Concept: Titanium dioxide
The increasing prevalence of tattoos provoked safety concerns with respect to particle distribution and effects inside the human body. We used skin and lymphatic tissues from human corpses to address local biokinetics by means of synchrotron X-ray fluorescence (XRF) techniques at both the micro (μ) and nano (ν) scale. Additional advanced mass spectrometry-based methodology enabled to demonstrate simultaneous transport of organic pigments, heavy metals and titanium dioxide from skin to regional lymph nodes. Among these compounds, organic pigments displayed the broadest size range with smallest species preferentially reaching the lymph nodes. Using synchrotron μ-FTIR analysis we were also able to detect ultrastructural changes of the tissue adjacent to tattoo particles through altered amide I α-helix to β-sheet protein ratios and elevated lipid contents. Altogether we report strong evidence for both migration and long-term deposition of toxic elements and tattoo pigments as well as for conformational alterations of biomolecules that likely contribute to cutaneous inflammation and other adversities upon tattooing.
Titanium dioxide (TiO2) nanoparticles (NPs) are manufactured worldwide in large quantities for use in a wide range of applications. TiO2 NPs possess different physicochemical properties compared to their fine particle (FP) analogs, which might alter their bioactivity. Most of the literature cited here has focused on the respiratory system, showing the importance of inhalation as the primary route for TiO2 NP exposure in the workplace. TiO2 NPs may translocate to systemic organs from the lung and gastrointestinal tract (GIT) although the rate of translocation appears low. There have also been studies focusing on other potential routes of human exposure. Oral exposure mainly occurs through food products containing TiO2 NP-additives. Most dermal exposure studies, whether in vivo or in vitro, report that TiO2 NPs do not penetrate the stratum corneum (SC). In the field of nanomedicine, intravenous injection can deliver TiO2 nanoparticulate carriers directly into the human body. Upon intravenous exposure, TiO2 NPs can induce pathological lesions of the liver, spleen, kidneys, and brain. We have also shown here that most of these effects may be due to the use of very high doses of TiO2 NPs. There is also an enormous lack of epidemiological data regarding TiO2 NPs in spite of its increased production and use. However, long-term inhalation studies in rats have reported lung tumors. This review summarizes the current knowledge on the toxicology of TiO2 NPs and points out areas where further information is needed.
The nanoparticle industry is expected to become a trillion dollar business in the near future. Therefore, the unintentional introduction of nanoparticles into the environment is increasingly likely. However, currently applied risk-assessment practices require further adaptation to accommodate the intrinsic nature of engineered nanoparticles. Combining a chronic flow-through exposure system with subsequent acute toxicity tests for the standard test organism Daphnia magna, we found that juvenile offspring of adults that were previously exposed to titanium dioxide nanoparticles exhibit a significantly increased sensitivity to titanium dioxide nanoparticles compared with the offspring of unexposed adults, as displayed by lower 96 h-EC(50) values. This observation is particularly remarkable because adults exhibited no differences among treatments in terms of typically assessed endpoints, such as sensitivity, number of offspring, or energy reserves. Hence, the present study suggests that ecotoxicological research requires further development to include the assessment of the environmental risks of nanoparticles for the next and hence not directly exposed generation, which is currently not included in standard test protocols.
In this work, we report a direct synthesis of vertically aligned ZnO nanowires on fluorine-doped tin oxide-coated substrates using the chemical vapor deposition (CVD) method. ZnO nanowires with a length of more than 30 μm were synthesized, and dye-sensitized solar cells (DSSCs) based on the as-grown nanowires were fabricated, which showed improvement of the device performance compared to those fabricated using transferred ZnO nanowires. Dependence of the cell performance on nanowire length and annealing temperature was also examined. This synthesis method provided a straightforward, one-step CVD process to grow relatively long ZnO nanowires and avoided subsequent nanowire transfer process, which simplified DSSC fabrication and improved cell performance.
Highly efficient room-temperature ultraviolet (UV) luminescence is obtained in heterostructures consisting of 10-nm-thick ultrathin ZnO films grown on Si nanopillars fabricated using self-assembled silver nanoislands as a natural metal nanomask during a subsequent dry etching process. Atomic layer deposition was applied for depositing the ZnO films on the Si nanopillars under an ambient temperature of 200°C. Based on measurements of photoluminescence (PL), an intensive UV emission corresponding to free-exciton recombination (approximately 3.31 eV) was observed with a nearly complete suppression of the defect-associated, broad-range visible emission peak. As compared to the ZnO/Si substrate, the almost five-times-of-magnitude enhancement in the intensity of PL, which peaked around 3.31 eV in the present ultrathin ZnO/Si nanopillars, is presumably attributed to the high surface/volume ratio inherent to the Si nanopillars. This allowed considerably more amount of ZnO material to be grown on the template and led to markedly more efficient intrinsic emission.
In a mixed solvent of water and ethanol, polystyrene/titanium dioxide (PSt/TiO2) composite particles of core-shell structure were prepared by hydrolysis of tetrabutyl titanate in the presence of cationic PSt particles or anionic PSt particles surface-treated using gamma-aminopropyl triethoxysilane. Hollow TiO2 particles were obtained through calcination of the PSt/TiO2 core-shell particles to burn off the PSt core or through dissolution of the core by tetrahydrofuran (THF). An alternative process constituted of preheating the PSt/TiO2 particles at 200[degree sign]C to allow partial crystallization followed by calcination or PSt dissolution by THF. The outcome TiO2 particles thus prepared were examined by TEM, and hollow TiO2 particles were observed. The crystalline phase structure and phase transformation were characterized, which revealed that preheating before the removal of the PSt core was useful to achieve the desired hollow TiO2 particles, and the calcination process was beneficial to the formation of anatase and rutile structures. The tests of TiO2 particles as catalyst in the photodegradation of Rhodamine B demonstrated that a much higher catalytic activity was observed with the TiO2 hollow particles prepared through calcination combined with preheating.
In this study, zinc oxide (ZnO) nanorod arrays were synthesized using a simple hydrothermal reaction on ZnO seeds/n-silicon substrate. Several parameters were studied, including the heat-treatment temperature to produce ZnO seeds, zinc nitrate concentration, pH of hydrothermal reaction solution, and hydrothermal reaction time. The optimum heat-treatment temperature to produce uniform nanosized ZnO seeds was 400°C. The nanorod dimensions depended on the hydrothermal reaction parameters. The optimum hydrothermal reaction parameters to produce blunt tip-like nanorods (770 nm long and 80 nm in top diameter) were 0.1 M zinc nitrate, pH 7, and 4 h of growth duration. Phase analysis studies showed that all ZnO nanorods exhibited a strong (002) peak. Thus, the ZnO nanorods grew in a c-axis preferred orientation. A strong ultraviolet (UV) emission peak was observed for ZnO nanorods grown under optimized parameters with a low, deep-level emission peak, which indicated high optical property and crystallinity of the nanorods. The produced ZnO nanorods were also tested for their UV-sensing properties. All samples responded to UV light but with different sensing characteristics. Such different responses could be attributed to the high surface-to-volume ratio of the nanorods that correlated with the final ZnO nanorods morphology formed at different synthesis parameters. The sample grown using optimum synthesis parameters showed the highest responsivity of 0.024 A/W for UV light at 375 nm under a 3 V bias.
In this study, the authors report the production of nanocomposite-enhanced phase-change materials (NEPCMs) using the direct-synthesis method by mixing paraffin with alumina (Al2O3), titania (TiO2), silica (SiO2), and zinc oxide (ZnO) as the experimental samples. Al2O3, TiO2, SiO2, and ZnO were dispersed into three concentrations of 1.0, 2.0, and 3.0 wt.%. Through heat conduction and differential scanning calorimeter experiments to evaluate the effects of varying concentrations of the nano-additives on the heat conduction performance and thermal storage characteristics of NEPCMs, their feasibility for use in thermal storage was determined. The experimental results demonstrate that TiO2 is more effective than the other additives in enhancing both the heat conduction and thermal storage performance of paraffin for most of the experimental parameters. Furthermore, TiO2 reduces the melting onset temperature and increases the solidification onset temperature of paraffin. This allows the phase-change heat to be applicable to a wider temperature range, and the highest decreased ratio of phase-change heat is only 0.46%, compared to that of paraffin. Therefore, this study demonstrates that TiO2, added to paraffin to form NEPCMs, has significant potential for enhancing the thermal storage characteristics of paraffin.
This work presents a novel white light device. An yttrium aluminum garnet (YAG) phosphor-incorporated zinc oxide (ZnO) film is deposited on a slide glass substrate by ultrasonic spray pyrolysis. A nanoflower consisting of a hexagonal nanopetal is formed on the surfaces of the samples, and the sizes of the nanopetal are approximately 200 to 700 nm. Additionally, the nanopetal becomes blunted with an increasing incorporated amount of YAG. As the incorporated amount is 1.5 and 2.5 wt.%, the photoluminescence color of the YAG-incorporated ZnO film is nearly white, possibly contributing to the YAG emission and the band-to-deep level transition in the ZnO film.
The prototypical photocatalyst TiO2 exists in different polymorphs, the most common forms are the anatase- and rutile-crystal structures. Generally, anatase is more active than rutile, but no consensus exists to explain this difference. Here we demonstrate that it is the bulk transport of excitons to the surface that contributes to the difference. Utilizing high -quality epitaxial TiO2 films of the two polymorphs we evaluate the photocatalytic activity as a function of TiO2-film thickness. For anatase the activity increases for films up to ~5 nm thick, while rutile films reach their maximum activity for ~2.5 nm films already. This shows that charge carriers excited deeper in the bulk contribute to surface reactions in anatase than in rutile. Furthermore, we measure surface orientation dependent activity on rutile single crystals. The pronounced orientation-dependent activity can also be correlated to anisotropic bulk charge carrier mobility, suggesting general importance of bulk charge diffusion for explaining photocatalytic anisotropies.