Effect on Electron Structure and Magneto-Optic Property of Heavy W-Doped Anatase TiO2

The spin or nonspin state of electrons in W-doped anatase TiO₂ is very difficult to judge experimentally because of characterization method limitations. Hence, the effect on the microscopic mechanism underlying the visible-light effect of W-doped anatase TiO₂ through the consideration of electronic spin or no-spin states is still unknown. To solve this problem, we establish supercell models of W-doped anatase TiO₂ at different concentrations, followed by geometry optimization and energy calculation based on the first-principle planewave norm conserving pseudo-potential method of the density functional theory. Calculation results showed that under the condition of nonspin the doping concentration of W becomes heavier, the formation energy becomes greater, and doping becomes more difficult. Meanwhile, the total energy increases, the covalent weakens and ionic bonds strengthens, the stability of the W-doped anatase TiO₂ decreases, the band gap increases, and the blue-shift becomes more significant with the increase of W doping concentration. However, under the condition of spin, after the band gap correction by the GGA+U method, it is found that the semimetal diluted magnetic semiconductors can be formed by heavy W-doped anatase TiO₂. Especially, a conduction electron polarizability of as high as near 100% has been found for the first time in high concentration W-doped anatase TiO₂. It will be able to be a promising new type of dilute magnetic semiconductor. And the heavy W-doped anatase TiO₂ make the band gap becomes narrower and absorption spectrum red-shift.     

Cellular Toxicity of TiO2 Nanoparticles in Anatase and Rutile Crystal Phase

Titanium dioxide nanoparticles are massively produced and widely used in daily life, which has posed potential risk to human health. However, the molecular mechanism of TiO₂ nanoparticles (NPs) with different crystal phases is not clear. In this study, the characterization of two crystalline phases of TiO₂ NPs is evaluated by transmission electron microscopy and X-ray absorption fine structure spectrum; an interaction of these TiO₂ NPs with HaCaT cells is studied in vitro using transmission electron microscopy, chemical precipitation method, and X-ray absorption fine structure spectrometry. The coordination and surface properties indicate that only the anatase–TiO₂ NPs allow spontaneous reactive oxygen species (ROS) generation, but rutile–TiO₂ NPs do not after dispersion. The interaction between TiO₂ NPs and cellular components might also generate ROS for both anatase–TiO₂ NPs and rutile–TiO₂ NPs. The ROS generation could lead to cellular toxicity if the level of ROS production overwhelms the antioxidant defense of the cell or induces the mitochondrial apoptotic mechanisms. Furthermore, Ti had a direct combination with some protein or DNA after NPs enter the cell, which could also lead to cellular toxicity.     

Low-Temperature Synthesis of Anatase TiO2 Nanoparticles with Tunable Surface Charges for Enhancing Photocatalytic Activity

In this work, the positively or negatively charged anatase TiO₂ nanoparticles were synthesized via a low temperature precipitation-peptization process (LTPPP) in the presence of poly(ethyleneimine) (PEI) and poly(sodium4- styrenesulfonate) (PSS). X-ray diffraction (XRD) pattern and high-resolution transmission electron microscope (HRTEM) confirmed the anatase crystalline phase. The charges of the prepared TiO₂, PEI-TiO₂ and PSS-TiO₂ nanoparticles were investigated by zeta potentials. The results showed that the zeta potentials of PEI-TiO₂ nanoparticles can be tuned from +39.47 mV to +95.46 mV, and that of PSS-TiO₂ nanoparticles can be adjusted from −56.63 mV to −119.32 mV. In comparison with TiO₂, PSS-TiO₂ exhibited dramatic adsorption and degradation of dye molecules, while the PEI modified TiO₂ nanoparticles showed lower photocatalytic activity. The photocatalytic performances of these charged nanoparticles were elucidated by the results of UV-vis diffuse reflectance spectra (DRS) and the photoluminescence (PL) spectra, which indicated that the PSS-TiO₂ nanoparticles showed a lower recombination rate of electron-hole pairs than TiO₂ and PEI-TiO₂.     

P38-Nrf-2 Signaling Pathway of Oxidative Stress in Mice Caused by Nanoparticulate TiO2

Some recent studies have been previously suggested that nanoparticulate titanium dioxide (TiO₂) damaged liver function and decreased immunity of mice, but the spleen injury and its oxidative stress mechanism are still unclear. To understand the spleen injury induced by intragastric administration of nanoparticulate anatase TiO₂ for consecutive 30 days, the spleen pathological changes, the oxidative stress, and p38 and c-Jun N-terminal kinase signaling pathways, along with nuclear factor-κB and nuclear factor-E2-related factor-2 (Nrf-2), were investigated as the upstream events of oxidative stress in the mouse spleen from exposure to nanoparticulate TiO₂. The results suggested that nanoparticulate TiO₂ caused congestion and lymph nodule proliferation of spleen tissue, which might exert its toxicity through oxidative stress, as it caused significant increases in the mouse spleen reactive oxygen species accumulations, subsequently leading to the strong lipid peroxidation and the significant expression of heme oxygenase-1 via the p38-Nrf-2 signaling pathway. The studies on the mechanism by which nanoparticulate TiO₂ induced the p38-Nrf-2 signaling pathway are helpful to a better understanding of the nanoparticulate TiO₂-induced oxidative stress and reduction of immune capacity.     

延迟投饵对厚颌鲂仔鱼的影响

在室内养殖条件下,研究厚颌鲂仔鱼的摄食、耐饥饿和恢复生长能力.试验结果表明:(1)仔鱼在孵出后2～3 d开口摄食,卵黄囊在之后的2 d耗尽,饥饿仔鱼在12～13日龄达到不可逆点(PNR);(2)饥饿仔鱼的初次摄食率在卵黄囊耗尽时达到最高,保持在80%以上的时间为7 d;(3)仔鱼在PNR后死亡率急剧增加,PNR后第3 d仔鱼全部死亡;(4)经恢复生长试验,延迟3 d投饵对仔鱼的存活率影响不大,延迟3～6 d投饵对仔鱼全长生长影响不大.     

BmNPV Resistance of Silkworm Larvae Resulting from the Ingestion of TiO2 Nanoparticles

Bombyx mori nucleopolyhedrovirus (BmNPV) causes infection in the silkworm that is often lethal. The infection is hard to prevent, partly because of the nature of the virus particles and partly because of the different strains of B. mori. Titanium dioxide nanoparticles (TiO₂ NPs) have been demonstrated to have antimicrobial properties. The present study investigated whether TiO₂ NPs added to an artificial diet can increase the resistance of B. mori larvae to BmNPV and examined the molecular mechanism behind any resistance shown. The results indicated that ingested TiO₂ NPs decreased reactive oxygen species and NO accumulation in B. mori larvae under BmNPV infection, which in turn led to a decrease in their growth inhibition and mortality. In addition, the TiO₂ NPs significantly promoted the expression of resistance-related genes, including those encoding superoxide dismutase, catalase, glutathione peroxidase, acetylcholine esterase, carboxylesterase, heat shock protein 21, glutathione S transferase o1, P53, and transferring and of genes encoding cytochrome p302 and nitric oxide synthase. These findings are a useful addition to the understanding of the mechanism of BmNPV resistance of B. mori larvae in response to TiO₂ NPs addition. Such information also provides a theoretical basis for the use of TiO₂ NPs in sericulture.     

In Vitro Toxicity Evaluation of 25-nm Anatase TiO2 Nanoparticles in Immortalized Keratinocyte Cells

Titanium dioxide (TiO(2)) nanoparticles (NPs) are massively fabricated and widely used in daily life, and thus potential risk has been posed to human health. However, the mechanism of the interaction between TiO(2) NPs and cells is still unclear. In this study, the interaction of anatase TiO(2) NPs with HaCaT cells is studied in vitro with multi-techniques. The TiO(2) NPs not only insert into cells through endocytic pathway but also penetrate into the cell. The TiO(2) NPs could produce reactive oxygen species (ROS) after dispersion spontaneously. Furthermore, the interaction between TiO(2) NPs and cellular components might also generate ROS. The ROS generation could lead to cellular toxicity if the level of ROS production overwhelms the antioxidant defense. Cytoskeletal components, particularly the microfilaments and microtubules, cause modifications upon exposure to TiO(2) NPs. With all results, the toxicological effects of TiO(2) NPs on HaCaT cell can be simplified into six events.     

A glucose biosensor based on TiO(2)-Graphene composite

A novel glucose biosensor was developed based on the adsorption of glucose oxidase at a TiO(2)-Graphene (GR) nanocomposite electrode. A TiO(2)-GR composite was synthesized from a colloidal mixture of TiO(2) nanparticles and graphene oxide (GO) nanosheets by an aerosol assisted self-assembly (AASA). The particle morphology of all TiO(2)-GR composites was spherical in shape. It was observed that micron-sized TiO(2) particles were encapsulated by GR nanosheets and that the degree of encapsulation was proportional to the ratio of GO/TiO(2). The amperometric response of the glucose biosensor fabricated by the TiO(2)-GR composite was linear against a concentration of glucose ranging from 0 to 8mM at -0.6V. The highest sensitivity was noted at about 6.2μA/mMcm(2). The as prepared glucose biosensor based on the TiO(2)-GR composite showed higher catalytic performance for glucose redox than a pure TiO(2) and GR biosensor.     

Effect of the photocatalytic activity of TiO(2) on plasmid DNA

We investigated the photodynamic DNA strand-breaking activity of TiO(2). A solution of super-coiled pBR 322 DNA was irradiated with 5 J/cm(2) of UVA in the presence of TiO(2) and the products were analyzed by using gel electrophoresis. The ratio of open-circular DNA to super-coiled circular DNA was calculated from the resulting peak areas as a DNA strand-breaking index (SBI). The SBI of anatase-structure TiO(2) (band gap=3.23 eV) was greater than that of rutile structure (band gap=3.06 eV), and the level of SBI correlated with the photocatalytic activity for degradation of 2-propanol. The inhibitory effects of active oxygen scavengers, including DMSO, glutathione and histidine, on the DNA strand-breaking activity were examined. All of the scavengers except ascorbic acid showed inhibitory effects, as did several polyhydric alcohols including mannitol, a well-known hydroxyl radical scavenger. These results suggest that the photodynamic DNA strand-breaking activity of TiO(2) is due to active oxygen species, especially hydroxyl radicals. Polyhydric alcohols showed an inverse correlation between the inhibitory effect on DNA strand-breaking activity and the octanol/water partition coefficient (logP).     

Genotoxicity of inhaled nanosized TiO(2) in mice

In vitro studies have suggested that nanosized titanium dioxide (TiO(2)) is genotoxic. The significance of these findings with respect to in vivo effects is unclear, as few in vivo studies on TiO(2) genotoxicity exist. Recently, nanosized TiO(2) administered in drinking water was reported to increase, e.g., micronuclei (MN) in peripheral blood polychromatic erythrocytes (PCEs) and DNA damage in leukocytes. Induction of micronuclei in mouse PCEs was earlier also described for pigment-grade TiO(2) administered intraperitoneally. The apparent systemic genotoxic effects have been suggested to reflect secondary genotoxicity of TiO(2) due to inflammation. However, a recent study suggested that induction of DNA damage in mouse bronchoalveolar lavage (BAL) cells after intratracheal instillation of nanosized or fine TiO(2) is independent of inflammation. We examined here, if inhalation of freshly generated nanosized TiO(2) (74% anatase, 26% brookite; 5 days, 4 h/day) at 0.8, 7.2, and (the highest concentration allowing stable aerosol production) 28.5 mg/m(3) could induce genotoxic effects in C57BL/6J mice locally in the lungs or systematically in peripheral PCEs. DNA damage was assessed by the comet assay in lung epithelial alveolar type II and Clara cells sampled immediately following the exposure. MN were analyzed by acridine orange staining in blood PCEs collected 48 h after the last exposure. A dose-dependent deposition of Ti in lung tissue was seen. Although the highest exposure level produced a clear increase in neutrophils in BAL fluid, indicating an inflammatory effect, no significant effect on the level of DNA damage in lung epithelial cells or micronuclei in PCEs was observed, suggesting no genotoxic effects by the 5-day inhalation exposure to nanosized TiO(2) anatase. Our inhalation exposure resulted in much lower systemic TiO(2) doses than the previous oral and intraperitoneal treatments, and lung epithelial cells probably received considerably less TiO(2) than BAL cells in the earlier intratracheal study.     

Effects of metal oxide nanoparticles (TiO2, Al2O3, SiO2 and ZnO) on waste activated sludge anaerobic digestion

The effect of metal oxide nanoparticles (nano-TiO2, nano-Al2O3, nano-SiO2 and nano-ZnO) on anaerobic digestion was investigated by fermentation experiments using waste activated sludge as the substrates. Nano-TiO2, nano-Al2O3 and nano-SiO2 in doses up to 150 milligram per gram total suspended solids (mg/g-TSS) showed no inhibitory effect, whereas nano-ZnO showed inhibitory effect with its dosages increased. The methane generation was the same as that in the control when in the presence of 6 mg/g-TSS of nano-ZnO, however, which decreased respectively to 77.2% and 18.9% of the control at 30 and 150 mg/g-TSS. The released Zn2+ from nano-ZnO was an important reason for its inhibitory effect on methane generation. It was found that higher dosages of nano-ZnO inhibited the steps of sludge hydrolysis, acidification and methanation. Also, the activities of protease, acetate kinase (AK) and coenzyme F420 were inhibited by higher dosages of nano-ZnO during WAS anaerobic digestion.     

Optimisation of the Photonic Efficiency of TiO2 Decorated on MWCNTs for Methylene Blue Photodegradation

MWCNTs/TiO₂ nanocomposite was prepared by oxidising MWCNT in H₂SO₄/HNO₃ then decorating it with TiO₂-p25 nanopowder. The composites were characterised using XRD, TEM, FT-IR PL and UV−vis spectroscopy. The TEM images have shown TiO₂ nanoparticles immobilised onto the sidewalls of the MWCNTs. The UV-vis spectrum confirms that the nanocomposites can significantly absorb more light in the visible regions compared with the commercial TiO₂ (P25). The catalytic activity of these nanocomposites was determined by photooxidation of MB aqueous solution in the presence of visible light. The MWCNTs/TiO₂ (1:3) mass ratio showed maximum degradation efficiency. However, its activity was more favourable in alkaline and a neutral pH than an acidic medium.     

The Effects of Early Feeding Experience on Long-term Seed Choice by Canaries (Serinus canaria)

Early experience has been found to have long-term effects on behaviour such as social imprinting and song learning. In this paper we investigate whether early experience with particular types of food can lead to long-term feeding preferences in canaries. For 8 wk following the onset of independent foraging, two groups of naive fledgling canaries were reared on different diets. One group had a choice of four seed types, while individuals in the other group received only one type of seed. After this training period, all the birds were given a mixed seed diet for a further 15 wk, and then their preference for the original seeds was tested. All six birds that had been given four seeds during the training period showed the same preference, namely: hemp > niger > millet > linseed. However, all the birds that had been trained on one seed type only, still preferred the seed on which they had been trained. After a further 23 wk on a mixed-seed diet, birds from the restricted early diet group showed no further preference for the seed on which they were trained, and their seed choice at this stage was similar to the birds that had received four seeds. We conclude that early experience can affect food choice in canaries for at least 15 wk, but is subordinate to other influences in the longer term.     

Nanoparticulate platinum(II) anticancer drug: synthesis and characterization of amphiphilic cyclotriphosphazene-platinum(II) conjugates

Novel cyclotriphosphazene-platinum(II) conjugates were prepared by hydrolysis and platination of the amphiphilic cyclotriphosphazenes grafted with equimolar hydrophilic methoxy-poly(ethylene glycol) (MPEG) and hydrophobic oligopeptide. These macromolecular conjugates were found to form stable nanoparticles with a mean diameter of approximately 90-200 nm depending on the hydrophobicity of the conjugated (diamine)platinum moieties. The nanoparticulate platinum(II) conjugates have shown temperature and concentration dependent particle sizes. However, the particle sizes of the conjugates were found to decrease to a certain size as the solution concentration was decreased but remained stable even at 10 microM, which is enough for systemic delivery by injection. The conjugates exhibited lower in vitro cytotoxicity than cisplatin but reasonably good activity against selected human tumor cell lines.     

Melatonin and TiO2 NPs Application-Induced Changes in Growth,Photosynthesis, Antioxidant Enzymes Activities and Secondary Metabolites in Stevia (Stevia rebaudiana Bertoni) Under Drought Stress Conditions

Journal of Plant Growth Regulation - Drought stress is one of the major constraints on the growth and productivity of crop plants. Recently, new approaches have been employed in order to cope with...     

Photodynamic activity of platinum(IV) chloride surface-modified TiO2 irradiated with visible light

The visible light-induced phototoxicity of titanium dioxide modified with platinum(IV) chloride complexes, [TiO2/PtCl4], was tested. In vitro experiments with the mouse melanoma cells (S-91) have demonstrated phototoxicity of the [TiO2/PtCl4] material. Detection of efficiently generated various reactive oxygen species (.OH, O2. -, H2O2, 1O2) and also reactive chlorine species has proven the photodynamic activity of the tested material, induced by visible light (lambda>455 nm). The cellular death (recognized as a necrosis) is a result of the cell membrane peroxidation.     

Spatiotemporal Effects of Supplementary Feeding of Wild Boar (Sus scrofa) on Artificial Ground Nest Depredation

Supplementary feeding of ungulates, being widely used in game management, may have unwanted consequences. Its role in agricultural damage is well-studied, but few studies have considered the potential for the practice to attract ground nest predators. Our goal was to identify the factors influencing ground nest predation in the vicinity of year-round supplementary feeding sites for wild boar and to characterise their spatiotemporal scope. We conducted two separate artificial ground nest experiments in five different hunting districts in south-eastern Estonia. The quantity of food provided and distance of a nest from the feeding site were the most important factors determining predation risk. Larger quantities of food resulted in higher predation risk, while predation risk responded in a non-linear fashion to distance from the feeding site. Although predation risk eventually decreases if supplementary feeding is ceased for at least four years, recently abandoned feeding sites still pose a high predation risk.