Dissolution Of Zinc Oxide Research Articles

Enhancing the Electrochemical Performance of ZnO-Co3O4 and Zn-Co-O Supercapacitor Electrodes Due to the In Situ Electrochemical Etching Process and the Formation of Co3O4 Nanoparticles

Zinc oxide (ZnO) and materials based on it are often used to create battery-type supercapacitor electrodes and are considered as promising materials for hybrid asymmetric supercapacitors. However, when creating such electrodes, it is necessary to take into account the instability and degradation of zinc oxide in aggressive environments with a non-neutral pH. To the best of our knowledge, studies of the changes in the properties of ZnO-containing electrodes in alkaline electrolytes have not been carried out. In this work, changes in the structure and properties of these electrodes under alkaline treatment were investigated using the example of ZnO-containing composites, which are often used for the manufacturing of supercapacitor electrodes. Supercapacitor electrodes made of two materials containing ZnO were studied: (i) a heterogeneous ZnO-Co3O4 system, and (ii) a hexagonal h-Zn-Co-O solid solution. A comparison was made between the structure and properties of these materials before and after in situ electrochemical oxidation in the process of measuring cyclic voltammetry and galvanostatic charge/discharge. It has been shown that the structure of both nanoparticles of the heterogeneous ZnO-Co3O4 system and the h-Zn-Co-O solid solution changes due to the dissolution of ZnO in the alkaline electrolyte 3.5 M KOH, with the short-term alkaline treatment producing cobalt and zinc hydroxides, and long-term exposure leading to electrochemical cyclic oxidation–reduction, forming cobalt oxide Co3O4. Since the resulting cobalt oxide nanoparticles are immobilized in the electrode structure, a considerable specific capacity of 446 F g−1 or 74.4 mA h g−1 is achieved at a mass loading of 0.0105 g. The fabricated hybrid capacitor showed a good electrochemical performance, with a series resistance of 0.2 Ohm and a capacitance retention of 87% after 10,000 cycles.

In Situ Monitoring of Aptamer-Protein Binding on a ZnO Surface Using Spectroscopic Ellipsometry.

The dissolution of zinc oxide is investigated using spectroscopic ellipsometry to investigate its suitability as a platform for biosensing applications. The results indicate that once the ZnO surface has been functionalised, it is suitably protected, and no significant dissolving of the ZnO occurs. The binding kinetics of the SARS-CoV-2 spike protein on aptamer-functionalised zinc oxide surfaces are subsequently investigated. Values are extracted for the refractive index and associated optical constants for both the aptamer layer used and the protein itself. It is shown that upon an initial exposure to the protein, a rapid fluctuation in the surface density is observed. After around 20 min, this effect stabilises, and a fixed increase in the surface density is observed, which itself increases as the concentration of the protein is increased. This technique and setup are demonstrated to have a limit-of-detection down to 1 nanomole (nM) and display a linear response to concentrations up to 100 nM.

Insitu electron microscopy techniques for nanoparticle dispersion analysis of commercial sunscreen

Nanoparticles are common active ingredients within many commercial products including sunscreen. Consequently, accurate characterisation of nanoparticles in these products is vital to enhance product design, whilst also understanding the toxicological implications of these nanoparticles. Whilst bulk techniques are useful in providing some information, they often cannot resolve individual particles, and therefore electron microscopy can be used for high-resolution nanoparticle characterisation. However, conventional high vacuum dry TEM does not accurately represent nanoparticle dispersions and other in situ methods must be used. Here, we use a combination of techniques including liquid cell transmission electron microscopy (LCTEM), cryogenic (cryo)-TEM and cryo-scanning electron microscopy (SEM) to characterise a commercial sunscreen containing titanium dioxide (TiO2) and zinc oxide (ZnO) nanoparticles. Our work illustrates that whilst LCTEM does not require any sample preparation more beam artefacts can occur causing ZnO dissolution with only TiO2 nanoparticles visualised. Comparatively, cryo-TEM allows characterisation of both ZnO and TiO2, yet only cryo-SEM could be used to analyse the pure product (without dilution) but biased the characterisation to the larger fraction of nanoparticles and agglomerates. Ultimately, only with a combination of different in situ EM techniques can an accurate characterisation of commercial products be achieved in order to ensure effective and safe product design and manufacture.

The pH dependence of dissolution kinetics of zinc oxide

Zinc oxide (ZnO) powders are used as feed additives for supplementation in diet of animals. Because zinc dissolution rate strongly influences the digestibility of zinc by animals and their stomach has variable pH, the dissolution kinetics of ZnO are studied at the several pH of relevance between 2 and 4. The dissolution of ZnO has been investigated with the help of modeling the dissolution kinetics measured in vitro at various pH. Dissolution is faster in acidic medium. But the acceleration of dissolution at low pH is moderate compared to what would be expected on the basis of the strong pH dependence of ZnO solubility. The concentration of Zn2+ in the quiescent medium at the surface of ZnO particles is much lower than its solubility. It is proposed as a rationale, that hydroxide anions released during dissolution accumulate at the surface of the positively charged ZnO surface, and that the dissolution kinetics is mainly controlled by the diffusion of H+ ions from the bulk solution to the surface.

Growth Inhibition of Gram-Positive and Gram-Negative Bacteria by Zinc Oxide Hedgehog Particles.

PurposeNanomaterials for antimicrobial applications have gained interest in recent years due to the increasing bacteria resistance to conventional antibiotics. Wound sterilization, water treatment and surface decontamination all avail from multifunctional materials that also possess excellent antibacterial properties, eg zinc oxide (ZnO). Here, we assess and compare the effects of synthesized hedgehog-like ZnO structures and commercial ZnO particles with and without mixing on the inactivation of bacteria on surfaces and in liquid environments.MethodsGram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria in microbial culture medium were added to reverse spin bioreactors that contained different concentrations of each ZnO type to enable dynamic mixing of the bacteria-ZnO suspensions. Optical density of the bacteria-ZnO suspensions was measured in real-time and the number of viable bacteria after 24 h exposure was determined using standard microbiological techniques. The concentration of zinc ion generated from ZnO dissolution in different liquid types was estimated from the dynamic interaction exposure. Static antibacterial tests without agitation in liquid media and on agar surface were performed for comparison.ResultsA correlation between increasing ZnO particle concentration and reduction in viable bacteria was not monotonous. The lowest concentration tested (10 µg/mL) even stimulated bacteria growth. The hedgehog ZnO was significantly more antibacterial than commercial ZnO particles at higher concentrations (up to 1000 µg/mL tested), more against E. coli than S. aureus. Minimum inhibitory concentration in microwell plates was correlated with those results. No inhibition was detected for any ZnO type deposited on agar surface. Zinc ion release was greatly suppressed in cultivation media. Scanning electron microscopy images revealed that ZnO needles can pierce membrane of bacteria whereas the commercial ZnO nanoparticles rather agglomerate on the cell surface.ConclusionThe inhibition effects are thus mainly controlled by the interaction dynamics between bacteria and ZnO, where mixing greatly enhances antibacterial efficacy of all ZnO particles. The efficacy is modulated also by ZnO particle shapes, where hedgehog ZnO has superior effect, in particular at lower concentrations. However, at too low concentrations, ZnO can stimulate bacteria growth and must be thus used with caution.

Composite coatings with polymeric modified ZnO nanoparticles and nanocontainers with inhibitor for corrosion protection of low carbon steel

Incorporation of zinc oxide (ZnO) nanoparticles and ZnO based nanocontainers with corrosion inhibitor Safranin into the matrix of standard zinc coatings is applied for preparation of coatings with improved corrosion protection for mild steel. A cationic polyelectrolyte polyethylenimine (PEI) is used to stabilize the ZnO suspension before electrodeposition of the ZnO nanoparticles on the steel surface. Encapsulation of Safranin is realized in polymer coatings on ZnO nanoparticles prepared using layer-by-layer assembly of polyacrylic acid (PAA) and PEI. The average size and surface charge of the PEI coated ZnO nanoparticles and ZnO based nanocontainers with inhibitor are identified using dynamic and electric light scattering methods and microelectrophoresis. The ZnO nanoparticles or ZnO nanocontainers are electrodeposited on steel (cathode) substrates at pH 7.5 to minimize the effect of ZnO dissolution. In a second step, ordinary zinc coatings are electrodeposited on the ZnO nanoparticles or ZnO nanocontainers covered steel samples from zinc sulfate electrolyte at pH 4.5-5.0. The surface morphology of the coatings and their corrosion behavior are studied by scanning electron microscopy and electrochemical methods potentiodynamic polarization and polarization resistance. The results show better corrosion protection of steel by composite coatings as compare to the bare zinc coating. The composite coating with inhibitor shows better protective characteristics in comparison with the other one. The two-step approach described herein can be used for preparation of composite coatings where preservation of particles functionality is required.

Stability of TiO2-coated ZnO photocatalytic thin films for photodegradation of methylene blue

Investigations on the stability of titanium dioxide (TiO2)-coated zinc oxide (ZnO) thin films upon repeated uses for methylene blue (MB) degradation were conducted. Photocorrosion of ZnO, upon exposure to light in aqueous media, can affect the photocatalytic performance due to loss of material. Hence, coating with a more stable metal oxide was seen as a way to suppress the effects of photocorrosion. In this study, homogeneous wurtzite ZnO nanostructured thin films were obtained from thermal oxidation of sputter-deposited Zn films on glass substrates. TiO2 was subsequently deposited onto the ZnO nanostructured thin films using a reactive magnetron sputtering system in an admixture of argon and oxygen gases. After deposition, the thin films were annealed at 500 °C for 1 h. The photocatalytic efficiency and stability of the thin films were investigated after multiple degradation cycles. The addition of a TiO2 film increased the surface roughness and blueshifted the absorption edge of the ZnO thin films. The coated films obtained up to 94.3% degradation efficiency of MB after a 180-min exposure cycle using a solar light simulator. After three cycles, degradation efficiency decreased for the uncoated ZnO photocatalysts. Analysis of the MB solution after one degradation cycle revealed the presence of Zn2+ ions attributed to the effects of photocorrosion. Higher Zn2+ concentrations were observed when the ZnO surface is uncoated. This study showed that the addition of a thin, antiphotocorrosion material such as TiO2 layer decreased the dissolution of ZnO caused by photocorrosion without a significant reduction in the photodegradation efficiency.

High-temperature annealing of ZnO nanoparticles increases the dissolution magnitude and rate in water by altering O vacancy distribution

The effects and mechanism of high-temperature annealing, a frequently-used strategy to modulate the properties of nanoparticles (NPs), on the dissolution of zinc oxide (ZnO) NPs are investigated in this study. The results show that annealing increases the ZnO NPs dissolution magnitude via increasing O vacancy abundance on the surface and in the bulk crystal. The face-dependent distribution of O vacancy is revealed by characterizing ZnO single crystal, and the (000-1) face has a higher abundance than the (10-10) face. Particularly, O vacancy abundance in the bulk (000-1) is about 3 times higher than in the bulk (10-10). Annealing further strengthens the face-dependence of O vacancy distribution, therefore both raw and annealed (000-1) faces contribute dominantly to the dissolution of ZnO NPs. Typical topographies of the surface defect sites on the (000-1) face and their evolutions during dissolution are collected. Annealing promotes the formation of larger and deeper etching pits. Elevated solution temperature and annealing synergize to further accelerate ZnO dissolution. The dissolution behaviors of ZnO NPs with different annealing statuses, surface properties, and solution temperatures investigated in this study have potential implications to the evaluations of environmental fate and risk of metal oxide NPs.

Zinc oxide end-capped Fe3O4@mSiO2 core-shell nanocarriers as targeted and responsive drug delivery system for chemo-/ions synergistic therapeutics

Multifunctional core-shell nanocarriers based on zinc oxide (ZnO)-gated magnetic mesoporous silica nanoparticles (MMSN) were prepared for cancer treatment through magnetic targeting and pH-triggered controlled drug release. Under an external magnetic field, the MMSN could actively deliver chemotherapeutic agent, daunomycin (DNM), to the targeted sites. At neutral aqueous, the functionalized MMSN could stably accommodate the DNM molecules since the mesopores were capped by the ZnO gatekeepers. In contrast, at the acid intercellular environment, the gatekeepers would be removed to control the release of drugs due to the dissolution of ZnO. Meanwhile, ZnO quantum dots not only rapidly dissolve in an acidic condition of cancer cells but also enhance the anti-cancer effect of Zn2+. An in vitro controlled release proliferation indicated that the acid sensitive ZnO gatekeepers showed well response by the ‘on-off’ switch of the pores. Cellular experiments against cervical cancer cell (HeLa cells) further showed that functionalized MMSN significantly suppressed cancer cells growth through synergistic effects between the chemotherapy and Zn2+ ions with monitoring the treatment process. These results suggested that the ZnO-gated MMSN platform is a promising approach to serve as a pH-sensitive system for chemotherapies delivery and Zn2+ controlled release for further application in the treatment of various cancers by synergistic effects.

DNA Adsorption by ZnO Nanoparticles near Its Solubility Limit: Implications for DNA Fluorescence Quenching and DNAzyme Activity Assays.

Zinc oxide (ZnO) is a highly important material, and Zn(2+) is a key metal ion in biology. ZnO and Zn(2+) interconvert via dissolution and hydrolysis/condensation. In this work, we explore their interactions with DNA, which is important for biointerface, analytical, and bioinorganic chemistry. Fluorescently labeled DNA oligonucleotides were adsorbed by a low concentration (around 5 μg/mL) of ZnO nanoparticles, near the solubility limit. Right after mixing, fluorescence quenching occurred, indicating DNA adsorption. Then, fluorescence recovered, attributable to ZnO dissolution. The dissolution rate followed A5 > T5 > C5. Dissolution was slower with longer DNA. The adsorption affinity was also measured by a displacement assay to be G5 > C5 > T5 > A5, suggesting that tightly adsorbed DNA can retard ZnO dissolution. Electrostatic interactions are important for DNA adsorption because ZnO is positively charged at neutral pH, and a high salt concentration inhibits DNA adsorption. Next, in situ formation of ZnO from Zn(2+) was studied. First, titrating Zn(2+) into a fluorescently labeled oligonucleotide at pH 7.5 resulted in an abrupt fluorescence quenching beyond 0.2 mM Zn(2+). At pH 6, quenching occurred linearly with the Zn(2+) concentration, suggesting the effect of Zn(2+) precipitation at pH 7.5. Second, a Zn(2+)-dependent DNA-cleaving DNAzyme was studied. This DNAzyme was inhibited at higher than 2 mM Zn(2+), attributable to Zn(2+) precipitation and adsorption of the DNAzyme. This paper has established the interplay between DNA, Zn(2+), and ZnO. This understanding can avoid misinterpretation of DNA assay results and adds knowledge to DNA immobilization.

Growth of a Novel Nanostructured ZnO Urchin: Control of Cytotoxicity and Dissolution of the ZnO Urchin

The applications of zinc oxide (ZnO) nanowires (NWs) in implantable wireless devices, such as diagnostic nanobiosensors and nanobiogenerators, have recently attracted enormous attention due to their unique properties. However, for these implantable nanodevices, the biocompatibility and the ability to control the behaviour of cells in contact with ZnO NWs are demanded for the success of these implantable devices, but to date, only a few contrasting results from their biocompatibility can be found. There is a need for more research about the biocompatibility of ZnO nanostructures and the adhesion and viability of cells on the surface of ZnO nanostructures. Here, we introduce synthesis of a new nature-inspired nanostructured ZnO urchin, with the dimensions of the ZnO urchin’s acicula being controllable. To examine the biocompatibility and behaviour of cells in contact with the ZnO urchin, the Madin-Darby canine kidney (MDCK) epithelial cell line was chosen as an in vitro experimental model. The results of the viability assay indicated that, compared to control, the number of viable cells attached to the surface of the ZnO urchin and its surrounding area were reduced. The measurements of the Zn contents of cell media confirmed ZnO dissolution, which suggests that the ZnO dissolution in cell culture medium could lead to cytotoxicity. A purposeful reduction of ZnO cytotoxicity was achieved by surface coating of the ZnO urchin with poly(vinylidene fluorid-co-hexafluoropropylene) (PVDF-HFP), which changed the material matrix to slow the Zn ion release and consequently reduce the cytotoxicity of the ZnO urchin without reducing its functionality.Electronic supplementary materialThe online version of this article (doi:10.1186/s11671-015-1145-3) contains supplementary material, which is available to authorized users.

Effects of Natural Organic Matter Properties on the Dissolution Kinetics of Zinc Oxide Nanoparticles.

The dissolution of zinc oxide (ZnO) nanoparticles (NPs) is a key step of controlling their environmental fate, bioavailability, and toxicity. Rates of dissolution often depend upon factors such as interactions of NPs with natural organic matter (NOM). We examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution using anodic stripping voltammetry to directly measure dissolved zinc concentrations. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg C L(-1)) for Suwannee River humic and fulvic acids and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. The findings of this study facilitate a better understanding of the fate of ZnO NPs in organic-rich aquatic environments and highlight SUVA as a facile and useful indicator of NOM interactions with metal-based nanoparticles.

Dissolution of zinc oxide in a protic ionic liquid with the 1-methylimidazolium cation and electrodeposition of zinc from ZnO/ionic liquid and ZnO/ionic liquid–water mixtures

Abstract We show that zinc oxide can be dissolved in the protic ionic liquid 1-methylimidazolium trifluoromethylsulfonate, [MIm]TfO at quite a high concentration (~ 2.5 mol/L). FTIR and Raman spectra revealed the association of zinc ions with 1-methylimidazole. The ZnO/[MIm]TfO solutions and their mixtures with water were employed as electrolytes for the electrodeposition of zinc. High current density electrodeposition of zinc can be achieved in the employed electrolytes. Spongy-like zinc structures with a high porosity were obtained in ZnO/[MIm]TfO and the formation of Au1.2Zn8.8 alloy was observed. Compact and hexagonal zinc deposits were found in the presence of water. The present results show the potential of ionic liquids as electrolytes for rechargeable zinc–air batteries.

Implications of the stability behavior of zinc oxide nanoparticles for toxicological studies

The increasing use of zinc oxide (ZnO) nano- particles in sunscreens and other cosmetic products demands a risk assessment that has to be done in toxico- logical studies. Such investigations require profound knowledge of the behavior of ZnO in cell culture media. The current study was performed to get well-dispersed suspensions of a hydrophilic (ZnO-hydro) and a lipophilic coated (ZnO-lipo) ZnO nanomaterial for use in in vitro tests. Therefore, systematic tests were carried out with common dispersants (phosphate, lecithin, proteins) to elu- cidate chemical and physical changes of ZnO nanoparticles in water and physiological solutions (PBS, DMEM). Non- physiological stock suspensions were prepared using ultrasonication. Time-dependent changes of pH, conduc- tivity, zeta potential, particle size and dissolution were recorded. Secondly, the stock suspensions were added to physiological media with or without albumin (BSA) or serum (FBS), to examine characteristics such as agglom- eration and dissolution. Stable stock suspensions were obtained using phosphate as natural and physiological electrostatic stabilizing agent. Lecithin proved to be an effective wetting agent for ZnO-lipo. Although the particle size remained constant, the suspension changed over time. The pH increased as a result of ZnO dissolution and for- mation of zinc phosphate complexes. The behavior of ZnO in physiological media was found to depend strongly on the additives used. Applying only phosphate as additive, ZnO- hydro agglomerated within minutes. In the presence of lecithin or BSA/serum, agglomeration was inhibited. ZnO dissolution was higher under physiological conditions than in the stock suspension. Serum especially promoted this process. Using body-related dispersants (phosphate, leci- thin) non-agglomerating stock suspensions of hydrophilic and lipophilic ZnO were prepared as a prerequisite to perform meaningful toxicological investigation. Both nanomaterials showed a non-negligible dissolution behav- ior that strongly depended on the surrounding conditions. Agglomeration of ZnO particles in physiological media is a complex function of particle coating, used dispersants and serum proteins if supplemented. The present study gives a clear guideline how to prepare and handle suspensions with ZnO for in vitro testing and allows the correlation between the chemical-physical particles behavior with findings from toxicological tests.

Superior Antibacterial Activity of Zinc Oxide/Graphene Oxide Composites Originating from High Zinc Concentration Localized around Bacteria

New materials with good antibacterial activity and less toxicity to other species attract numerous research interest. Taking advantage of zinc oxide (ZnO) and graphene oxide (GO), the ZnO/GO composites were prepared by a facile one-pot reaction to achieve superior antibacterial properties without damaging other species. In the composites, ZnO nanoparticles (NPs), with a size of about 4 nm, homogeneously anchored onto GO sheets. The typical bacterium Escherichia coli and HeLa cell were used to evaluate the antibacterial activity and cytotoxicity of the ZnO/GO composites, respectively. The synergistic effects of GO and ZnO NPs led to the superior antibacterial activity of the composites. GO helped the dispersion of ZnO NPs, slowed the dissolution of ZnO, acted as the storage site for the dissolved zinc ions, and enabled the intimate contact of E. coli with ZnO NPs and zinc ions as well. The close contact enhanced the local zinc concentration pitting on the bacterial membrane and the permeability of the bacterial membrane and thus induced bacterial death. In addition, the ZnO/GO composites were found to be much less toxic to HeLa cells, compared to the equivalent concentration of ZnO NPs in the composites. The results indicate that the ZnO/GO composites are promising disinfection materials to be used in surface coatings on various substrates to effectively inhibit bacterial growth, propagation, and survival in medical devices.

Quantification of ZnO Nanoparticle Uptake, Distribution, and Dissolution within Individual Human Macrophages

The usefulness of zinc oxide (ZnO) nanoparticles has led to their wide distribution in consumer products, despite only a limited understanding of how this nanomaterial behaves within biological systems. From a nanotoxicological viewpoint the interaction(s) of ZnO nanoparticles with cells of the immune system is of specific interest, as these nanostructures are readily phagocytosed. In this study, rapid scanning X-ray fluorescence microscopy was used to assay the number ZnO nanoparticles associated with ∼1000 individual THP-1 monocyte-derived human macrophages. These data showed that nanoparticle-treated cells endured a 400% elevation in total Zn levels, 13-fold greater than the increase observed when incubated in the presence of an equitoxic concentration of ZnCl2. Even after excluding the contribution of internalized nanoparticles, Zn levels in nanoparticle treated cells were raised ∼200% above basal levels. As dissolution of ZnO nanoparticles is critical to their cytotoxic response, we utilized a strategy combining ion beam milling, X-ray fluorescence and scanning electron microscopy to directly probe the distribution and composition of ZnO nanoparticles throughout the cellular interior. This study demonstrated that correlative photon and ion beam imaging techniques can provide both high-resolution and statistically powerful information on the biology of metal oxide nanoparticles at the single-cell level. Our approach promises ready application to broader studies of phenomena at the interface of nanotechnology and biology.

Dissolution of ZnO Nanoparticles at Circumneutral pH: A Study of Size Effects in the Presence and Absence of Citric Acid

Understanding size-dependent processes, including dissolution, of engineered nanoparticles is essential in addressing the potential environmental and health impacts of these materials as well as their long-term stability. In this study, experimental measurements of size-dependent dissolution of well-characterized zinc oxide (ZnO) nanoparticles with particle diameters in the range of 4 to 130 nm have been measured at circumneutral pH (pH 7.5) and compared. Dissolution was found to be enhanced with smaller ZnO nanoparticles compared to larger-sized particles, even though the nanoparticles were present in solution as aggregates with hydrodynamic diameters on the order of 1-3 μm in size. The presence of citric acid significantly enhanced the extent of ZnO dissolution for all sizes, and the greatest enhancement was observed for the 4 nm particles. Although these results are found to be in qualitative agreement with theoretical predictions, a linearized form of the Kelvin equation to calculate a surface free energy yielded quantities inconsistent with expected values from the literature. Reasons for this inconsistency are discussed and include potential deviations of solubility behavior from classical thermodynamics as a result of a lack of detailed knowledge of surface structure and surface properties, including the presence of different surface crystal facets, and the aggregation state.

Solubility of nano‐zinc oxide in environmentally and biologically important matrices

Increasing manufacture and use of engineered nanoparticles is leading to a greater probability for release of engineered nanoparticles into the environment and exposure to organisms. In particular, zinc oxide (ZnO) is toxic, although it is unclear whether this toxicity is due to the zinc oxide nanoparticles, dissolution to Zn(2+) , or some combination thereof. The goal of this study was to determine the relative solubilities of both commercially available and in-house synthesized ZnO in matrices used for environmental fate and transport or biological toxicity studies. Dissolution of ZnO was observed in nanopure water (7.18-7.40 mg/L dissolved Zn, as measured by filtration) and Roswell Park Memorial Institute medium (RPMI-1640) (∼5 mg/L), but much more dissolution was observed in Dulbecco's modified Eagle's medium, in which the dissolved Zn concentration exceeded 34 mg/L. Moderately hard water exhibited low Zn solubility, likely because of precipitation of a Zn carbonate solid phase. Precipitation of a Zn-containing solid phase in RPMI also appeared to limit Zn solubility. Equilibrium conditions with respect to ZnO solubility were not apparent in these matrices, even after more than 1,000 h of dissolution. These results suggest that solution chemistry exerts a strong influence on ZnO dissolution and can result in limits on Zn solubility from precipitation of less soluble solid phases.

Use of a rapid cytotoxicity screening approach to engineer a safer zinc oxide nanoparticle through iron doping.

The establishment of verifiably safe nanotechnology requires the development of assessment tools to identify hazardous nanomaterial properties that could be modified to improve nanomaterial safety. While there is a lot of debate of what constitutes appropriate safety screening methods, one approach is to use the assessment of cellular injury pathways to collect knowledge about hazardous material properties that could lead to harm to humans and the environment. We demonstrate the use of a multiparameter cytotoxicity assay that evaluates toxic oxidative stress to compare the effects of titanium dioxide (TiO(2)), cerium oxide (CeO(2)), and zinc oxide (ZnO) nanoparticles in bronchial epithelial and macrophage cell lines. The nanoparticles were chosen on the basis of their volume of production and likelihood of spread to the environment. Among the materials, dissolution of ZnO nanoparticles and Zn(2+) release were capable of ROS generation and activation of an integrated cytotoxic pathway that includes intracellular calcium flux, mitochondrial depolarization, and plasma membrane leakage. These responses were chosen on the basis of the compatibility of the fluorescent dyes that contemporaneously assess their response characteristics by a semiautomated epifluorescence procedure. Purposeful reduction of ZnO cytotoxicity was achieved by iron doping, which changed the material matrix to slow Zn(2+) release. In summary, we demonstrate the utility of a rapid throughput, integrated biological oxidative stress response pathway to perform hazard ranking of a small batch of metal oxide nanoparticles, in addition to showing how this assay can be used to improve nanosafety by decreasing ZnO dissolution through Fe doping.

Fabrication of lithium-doped zinc oxide film by anodic oxidation and its ferroelectric behavior

A lithium-doped zinc oxide (ZnO) film was obtained by the anodic oxidation of a zinc sheet in a lithium hydroxide (LiOH) solution under an external DC voltage. The formation of the ZnO film on the surface of the Zn sheet is attributed to two simultaneous processes: the electrochemical oxidation of Zn to ZnO, and the chemical dissolution of ZnO. It was also confirmed that Li element was successfully introduced into the lattice of the ZnO film. The curves of the polarization versus applied field were measured to be hysteresis loops, suggesting ferroelectricity of the Li-doped ZnO film. The remanent polarization and the coercive field of the film were measured to be 4.7 × 10 −3 C m −2 and 1.2 × 10 7 V m −1, respectively. This ferroelectricity is believed to be the result of the occupation of off-centered positions in oxygen tetrahedra by the Li + ions.