Inducing upwards band bending by surface stripping ZnO nanowires with argon bombardment.

Metal oxide semiconductors such as ZnO have attracted much scientific attention due their material and electrical properties and their ability to form nanostructures that can be used in numerous devices. However, ZnO is naturally n-type and tailoring its electrical properties towards intrinsic or p-type in order to optimise device operation have proved difficult. Here, we present an x-ray photon-electron spectroscopy and photoluminescence study of ZnO nanowires that have been treated with different argon bombardment treatments including with monoatomic beams and cluster beams of 500 atoms and 2000 atoms with acceleration volte of 0.5 keV-20 keV. We observed that argon bombardment can remove surface contamination which will improve contact resistance and consistency. We also observed that using higher intensity argon bombardment stripped the surface for nanowires causing a reduction in defects and surface OH- groups both of which are possible causes of the n-type nature and observed a shift in the valance band edge suggest a shift to a more p-type nature. These results indicate a simple method for tailoring the electrical characteristic of ZnO.

Influence of Surface Compositions on the Reactivity of Pyrite toward Aqueous U(VI).

Pyrite plays a significant role in governing the mobility of toxic uranium in an anaerobic environment via an oxidation-reduction process occurring at the mineral-water interface, but the factors influencing the reaction kinetics remain poorly understood. In this study, natural pyrites with different impurities (Pb, As, and Si) and different surface pretreatments were used to react with aqueous U(VI) from pH ∼3.0 to ∼9.5. Both aqueous and solid results indicated that freshly crushed pyrites, which do have more surface Fe2+/Fe3+ and S2- sites that were generated from breakage of Fe(S)-S bonds during ball milling, exhibited a much stronger reactivity than those treated with acid washing. Besides, U(VI) reduction which involves the possible intermediate U(V) and the formation of hyperstoichiometric UO2+x(s) was found to preferentially occur at Pb- and As-rich spots on the pyrite surface, suggesting that the incorporated impurities could act as reactive sites because of the generation of lattice defects and galena- and arsenopyrite-like local configurations. These reactive surface sites can be removed by acid washing, leaving a pyrite surface nearly inert toward aqueous U(VI). Thus, reactivity of pyrite toward U(VI) is largely governed by its surface compositions, which provides an insight into the chemical behavior of both pyrite and uranium in various environments.

XANES-Based Determination of Redox Potentials Imposed by Steel Corrosion Products in Cement-Based Media.

The redox potential (Eh) in a cementitious nuclear waste repository is critical to the retardation behavior of redox-sensitive radionuclides (RNs), and largely controlled by embedded steel corrosion but hard to be determined experimentally. Here, we propose an innovative Eh determination method based on chemical/spectroscopic measurements. Oxidized nuclides (UVI, SeIV, MoVI, and SbV) were employed as species probes to detect the Eh values imposed by steel (Fe0) and steel corrosion products (magnetite/hematite, and magnetite/goethite couples) in cement pore water. Nuclides showed good sorption affinity, especially toward Fe0, in decreasing Kd order for U > Sb > Se > Mo under both N2 and H2 atmospheres. The reduced nuclide species were identified as UO2, U4O9, FeSe, FeSe2, Se0, Sb0, and Sb2O3, but no redox transformation occurred for Mo. Eh values were obtained by using the Nernst equation. Remarkably, their values fell in a small range centered around -456 mV at pH ∼ 13.5 for both Fe0 and Fe-oxyhydroxides couples. This Eh value appears to be controlled by the nanocrystalline Fe(OH)2/Fe(OH)3 or (Fe1- x,Ca x)(OH)2/Fe(OH)3 couple, whose presence was confirmed by pair distribution function analyses. This approach could pave the way for describing the Eh gradient in reinforced concrete where traditional Eh measurements are not feasible.

Investigation into the effects of surface stripping ZnO nanosheets.

ZnO nanosheets are polycrystalline nanostructures that are used in devices including solar cells and gas sensors. However, for efficient and reproducible device operation and contact behaviour the conductivity characteristics must be controlled and surface contaminants removed. Here we use low doses of argon bombardment to remove surface contamination and make reproducible lower resistance contacts. Higher doses strip the surface of the nanosheets altering the contact type from near-ohmic to rectifying by removing the donor-type defects, which photoluminescence shows to be concentrated in the near-surface. Controlled doses of argon treatments allow nanosheets to be customised for device formation.

XPS investigation of titanium contact formation to ZnO nanowires.

Ti is often used to form an initial Ohmic interface between ZnO and Au due to its low work function, and the TiO2/ZnO heterojunction is also of great importance for many practical applications of nanoparticles. Here, Ti has been controllably deposited onto hydrothermally grown ZnO nanowires and the formation of metal-semiconductor contact has been investigated using x-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectroscopy and scanning electron microscopy. XPS results showed that that the Ti initially reacts with surface oxygen species to form TiO2, and further deposition results in the formation of oxides with oxidation state numbers lower than four, and eventually metallic Ti on top of the TiO2. The formation of TiC was also observed. XPS showed that the onset of metallic Ti coincided with a Zn 3p core level shift to lower binding energy, indicating upwards band bending and the formation of a rectifying contact. Annealing caused a near-complete conversion of the metallic Ti to TiO2 and caused the Zn 3p to shift back to its original higher binding energy, resulting in downwards band bending and a more Ohmic contact. PL measurements showed that the optical properties of the nanowires are not affected by the contact formation.

In-situ synthesis of magnetic iron-oxide nanoparticle-nanofibre composites using electrospinning.

We demonstrate a facile, one-step process to form polymer scaffolds composed of magnetic iron oxide nanoparticles (MNPs) contained within electrospun nano- and micro-fibres of two biocompatible polymers, Poly(ethylene oxide) (PEO) and Poly(vinyl pyrrolidone) (PVP). This was achieved with both needle and free-surface electrospinning systems demonstrating the scalability of the composite fibre manufacture; a 228 fold increase in fibre fabrication was observed for the free-surface system. In all cases the nanoparticle-nanofibre composite scaffolds displayed morphological properties as good as or better than those previously described and fabricated using complex multi-stage techniques. Fibres produced had an average diameter (Needle-spun: 125±18nm (PEO) and 1.58±0.28µm (PVP); Free-surface electrospun: 155±31nm (PEO)) similar to that reported previously, were smooth with no bead defects. Nanoparticle-nanofibre composites were characterised using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS) (Nanoparticle average diameter ranging from 8±3nm to 27±5nm), XRD (Phase of iron oxide nanoparticles identified as magnetite) and nuclear magnetic resonance relaxation measurements (NMR) (T1/T2: 32.44 for PEO fibres containing MNPs) were used to verify the magnetic behaviour of MNPs. This study represents a significant step forward for production rates of magnetic nanoparticle-nanofibre composite scaffolds by the electrospinning technique.

Genetic toxicity assessment of engineered nanoparticles using a 3D in vitro skin model (EpiDerm™).

BACKGROUND: The rapid production and incorporation of engineered nanomaterials into consumer products alongside research suggesting nanomaterials can cause cell death and DNA damage (genotoxicity) makes in vitro assays desirable for nanosafety screening. However, conflicting outcomes are often observed when in vitro and in vivo study results are compared, suggesting more physiologically representative in vitro models are required to minimise reliance on animal testing. METHOD: BASF Levasil® silica nanoparticles (16 and 85 nm) were used to adapt the 3D reconstructed skin micronucleus (RSMN) assay for nanomaterials administered topically or into the growth medium. 3D dose-responses were compared to a 2D micronucleus assay using monocultured human B cells (TK6) after standardising dose between 2D / 3D assays by total nanoparticle mass to cell number. Cryogenic vitrification, scanning electron microscopy and dynamic light scattering techniques were applied to characterise in-medium and air-liquid interface exposures. Advanced transmission electron microscopy imaging modes (high angle annular dark field) and X-ray spectrometry were used to define nanoparticle penetration / cellular uptake in the intact 3D models and 2D monocultured cells. RESULTS: For all 2D exposures, significant (p < 0.002) increases in genotoxicity were observed (≥100 µg/mL) alongside cell viability decreases (p < 0.015) at doses ≥200 µg/mL (16 nm-SiO2) and ≥100 µg/mL (85 nm-SiO2). In contrast, 2D-equivalent exposures to the 3D models (≤300 µg/mL) caused no significant DNA damage or impact on cell viability. Further increasing dose to the 3D models led to probable air-liquid interface suffocation. Nanoparticle penetration / cell uptake analysis revealed no exposure to the live cells of the 3D model occurred due to the protective nature of the skin model's 3D cellular microarchitecture (topical exposures) and confounding barrier effects of the collagen cell attachment layer (in-medium exposures). 2D monocultured cells meanwhile showed extensive internalisation of both silica particles causing (geno)toxicity. CONCLUSIONS: The results establish the importance of tissue microarchitecture in defining nanomaterial exposure, and suggest 3D in vitro models could play a role in bridging the gap between in vitro and in vivo outcomes in nanotoxicology. Robust exposure characterisation and uptake assessment methods (as demonstrated) are essential to interpret nano(geno)toxicity studies successfully.

Effects of Vacuum Annealing on the Conduction Characteristics of ZnO Nanosheets.

ZnO nanosheets are a relatively new form of nanostructure and have demonstrated potential as gas-sensing devices and dye sensitised solar cells. For integration into other devices, and when used as gas sensors, the nanosheets are often heated. Here we study the effect of vacuum annealing on the electrical transport properties of ZnO nanosheets in order to understand the role of heating in device fabrication. A low cost, mass production method has been used for synthesis and characterisation is achieved using scanning electron microscopy (SEM), photoluminescence (PL), auger electron spectroscopy (AES) and nanoscale two-point probe. Before annealing, the measured nanosheet resistance displayed a non-linear increase with probe separation, attributed to surface contamination. Annealing to 300 °C removed this contamination giving a resistance drop, linear probe spacing dependence, increased grain size and a reduction in the number of n-type defects. Further annealing to 500 °C caused the n-type defect concentration to reduce further with a corresponding increase in nanosheet resistance not compensated by any further sintering. At 700 °C, the nanosheets partially disintegrated and the resistance increased and became less linear with probe separation. These effects need to be taken into account when using ZnO nanosheets in devices that require an annealing stage during fabrication or heating during use.

The effects of surface stripping ZnO nanorods with argon bombardment.

ZnO nanorods are used in devices including field effects transistors, piezoelectric transducers, optoelectronics and gas sensors. However, for efficient and reproducible device operation and contact behaviour, surface contaminants must be removed or controlled. Here we use low doses of argon bombardment to remove surface contamination and make reproducible lower resistance contacts. Higher doses strip the surface of the nanorods allowing intrinsic surface measurements through a cross section of the material. Photoluminescence finds that the defect distribution is higher at the near-surface, falling away in to the bulk. Contacts to the n-type defect-rich surface are near-Ohmic, whereas stripping away the surface layers allows more rectifying Schottky contacts to be formed. The ability to select the contact type to ZnO nanorods offers a new way to customize device behaviour.

Controlling the Electrical Transport Properties of Nanocontacts to Nanowires.

The ability to control the properties of electrical contacts to nanostructures is essential to realize operational nanodevices. Here, we show that the electrical behavior of the nanocontacts between free-standing ZnO nanowires and the catalytic Au particle used for their growth can switch from Schottky to Ohmic depending on the size of the Au particles in relation to the cross-sectional width of the ZnO nanowires. We observe a distinct Schottky to Ohmic transition in transport behavior at an Au to nanowire diameter ratio of 0.6. The current-voltage electrical measurements performed with a multiprobe instrument are explained using 3-D self-consistent electrostatic and transport simulations revealing that tunneling at the contact edge is the dominant carrier transport mechanism for these nanoscale contacts. The results are applicable to other nanowire materials such as Si, GaAs, and InAs when the effects of surface charge and contact size are considered.

ZnO nanowires with Au contacts characterised in the as-grown real device configuration using a local multi-probe method.

We demonstrate here a method using a multi-probe UHV instrument to isolate and measure individual metal contacts controllably fabricated on the tips of free standing ZnO nanowires (NWs). The measurements show Au can form reliable Ohmic and rectifying contacts by exercising control over the surface properties. In the as-grown state the Au contacts display low-resistance characteristics which are determined by the adsorbed species and defects on the NW surface. Subjecting the NWs to an oxidising agent (H2O2) increases the surface potential barrier creating more rectifying contacts. These developments are crucial for controllable NW array devices.

Detailed surface morphology of the 'lobster louse' copepod, Nicothoë astaci, a haematophagous gill parasite of the European lobster, Homarus gammarus.

The ectoparasitic copepod, Nicothoë astaci (the 'lobster louse'), infests the gills of the European lobster, Homarus gammarus. There have been limited studies on this haematophagous species; therefore knowledge of this parasite is rudimentary. The current study examines the surface morphology of this parasitic copepod, detached from the host, concentrating on adaptations of the suctorial mouthpart, the oral disc. Cryo-scanning electron microscopy revealed structural adaptations that facilitate attachment of these parasites to the gill filaments of their lobster host. The aperture of the feeding channel, through which host haemolymph is drawn, is only ca. 5µm in diameter. The edge of the oral disc is lined with numerous setae, whilst the surface of the disc is covered with large numbers of small (<1µm in diameter) teeth-like structures, which presumably pierce through, and grip, the cuticle lining of the host's gill. Overall, these structures are thought to provide a 'vacuum seal' to assist in pumping of blood, via peristalsis, into the alimentary canal of the copepod host.

Microwave-assisted synthesis of layered basic zinc acetate nanosheets and their thermal decomposition into nanocrystalline ZnO.

We have developed a low-cost technique using a conventional microwave oven to grow layered basic zinc acetate (LBZA) nanosheets (NSs) from a zinc acetate, zinc nitrate and HMTA solution in only 2 min. The as-grown crystals and their pyrolytic decomposition into ZnO nanocrystalline NSs are characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), atomic force microscopy (AFM), X-ray diffraction (XRD) and photoluminescence (PL). SEM and AFM measurements show that the LBZA NSs have typical lateral dimensions of 1 to 5 µm and thickness of 20 to 100 nm. Annealing in air from 200°C to 1,000°C results in the formation of ZnO nanocrystalline NSs, with a nanocrystallite size ranging from 16 nm at 200°C to 104 nm at 1,000°C, as determined by SEM. SEM shows evidence of sintering at 600°C. PL shows that the shape of the visible band is greatly affected by the annealing temperature and that the exciton band to defect band intensity ratio is maximum at 400°C and decreases by a factor of 15 after annealing at 600°C. The shape and thickness of the ZnO nanocrystalline NSs are the same as LBZA NSs. This structure provides a high surface-to-volume ratio of interconnected nanoparticles that is favorable for applications requiring high specific area and low resistivity such as gas sensing and dye-sensitized solar cells (DSCs). We show that resistive gas sensors fabricated with the ZnO NSs showed a response of 1.12 and 1.65 to 12.5 ppm and 200 ppm of CO at 350°C in dry air, respectively, and that DSCs also fabricated from the material had an overall efficiency of 1.3%. PACS: 81.07.-b; 62.23.Kn; 61.82.Fk.

A comparison of the structure of American (Homarus americanus) and European (Homarus gammarus) lobster cuticle with particular reference to shell disease susceptibility.

The integument of arthropods is an important first-line defence against the invasion of parasites and pathogens. Once damaged, this can be subject to colonisation by microbial agents from the surrounding environment, which in crustaceans can lead to a condition termed shell disease syndrome. This condition has been reported in several crustacean species, including crabs and lobsters. The syndrome is a progressive condition where the outer cuticle becomes pitted and eroded, and in extreme cases is compromised, leaving animals susceptible to septicaemia. This study examined the susceptibility of juvenile American (Homarus americanus) and European (Homarus gammarus) lobsters to shell disease, as a result of mechanical damage. Scanning electron microscopy was used as a method to identify differences in the cuticle structure and consequences of mechanical damage. Claw regions were aseptically punctured, whilst carapaces were abraded using sterile sandpaper, to mimic natural damage. After a period of between 10 and 12 weeks, lobsters were sacrificed, fixed and stored for later examination. The carapace and claws of juvenile American lobsters were shown to be thinner and more vulnerable to abrasion damage than their European counterparts. In addition, the number and distribution of setal pits and pore canal openings also differed between the two species of lobster. Mechanical damage resulted in the formation of shell disease lesions on the claw and carapace of both lobster species. However, American lobsters, unlike their European counterparts, had extensive bacterial colonisation on the margins of these lesions. Overall, it is concluded that the cuticle of the American lobster is more susceptible to damage and resulting microbial colonisation. This may have implications for susceptibility of both species of lobster to shell disease syndrome.

Metarhizium anisopliae pathogenesis of mosquito larvae: a verdict of accidental death.

Metarhizium anisopliae, a fungal pathogen of terrestrial arthropods, kills the aquatic larvae of Aedes aegypti, the vector of dengue and yellow fever. The fungus kills without adhering to the host cuticle. Ingested conidia also fail to germinate and are expelled in fecal pellets. This study investigates the mechanism by which this fungus adapted to terrestrial hosts kills aquatic mosquito larvae. Genes associated with the M. anisopliae early pathogenic response (proteinases Pr1 and Pr2, and adhesins, Mad1 and Mad2) are upregulated in the presence of larvae, but the established infection process observed in terrestrial hosts does not progress and insecticidal destruxins were not detected. Protease inhibitors reduce larval mortality indicating the importance of proteases in the host interaction. The Ae. aegypti immune response to M. anisopliae appears limited, whilst the oxidative stress response gene encoding for thiol peroxidase is upregulated. Cecropin and Hsp70 genes are downregulated as larval death occurs, and insect mortality appears to be linked to autolysis through caspase activity regulated by Hsp70 and inhibited, in infected larvae, by protease inhibitors. Evidence is presented that a traditional host-pathogen response does not occur as the species have not evolved to interact. M. anisopliae retains pre-formed pathogenic determinants which mediate host mortality, but unlike true aquatic fungal pathogens, does not recognise and colonise the larval host.

Factors that determine and limit the resistivity of high-quality individual ZnO nanowires.

Knowing and controlling the resistivity of an individual nanowire (NW) is crucial for the production of new sensors and devices. For ZnO NWs this is poorly understood; a 10(8) variation in resistivity has previously been reported, making the production of reproducible devices almost impossible. Here, we provide accurate resistivity measurements of individual NWs, using a four-probe scanning tunnelling microscope (STM), revealing a dependence on the NW dimensions. To correctly interpret this behaviour, an atomic level transmission electron microscopy technique was employed to study the structural properties of the NWs in relation to three growth techniques: hydrothermal, catalytic and non-catalytic vapour phase. All NWs were found to be defect free and structurally equivalent; those grown with a metallic catalyst were free from Au contamination. The resistivity measurements showed a distinct increase with decreasing NW diameter, independent of growth technique. The increasing resistivity at small NW diameters was attributed to the dominance of surface states removing electrons from the bulk. However, a fundamental variance in resistivity (10(2)) was observed and attributed to changes in occupied surface state density, an effect which is not seen with other NW materials such as Si. This is examined by a model to predict the effect of surface state occupancy on the measured resistivity and is confirmed with measurements after passivating the ZnO surface. Our results provide an understanding of the primary influence of the reactive nature of the surface and its dramatic effect on the electrical properties of ZnO NWs.

The role of iron redox state in the genotoxicity of ultrafine superparamagnetic iron oxide nanoparticles.

Ultrafine superparamagnetic iron oxide nanoparticles (USPION) hold great potential for revolutionising biomedical applications such as MRI, localised hyperthermia, and targeted drug delivery. Though evidence is increasing regarding the influence of nanoparticle physico-chemical features on toxicity, data however, is lacking that assesses a range of such characteristics in parallel. We show that iron redox state, a subtle though important physico-chemical feature of USPION, dramatically modifies the cellular uptake of these nanoparticles and influences their induction of DNA damage. Surface chemistry was also found to have an impact and evidence to support a potential mechanism of oxidative DNA damage behind the observed responses has been demonstrated. As human exposure to ferrofluids is predicted to increase through nanomedicine based therapeutics, these findings are important in guiding the fabrication of USPION to ensure they have characteristics that support biocompatibility.

NanoGenotoxicology: the DNA damaging potential of engineered nanomaterials.

With the rapid expansion in the nanotechnology industry, it is essential that the safety of engineered nanomaterials and the factors that influence their associated hazards are understood. A vital area governing regulatory health risk assessment is genotoxicology (the study of genetic aberrations following exposure to test agents), as DNA damage may initiate and promote carcinogenesis, or impact fertility. Of late, considerable attention has been given to the toxicity of engineered nanomaterials, but the importance of their genotoxic potential on human health has been largely overlooked. This comprehensive review focuses on the reported abilities of metal nanoparticles, metal-oxide nanoparticles, quantum dots, fullerenes, and fibrous nanomaterials, to damage or interact with DNA, and their ecogenotoxicity is also considered. Many of the engineered nanomaterials assessed were found to cause genotoxic responses, such as chromosomal fragmentation, DNA strand breakages, point mutations, oxidative DNA adducts and alterations in gene expression profiles. However, there are clear inconsistencies in the literature and it is difficult to draw conclusions on the physico-chemical features of nanomaterials that promote genotoxicity, largely due to study design. Hence, areas that require that further attention are highlighted and recommendations to improve our understanding of the genotoxic potential of engineered nanomaterials are addressed.