Surface-modification of indium tin oxide nanoparticles with titanium dioxide by a nonaqueous process and its photocatalytic properties

Indium tin oxide nanoparticles prepared by co-precipitation were re-dispersed in benzyl alcohol and modified successfully with titanium dioxide using titanium tetrachloride as precursor. The morphologies and the re-dispersing processes of both the initial and modified indium tin oxide nanoparticles were investigated, respectively. The photocatalytic properties of the modified nanoparticles were compared with commercial P25 photocatalyst. It was found that (i) the average diameter of the initial indium tin oxide nanoparticles was 10.7 nm and that of the surface-modified nanoparticles was 14.5 nm; (ii) the optimal ultrasonication time was 10.0 min and 8.0 min for the initial and surface-modified ITO nanoparticles, respectively; (iii) the modified particles possessed a higher photocatalytic activity than commercial P25 photocatalyst in the photodegradation of rhodamine B in aqueous medium at pH 5.00; (iv) the pH of the medium markedly influences the photodegradation efficiency.     

Microstructure and photocatalytic activity of titanium dioxide nanoparticles

Titanium dioxide nanoparticles with an average diameter of about 10 nm are fabricated using a sintering method. The degradation of methyl orange indicates that the photocatalytic efficiency is greatly enhanced, which is measured to be 62.81%. Transmission electron microscopy is used to investigate the microstructure of TiO 2 nanoparticles in order to correlate their photocatalytic properties. High-resolution transmission electron microscopy examinations show that all the nanoparticles belong to the anatase phase, and pure edge dislocations exist in some nanoparticles. The great enhancement of photocatalytic efficiency is attributed to two factors, the quantum size effect and the surface defects in the nanoparticles.     

Fabrication of a solution-processed thin-film transistor using zinc oxide nanoparticles and zinc acetate

We have fabricated a solution-processed ZnO thin-film transistor without vacuum deposition. ZnO nanoparticles were prepared by the polyol method from zinc acetate, polyvinyl pyrrolidone, and diethyleneglycol. The solution-processable semiconductor ink was prepared by dispersing the synthesized ZnO in a solvent. Inverted stagger type thin-film transistors were fabricated by spin casting the ZnO ink on the heavily doped Si wafer with 200 nm thick SiO₂, followed by evaporation of Cr/Au source and drain electrodes. After the drying and heat treatment at 600 C, a relatively dense ZnO film was obtained. The film characteristics were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). In order to obtain the electrical properties of the solution-derived transistor, the on–off ratio, threshold voltage, and mobility were measured.     

Electrochemical capacitance from carbon nanotubes decorated with titanium dioxide nanoparticles in acid electrolyte

The electrochemical activity of an electrode of carbon nanotubes (CNTs) attached with TiO₂ nanoparticles was investigated. A chemical-wet impregnation was used to deposit different TiO₂ particle densities onto the CNT surface, which was chemically oxidized by nitric acid. Transmission electron microscopy showed that each TiO₂ nanoparticle has an average size of 30-50 nm. Nitrogen physisorption measurement indicated that the porosity of CNTs is partially hindered by some titania aggregations at high surface coverage. Cyclic voltammetry measurements in 1 M H₂SO₄ showed that (i) an obvious redox peak can be found after the introduction of TiO₂ and (ii) the specific peak current is proportional to the TiO₂ loading. This enhancement of electrochemical activity was attributed to the fact that TiO₂ particles act as a redox site for the improvement of energy storage. According to our calculation, the electrochemical capacitance of TiO₂ nanocatalysts in acid electrolyte was estimated to be 180 F/g. Charge-discharge cycling demonstrated that the TiO₂-CNT composite electrode maintains stable cycleability of over 200 cycles.     

Optical nonlinearities of Au nanoparticles embedded in a zinc oxide matrix

Optical nonlinearities of Au nanoparticles embedded in zinc oxide (ZnO) matrix have been investigated by the Z-scan method at the wavelength of 532 nm using nanosecond Nd³⁺:YAG laser radiation. The nonlinear refractive index has been measured and the real part of the third-order nonlinear susceptibility is deduced. The results of the investigation of nonlinear refraction using the off-axis Z-scan configuration are presented and the mechanisms responsible for the nonlinear response are discussed. The nonlinear refraction is found to be negative (self-defocusing) in the vicinity of the surface plasmon resonance. Moreover, its strength is shown to be larger for materials having higher gold concentration. Finally, the prevailing influence of the electronic Kerr effect over the possible thermo-optical contribution is demonstrated.     

Synthesis and characterization of zinc oxide nanoparticles by laser ablation of zinc in liquid

We report formation of colloidal suspension of zinc oxide nanoparticles by pulsed laser ablation of a zinc metal target at room temperature in different liquid environment. We have used photoluminescence, atomic force microscopy and X-ray diffraction to characterize the nanoparticles. The sample ablated in deionized water showed the photoluminescence peak at 384 nm (3.23 eV), whereas peaks at 370 nm (3.35 eV) were observed for sample prepared in isopropanol. The use of water and isopropanol as a solvent yielded spherical nanoparticles of 14-20 nm while in acetone we found two types of particles, one spherical nanoparticles with sizes around 100 nm and another platelet-like structure of 1 μm in diameter and 40 nm in width. The absorption peak of samples prepared in deionized water and isopropanol are seen to be substantially blue shifted relative to that of the bulk zinc oxide due to the strong confinement effect. The technique offers an alternative for preparing the nanoparticles of active metal.     

Structural and photoluminescence properties of terbium-doped zinc oxide nanoparticles

We present in this paper a study of the structural and photoluminescence （PL） properties of terbium （Tb） doped zinc oxide （ZnO） nanoparticles synthesized by a simple low temperature chemical precipitation method, using zinc acetate and terbium nitrate in an isopropanol medium with diethanolamine （DEA） as the capping agent at 60 ℃. The as-prepared samples were heat treated and the PL of the annealed samples were studied. The prepared nanoparticles were characterized with X-ray diffraction （XRD）. The XRD patterns show the pattern of typical ZnO nanoparticles and correspond with the standard XRD pattern given by JCPDS card No. 36-1451, showing the hexagonal phase structure. The PL intensity was enhanced due to Tb^3＋ doping, and it decreased at higher concentrations of Tb^3＋ doping after reaching a certain optimum concentration. The PL spectra of Tb^3＋ doped samples exhibited blue, bluish green, and green emissions at 460 nm （5^D3 - 7^F3）, 484 nm （5^D4 - 7^F6）, and 530 nm （5^D4 - 7^F5）, respectively, which were more intense than the emissions for the undoped ZnO sample. Based on the results, an energy level schematic diagram was proposed to explain the possible electron transition processes.     

Sintering of titanium dioxide nanoparticles: a comparison between molecular dynamics and phenomenological modeling

Molecular dynamics simulations were used to determine the melting points of anatase and rutile nanoparticles. The melting points decrease with decrease in particle diameter and are in reasonable agreement with the empirical formula derived by Buffat and Borel. The phenomenological model of Koch and Friedlander is unable to predict the temperature rise during initial stages of sintering with acceptable accuracy. It is argued that the Koch and Friedlander assumption of linear surface reduction rate upon sintering may be inadequate for the time scales under consideration. A theoretical model using direct area measurement from molecular dynamics simulations and a single adjustable parameter is able to predict temperature rise during initial stages of sintering within acceptable error limits.     

Structural,morphological, optical and antibacterial activity of rod-shaped zinc oxide and manganese-doped zinc oxide nanoparticles

Pure ZnO and Mn-doped ZnO nanoparticles were synthesized by Co-precipitate method. The structural characterizations of the nanoparticles were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. UV–Vis, FTIR and photoluminescence (PL) spectroscopy were used for analysing the optical properties of the nanoparticles. XRD results revealed the formation of ZnO and Mn-doped ZnO nanoparticles with wurtzite crystal structure having average crystalline size of 39 and 20 nm. From UV–Vis studies, the optical band-gap energy of 3.20 and 3.25 eV was obtained for ZnO and Mn-doped ZnO nanoparticles, respectively. FTIR spectra confirm the presence of ZnO and Mn-doped ZnO nanoparticles. Photoluminescence analysis of all samples showed four main emission bands: a strong UV emission band, a weak blue band, a weak blue–green band and a weak green band indicating their high structural and optical qualities. The antibacterial efficiency of ZnO and Mn-doped ZnO nanoparticles were studied using disc diffusion method. The Mn-doped ZnO nanoparticles show better antibacterial activity when higher doping level is 10 at% and has longer duration of time.     

Acute toxicological impact of nano- and submicro-scaled zinc oxide powder on healthy adult mice

In this work, the acute oral toxicity of 20- and 120-nm ZnO powder at doses of 1-, 2-, 3-, 4-, 5-g/kg body weight was evaluated referred to the OECD guidelines for testing of chemicals. As the results, both 20- and 120-nm ZnO belong to non-toxic chemicals according to the Globally Harmonized Classification System (GHS) for the classification of chemicals. The distribution determination showed that Zn was mainly retained in the bone, kidney and pancreas after 20- and 120-nm ZnO administration. However, the results of blood measurement suggest that the increase in blood viscosity could be induced by low and median dose of 20-nm ZnO but high dose of 120-nm ZnO. The pathological examination showed that the 120-nm ZnO treated mice had dose–effect pathological damages in stomach, liver, heart and spleen, whereas, 20-nm ZnO displayed negative dose–effect damages in liver, spleen and pancreas. Therefore, we conclude that the liver, spleen, heart, pancreas and bone are the target organs for 20- and 120-nm ZnO oral exposure. More attention should be paid on the potential toxicity induced by low dose of 20-nm ZnO oral exposure.     

Investigation into the antibacterial activity of monodisperse BSA-conjugated zinc oxide nanoparticles

The antibacterial behavior of bovine serum albumin conjugated zinc oxide nanoparticles against Escherichia coli was investigated. The zinc oxide nanoparticles were synthesized by using bovine serum albumin as the structure directing agent. And the morphology and crystal phase of the zinc oxide nanoparticles were determined by transmission electron microscopy, X-ray diffractograms and Fourier transform infrared spectrograph techniques. The synthesized zinc oxide nanoparticles showed high antibacterial activity when compared with plain zinc oxide. And the antibacterial activity was assessed by measuring the growth inhibition and testing the zone of inhibition. Furthermore, the plausible mechanism of antibacterial behavior was attributed to the generation of reactive oxygen species by zinc oxide nanoparticles.     

Preparation, characterization and properties of novel covalently surface-functionalized zinc oxide nanoparticles

Novel covalently surface-modified zinc oxide (ZnO) nanoparticles (NP) (ZHIE) were successfully prepared, which have organic chains composed of hydrophilic amide and urethane linkages, and terminal amino groups on the surfaces, using zinc acetate monohydrate. FTIR spectroscopy, X-ray analysis and TEM observation suggested that the resultant ZHIE NPs have the mean sizes of about 10 nm in diameters, the organic chains linking the amino groups in the terminals and wurtzite crystal structure. UV-vis absorption spectrum of the ZHIE NPs in methanol showed maximum absorption band at 348 nm, supporting the TEM observations. Photoluminescent spectrum measurements depicted that the ZHIE NPs show broad visible emission band on the basis of trapped-electron emission. Cytotoxicity and phagocytosis assays suggested that the ZHIE NPs are noncytotoxic, and the ZHIE-labeled zymosan particles derived by conjugation of the ZHIE NPs with zymosan are internalized into the cells and generate fluorescence based on the ZHIE NPs.     

Influence of photo-induced superhydrophilicity of titanium dioxide nanoparticles on the anti-fouling performance of ultrafiltration membranes

Fouling is one of the most present prominent problems in almost all membrane processes. An increase in the membrane hydrophilicity is one of the effective ways to improve the membrane resistance to fouling. In this research, TiO₂ nanoparticles were deposited on the surface of composite ultrafiltration (UF) membrane, and then irradiated by ultraviolet (UV) light. The coating of the membrane surface with TiO₂ nanoparticles and radiation with (UV) light led to the considerable increase of hydrophilicity on the membrane surface. The deposition of TiO₂ nanoparticles was carried out through coordinance bonds with OH functional groups of the polymer on the membrane surface. The flux through a coated and (UV) light radiated membrane was increased to a large extent compared to a virgin membrane. In this research, the effect of different concentrations of TiO₂ nanoparticles in the presence and absence of (UV) irradiation was investigated, and the role of increasing of hydrophilicity on the anti-fouling property of membranes was studied. In order to characterize the membranes FTIR, XRD, SEM, water contact angle and cross-flow filtration were employed. This procedure is a useful technique for improvement of hydrophilicity to decrease (increase) fouling (anti-fouling performance) and enhance the permeation of membranes.     

Formation of microcapsules containing titanium dioxide nanoparticles by pulse expansion of a supercritical solution into a background gas

The formation of microcapsules with a core of TiO₂ nanoparticles in a shell of polyethylene glycol by pulse expansion (pulse duration of 400 µs) of a supersonic jet of TiO₂-suspension in a supercritical solution of polyethylene glycol (PEG 8000) in CO₂ into a background gas (He) is studied. It is shown that the size of capsules and the content of TiO₂ in them depend on the pressure of the background gas in the inlet chamber in the range from 0.125 to 3 atm. The upper (1.5 atm) and the lower (0.25 atm) limits of the pressure range, in which microcapsules with a relatively high content of titanium dioxide are formed, are determined.     

Comparison between aesthetic and thermal performances of copper oxide and titanium dioxide nano-particulate coatings

Nano-particulate coatings with high reflectance against solar irradiation can control undesirable thermal heating by sunlight absorption. It can reduce the energy consumption for air conditioning of houses and cars. For the objects covered by these coatings and subjected to human sight, e.g. roofing surfaces, high dazzle of reflected visible light can offend the human eyes and spoil the fine view of covered objects. The authors introduced a new optimization method in designing pigmented coatings which considers both thermal and aesthetic effects in previous studies. The optimization is possible by controlling the material, size and concentration of pigment particles. The proposed coatings maximize the reflectance of near infrared (NIR) region to care the thermal effects and minimize the visible (VIS) reflected energy to keep the dark tone because of aesthetic appeal. Two different types of copper oxide pigment particles namely cupric oxide (CuO) and cuprous oxide (Cu₂O) were considered in this study. The optimum characteristics and performances are obtained and compared with titanium dioxide (TiO₂) particle as a typical cool pigment. The results show that cupric oxide has much better performance for our objective.     

Size-mediated cytotoxicity of nanocrystalline titanium dioxide, pure and zinc-doped hydroxyapatite nanoparticles in human hepatoma cells

The evolution of the particle size distribution and the surface composition of silicon carbide and titanium carbide nanoparticle (NP) dispersions were studied. The pre-dispersions were prepared using two commonly used protocols for dispersion: stirring and sonication. Two dispersants were investigated (water and Pluronic F108 1?%) at two stages: pre-dispersion and during in vitro assays. Our data show that for each tested condition, different time-dependent results for the surface chemical composition as well as size and percentage of the agglomerates and the primary particles are observed. De-agglomeration and successive or simultaneous cleaning-wrapping cycles of the nanomaterial are observed and are related to the dispersion method and the medium as well as to the chemical stability of the NP surface. Biological response during in vitro assessment was also performed for one given pre-dispersion time condition and demonstrates that the preparation method significantly alters the results.     

Optimized method of dispersion of titanium dioxide nanoparticles for evaluation of safety aspects in cosmetics

Nanoparticles agglomerate when in contact with biological solutions, depending on the solutions’ nature. The agglomeration state will directly influence cellular response, since free nanoparticles are prone to interact with cells and get absorbed into them. In sunscreens, titanium dioxide nanoparticles (TiO₂-NPs) form mainly aggregates between 30 and 150 nm. Until now, no toxicological study with skin cells has reached this range of size distribution. Therefore, in order to reliably evaluate their safety, it is essential to prepare suspensions with reproducibility, irrespective of the biological solution used, representing the above particle size distribution range of NPs (30–150 nm) found on sunscreens. Thus, the aim of this study was to develop a unique protocol of TiO₂ dispersion, combining these features after dilution in different skin cell culture media, for in vitro tests. This new protocol was based on physicochemical characteristics of TiO₂, which led to the choice of the optimal pH condition for ultrasonication. The next step consisted of stabilization of protein capping with acidified bovine serum albumin, followed by an adjustment of pH to 7.0. At each step, the solutions were analyzed by dynamic light scattering and transmission electron microscopy. The final concentration of NPs was determined by inductively coupled plasma-optical emission spectroscopy. Finally, when diluted in dulbecco’s modified eagle medium, melanocytes growth medium, or keratinocytes growth medium, TiO₂–NPs displayed a highly reproducible size distribution, within the desired size range and without significant differences among the media. Together, these results demonstrate the consistency achieved by this new methodology and its suitability for in vitro tests involving skin cell cultures.     

Interaction between titanium dioxide nanoparticles and human serum albumin revealed by fluorescence spectroscopy in the absence of photoactivation

Titanium dioxide (TiO₂) nanoparticles (NPs) are widely used as an important kind of biomaterials. The interaction between TiO₂ (P25) at 20 nm in diameter and human serum albumin (HSA) was studied by fluorescence spectroscopy in this work. Under the simulative physiological conditions, fluorescence data revealed the presence of a single class of binding site on HSA and its binding constants (K_a) were 2.18±0.04×10⁴, 0.87±0.05×10⁴, 0.68±0.06×10⁴ M⁻¹ at 298, 304 and 310 K, respectively. In addition, according to the Van’t Hoff equation, the thermodynamic functions standard enthalpy (ΔH⁰) and standard entropy (ΔS⁰) for the reaction were calculated to be −75.18±0.15 kJ mol⁻¹ and −170.11±0.38 J mol⁻¹ K⁻¹. These results indicated that TiO₂ NPs bond to HSA mainly by van der Waals force and hydrogen bonding formation in low dielectric media, and the electrostatic interactions cannot be excluded. Furthermore, the effects of common ions on the binding constant of TiO₂ NPs-HSA complex were discussed.     

Toxicity of zinc oxide nanoparticles to zebrafish embryo: a physicochemical study of toxicity mechanism

The biological impact of engineered nanomaterials released into the aquatic environment is a major concern. In this work, the properties of ZnO nanoparticles (nano-ZnO, 30 nm) were characterized in a water suspension (E3 medium), and a zebrafish 96-h post fertilization (hpf) embryo–larval test was performed to assess the toxicity of nano-ZnO suspension. Nano-ZnO was found to readily form aggregates with different sizes; small aggregates (142.4–517.7 nm) were still suspended in E3 medium, but large aggregates (>1 μm) quickly deposited on the bottom of 24-well plates; nano-ZnO was partially dissolved to Zn species (Zn_(dis)) in E3 medium. In the nano-ZnO suspension, small aggregates, Zn_(dis), and large aggregates might jointly exert influence on the development of zebrafish embryos. The embryo toxicity test revealed that nano-ZnO killed zebrafish embryos (50 and 100 mg/L), retarded the embryo hatching (1–25 mg/L), reduced the body length of larvae, and caused tail malformation after the 96 hpf exposure. Zn_(dis) only partially contributed to the toxicity of nano-ZnO. This research highlights the need to further investigate the ecotoxicity of nano-ZnO in the water environment.     

Steady state and time resolved laser-induced fluorescence of garlic plants treated with titanium dioxide nanoparticles

The study involves investigation of the effect of the interaction of titanium dioxide nanoparticles with garlic plant by spectroscopy techniques. For this, garlic plants have been grown in the laboratory under controlled conditions of light flux, temperature, humidity, and nutrient media. The growth and biomass parameters in terms of shoot length, fresh, and dry mass are found to increase upon the treatment of titanium dioxide nanoparticles while a reduction is observed in the root length of the garlic plants. The steady state laser-induced fluorescence, time resolved laser-induced fluorescence, and ultraviolet visible spectra of the control and titanium dioxide nanoparticles-treated plants have been acquired. The curve fitting data reveal that titanium dioxide nanoparticles decrease the intensity and fluorescence intensity ratio of red and far red chlorophyll fluorescence bands indicating increase in the photosynthetic activity and chlorophyll content. The evaluation of life time of the excited chlorophyll molecule shows that life time is effected by the treatment of the titanium dioxide nanoparticles. The results pertaining to ultraviolet visible measurement indicate increase in the concentration of chlorophyll a, chlorophyll b, total chlorophyll, carotenoid, and quercetin in the leaves of garlic plants treated with titanium dioxide nanoparticles.