WO3composite was also investigated on gram positive (B. subtilis) and gram negative (P. aeroginosa) microbes for the first time.

Lysozyme-mediated biomineralization of titanium-tungsten oxide hybrid nanoparticles with high photocatalytic activity.

Titanium-tungsten oxide composites with greatly enhanced photocatalytic activity were synthesized by lysozyme-mediated biomineralization. It was shown for the first time that simple control of the onset of biomineralization could enable fine tuning of the composition and crystallinity of the composites to determine their photocatalytic performance.

Interpretation and prediction of fast particle irradiation impact by data-containing codes.

The problem of interpretation, estimation and prediction of impacts of nature or artificial irradiation on various materials by modern nuclear reaction codes is discussed. Advanced data-containing codes EMPIRE and TALYS are considered. The yields of radioactive isotopes in high-energy p+(183)W collision are calculated to illustrate the potentialities of the codes for the declared purposes. The reliability of codes of such a type is treated. Measurements of isomeric cross-section ratios and comparison of these experimental results with the calculated ones are proposed as a promising test of the reliability.

Mesoscale modeling of photoelectrochemical devices: light absorption and carrier collection in monolithic, tandem, Si|WO3 microwires.

We analyze mesoscale light absorption and carrier collection in a tandem junction photoelectrochemical device using electromagnetic simulations. The tandem device consists of silicon (E(g,Si) = 1.1 eV) and tungsten oxide (E(g,WO3) = 2.6 eV) as photocathode and photoanode materials, respectively. Specifically, we investigated Si microwires with lengths of 100 µm, and diameters of 2 µm, with a 7 µm pitch, covered vertically with 50 µm of WO3 with a thickness of 1 µm. Many geometrical variants of this prototypical tandem device were explored. For conditions of illumination with the AM 1.5G spectra, the nominal design resulted in a short circuit current density, J(SC), of 1 mA/cm(2), which is limited by the WO3 absorption. Geometrical optimization of photoanode and photocathode shape and contact material selection, enabled a three-fold increase in short circuit current density relative to the initial design via enhanced WO3 light absorption. These findings validate the usefulness of a mesoscale analysis for ascertaining optimum optoelectronic performance in photoelectrochemical devices.

Safety of retained microcatheters: an evaluation of radiofrequency heating in endovascular microcatheters with nitinol, tungsten, and polyetheretherketone braiding at 1.5 T and 3 T.

BACKGROUND: The use of ethylene-vinyl alcohol copolymer for liquid embolization of cranial vascular lesions has resulted in microcatheter fragments entrapped in patients following endovascular procedures. Undergoing subsequent diagnostic MRI examinations poses a safety concern due to the possibility of radiofrequency heating of the metallic braid incorporated into the microcatheter. Heating of nitinol, tungsten, and polyetheretherketone (PEEK) braided microcatheters was assessed and compared using a phantom model. METHODS: Microcatheters coupled with fluoroptic temperature probes were embedded in a polyacrylamide gel within a head and torso phantom. Experiments were performed at 1.5 T and 3 T, analyzing the effects of different catheter immersion lengths, specific absorption rate (SAR) levels, short clinical scans, long clinical scans, and microcatheter fragment lengths. RESULTS: The maximal increase in temperature for the nitinol braided microcatheter during a 15 min scan was 3.06°C using the T1 fast spin echo sequence at 1.5 T and 0.45°C using the balanced steady state free precession sequence at 3 T. The same scans for fragment lengths of 9, 18, 36, and 72 cm produced maximal temperature rises of 0.68, 0.80, 1.70, and 1.07°C at 1.5 T, respectively. The temperature changes at 3 T for these fragment lengths were 0.66, 0.83, 1.07, and 0.72°C, respectively. The tungsten and PEEK braided microcatheters did not demonstrate heating. CONCLUSIONS: Substantial heating of nitinol braided microcatheters occurred and was a function of SAR level and geometric considerations. SAR and time limitations on MR scanning are proposed for patients with this microcatheter entrapped in their vasculature. In contrast, tungsten and PEEK braided microcatheters showed potential safe use in MRI.

H2S photocatalytic oxidation over WO3/TiO2 Hombikat UV100.

Hydrogen sulfide (H2S) is a toxic, corrosive and malodorous compound with damaging effects even when present at a low concentration in air. Consequently, the development of efficient and environmentally friendly remediation technologies as an alternative to conventional techniques is justified for environmental reasons and public concern over human health and well-being. In the context of indoor air quality control, the use of photocatalysis over semi-conductor oxides could be a valuable alternative purification technology due to its wide-ranging effect and its easy way of implementation. The superiority of the TiO2 Hombikat UV100 photocatalyst in comparison with the Aeroxide© TiO2 P25 standard was already apparent in the UV-A photocatalytic oxidation of H2S. We report here on the first use of WO3/TiO2 UV100 photocatalysts for this reaction. Associating WO3 to TiO2 UV100 was not beneficial in terms of semiconductor coupling and of charge transfer between both phases. Even if such coupled wide band-gap oxide semi-conductor photocatalysts suffered from on-flow deactivation due to the formation of poisoning sulfates as ultimate reaction products continuously stored at the surface, by contrast, their ability to strongly lower and delay the release of SO2 to the gas phase was very positive for maintaining a weak selectivity into the unwanted SO2 by-product.

A TPD and AR based comparison of accelerator neutron irradiation fields between (7)Li and W targets for BNCT.

The characteristics of moderator assembly dimension was investigated for the usage of (7)Li(p,n) neutrons by 2.3-2.8MeV protons and W(p,n) neutrons by 50MeV protons. The indexes were the treatable protocol depth (TPD) and advantage depth (AD). Consequently, a configuration for W target with the Fe filter, Fluental moderator, Pb reflector showed the TPD of 5.8cm and AD of 9.3cm. Comparable indexes were found for the Li target in a geometry with the MgF2 moderator and Teflon reflector.

Solar photocatalytic activity of TiO2 modified with WO3 on the degradation of an organophosphorus pesticide.

In this study, the solar photocatalytic activity (SPA) of WO3/TiO2 photocatalysts synthesized by the sol-gel method with two different percentages of WO3 (2 and 5%wt) was evaluated using malathion as a model contaminant. For comparative purpose bare TiO2 was also prepared by sol-gel process. The powders were characterized by X-ray diffraction (XRD), Raman spectroscopy, diffuse reflectance UV-vis spectroscopy (DRUV-vis), specific surface area by the BET method (SSABET), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and scanning transmission electron microscopy with a high annular angle dark field detector (STEM-HAADF). The XRD, Raman, HRTEM and STEM-HAADF analyses indicated that WO3 was present as a monoclinic crystalline phase with nanometric cluster sizes (1.1 ± 0.1 nm for 2% WO3/TiO2 and 1.35 ± 0.3 nm for 5% WO3/TiO2) and uniformly dispersed on the surface of TiO2. The particle size of the materials was 19.4 ± 3.3 nm and 25.6 ± 3 nm for 2% and 5% WO3/TiO2, respectively. The SPA was evaluated on the degradation of commercial malathion pesticide using natural solar light. The 2% WO3/TiO2 photocatalyst exhibited the best photocatalytic activity achieving 76% of total organic carbon (TOC) abatement after 300 min compared to the 5% WO3/TiO2 and bare TiO2 photocatalysts, which achieved 28 and 47% mineralization, respectively. Finally, experiments were performed to assess 2% WO3/TiO2 catalyst activity on repeated uses; after several successive cycles its photocatalytic activity was retained showing long-term stability.

A full-sunlight-driven photocatalyst with super long-persistent energy storage ability.

A major drawback of traditional photocatalysts like TiO2 is that they can only work under illumination, and the light has to be UV. As a solution for this limitation, visible-light-driven energy storage photocatalysts have been developed in recent years. However, energy storage photocatalysts that are full-sunlight-driven (UV-visible-NIR) and possess long-lasting energy storage ability are lacking. Here we report, a Pt-loaded and hydrogen-treated WO3 that exhibits a strong absorption at full-sunlight spectrum (300-1,000 nm), and with a super-long energy storage time of more than 300 h to have formaldehyde degraded in dark. In this new material system, the hydrogen treated WO3 functions as the light harvesting material and energy storage material simultaneously, while Pt mainly acts as the cocatalyst to have the energy storage effect displayed. The extraordinary full-spectrum absorption effect and long persistent energy storage ability make the material a potential solar-energy storage and an effective photocatalyst in practice.

Synthesis and photocatalytic properties of ZnWO4 nanocrystals via a fast microwave-assisted method.

High crystallinity of ZnWO4 nanoparticles has been successfully synthesized via a highly effective and environmentally friendly microwave route by controlling the reaction time and temperature. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and Fourier infrared spectrum (FT-IR). The crystallinity was enhanced with the increase of the reaction temperature and time. The photocatalytic activities of ZnWO4 nanocrystals were evaluated by testing the photodegradation of rhodamine B (RhB) dye under ultraviolet (UV) light irradiation. The results indicated that as-prepared ZnWO4 was highly effective for the degradation of RhB. The degradation rate of RhB reached 98.01% after 6 h of UV illumination.

Facile one-step synthesis of inorganic-framework molecularly imprinted TiO2/WO3 nanocomposite and its molecular recognitive photocatalytic degradation of target contaminant.

Inorganic-framework molecularly imprinted TiO2/WO3 nanocomposites with molecular recognitive photocatalytic activity were first prepared successfully by a facile one-step sol-gel method using 2-nitrophenol and 4-nitrophenol as template molecules, and tetrabutyl orthotitanate as titanium source as well as the precursor of functional monomer which could complex with template molecules. The template molecules could be completely removed by means of high-temperature calcination, avoiding the traditional extraction procedures that are time- as well as solvent-consuming. Compared to nonimprinted TiO2/WO3, the molecularly imprinted TiO2/WO3 shows a much higher adsorption capacity and selectivity toward the template molecules. The enhancement in terms of adsorption capacity and selectivity can be attributed to the chemical interaction between target molecules and imprinted cavities, as well as size matching between imprinted cavities and target molecules. The photocatalytic activity of molecularly imprinted TiO2/WO3 toward the target molecules is more than two times that of non-imprinted TiO2/WO3, a result of selective adsorption of target molecules on molecularly imprinted TiO2/WO3. The formation pathway of intermediate products in 2-nitrophenol and 4-nitrophenol degradation process was provided. Moreover, molecularly imprinted TiO2/WO3 exhibits high stability. The results indicate that inorganic-framework molecularly imprinted TiO2/WO3 nanocomposites have a promising prospect in the treatment of wastewater for irrigation.

Damage investigation on tungsten and diamond diffractive optics at a hard x-ray free-electron laser.

Focusing hard x-ray free-electron laser radiation with extremely high fluence sets stringent demands on the x-ray optics. Any material placed in an intense x-ray beam is at risk of being damaged. Therefore, it is crucial to find the damage thresholds for focusing optics. In this paper we report experimental results of exposing tungsten and diamond diffractive optics to a prefocused 8.2 keV free-electron laser beam in order to find damage threshold fluence levels. Tungsten nanostructures were damaged at fluence levels above 500 mJ/cm(2). The damage was of mechanical character, caused by thermal stress variations. Diamond nanostructures were affected at a fluence of 59 000 mJ/cm(2). For fluence levels above this, a significant graphitization process was initiated. Scanning Electron Microscopy (SEM) and µ-Raman analysis were used to analyze exposed nanostructures.

Direct in situ observation of the electron-driven synthesis of Ag filaments on α-Ag2WO4 crystals.

In this letter, we report, for the first time, the real-time in situ nucleation and growth of Ag filaments on α-Ag2WO4 crystals driven by an accelerated electron beam from an electronic microscope under high vacuum. We employed several techniques to characterise the material in depth. By using these techniques combined with first-principles modelling based on density functional theory, a mechanism for the Ag filament formation followed by a subsequent growth process from the nano- to micro-scale was proposed. In general, we have shown that an accelerated electron beam from an electronic microscope under high vacuum enables in situ visualisation of Ag filaments with subnanometer resolution and offers great potential for addressing many fundamental issues in materials science, chemistry, physics and other fields of science.