Toxicity of manufactured nano-ZnO to Lemna minor

The rapid development of nanotechnology has led to a rise in the large-scale production and commercial use of engineered nano-ZnO. Engineered/manufactured nano-ZnO are applied in a broad range of products such as drugs, paints, cosmetics, abrasive agents and insulators. This can result in the unintended exposure of human beings to nano-ZnO and will inevitably result in the release of nano-ZnO in to the environment. Thus, it is necessary to assess the risk of nano-ZnO to the environment. In this thesis the toxicity of nano-ZnO was analysed using the aquatic, primary producer lesser duckweed (Lemna minor), and the mechanism of toxicity was analysed. Both short-term (one week) and long-term (six weeks) toxicity of nano-ZnO (uncoated) were determined. Results show that the toxicity of nano-ZnO added to the aquatic growth medium increases with increasing concentration and that toxicity accumulates with exposure time. A study of nano-ZnO dissolution reveals that the main reason for nano-ZnO toxicity on Lemna minor is the release of Zn ions. Nano-ZnO dissolution is pH dependent, and toxicity matches the release of Zn2+. Functional coating materials are commonly added to nano-ZnO particles to improve specific industrial applications. To test if coating materials contribute to nano-ZnO toxicity on lesser duckweed, the effect of silane coupling agent (KH550) coated nano-ZnO on Lemma minor was investigated. Results show that coating can decrease the release of Zn ions, which reduces toxicity to Lemna minor, in contrast to uncoated particles. Another commonly hypothesized reason for nano-ZnO toxicity is the formation of Reactive Oxygen Species (ROS) on the particles surface. As part of this thesis, the ROS formation induced by nano-ZnO was studied. Results show that nano-ZnO catalyse ROS formation and this can negatively affect duckweed growth. In conclusion, this work has detailed potentially toxic effects of nano-ZnO on Lemna minor. This study has also provides references for future research, and informs regulatory testing for nanoparticle toxicity. Specifically, the outcomes of this study emphasize the importance of exposure time, environmental parameters and coating material when analysing NPs toxicity. Firstly, impacts of longer exposure time should be studied. Secondly, environmental parameters such as pH and medium-composition need to be considered when investigating NPs toxicity. Lastly, coating of NPs should always be considered in the context of NPs toxicity, and similar NPs with different coatings require separate toxicity tests.

Modelling the nano-scale phenomena in condensed matter physics via computer-based numerical simulations

A review of the atomistic modelling of the behaviour of nano-scale structures and processes via molecular dynamics (MD) simulation method of a canonical ensemble is presented. Three areas of application in condensed matter physics are considered. We focus on the adhesive and indentation properties of the solid surfaces in nano-contacts, the nucleation and growth of nano-phase metallic and semi-conducting atomic and molecular films on supporting substrates, and the nano- and multi-scale crack propagation properties of metallic lattices. A set of simulations selected from these fields are discussed, together with a brief introduction to the methodology of the MD simulation. The pertinent inter-atomic potentials that model the energetics of the metallic and semi-conducting systems are also given.

Surface physics at the nano-scale via scanning probe microscopy and molecular dynamics simulations

Probe-based scanning microscopes, such as the STM and the AFM, are used to obtain the topographical and electronic structure maps of material surfaces, and to modify their morphologies on nanoscopic scales. They have generated new areas of research in condensed matter physics and materials science. We will review some examples from the fields of experimental nano-mechanics, nano-electronics and nano-magnetism. These now form the basis of the emerging field of Nano-technology. A parallel development has been brought about in the field of Computational Nano-science, using quantum-mechanical techniques and computer-based numerical modelling, such as the Molecular Dynamics (MD) simulation method. We will report on the simulation of nucleation and growth of nano-phase films on supporting substrates. Furthermore, a theoretical modelling of the formation of STM images of metallic clusters on metallic substrates will also be discussed within the non-equilibrium Keldysh Green function method to study the effects of coherent tunnelling through different atomic orbitals in a tip-sample geometry.

Minimising the risk of defects in nano-imprint forming

Nano-imprint forming (NIF) is among the most attractive manufacturing technologies offering high yield and low-cost fabrication of three-dimensional fine structures and patterns with resolution of few nanometres. Optimising NIF process is critical for achieving high quality products and minimising the risk of commonly observed defects. Using finite element analysis, the effect of various process parameters is evaluated and design rules for safe and reliable NIF fabrication formulated. This work is part of a major UK Grand Challenge project - 3D-Mintegration - for design, simulation, fabrication, assembly and test of next generation 3D-miniaturised systems.

Modelling of nano-imprint forming process for the production of miniaturised 3D structures

Nano-imprint forming (NIF) as manufacturing technology is ideally placed to enable high resolution, low-cost and high-throughput fabrication of three-dimensional fine structures and the packaging of heterogeneous micro-systems (S.Y. Chou and P.R. Krauss, 1997). This paper details a thermo-mechanical modelling methodology for optimising this process for different materials used in components such as mini-fluidics and bio-chemical systems, optoelectronics, photonics and health usage monitoring systems (HUMS). This work is part of a major UK Grand Challenge project - 3D-Mintegration - which is aiming to develop modelling and design technologies for the next generation of fabrication, assembly and test processes for 3D-miniaturised systems.

Enhanced toxicity of ‘bulk' titanium dioxide compared to ‘fresh' and ‘aged' nano-TiO2in marine mussels (Mytilus galloprovincialis)

Marine bivalves (Mytilus galloprovincialis) were exposed to titanium dioxide (10 mg L-1) either as engineered nanoparticles (nTiO(2); fresh, or aged under simulated sunlight for 7 days) or the bulk equivalent. Inductively coupled plasma-optical emission spectrometry analyses of mussel tissues showed higher Ti accumulation (>10-fold) in the digestive gland compared to gills. Nano-sized TiO2 showed greater accumulation than bulk, irrespective of ageing, particularly in digestive gland (>sixfold higher). Despite this, transcriptional expression of metallothionein genes, histology and histochemical analysis suggested that the bulk material was more toxic. Haemocytes showed significantly enhanced DNA damage, determined by the modified comet assay, for all treatments compared to the control, but no significant differences between the treatments. Our integrated study suggests that for this ecologically relevant organism photocatalytic ageing of nTiO(2) does not significantly alter toxicity, and that bulk TiO2 may be less ecotoxicologically inert than previously assumed.

Temporal variability in total, micro- and nano-phytoplankton primary production at a coastal site in the Western English Channel

Primary productivity and subsequent carbon cycling in the coastal zone have a significant impact on the global carbon budget. It is currently unclear how anthropogenic activity could alter these budgets but long term coastal time series of hydrological, biogeochemical and biological measurements represent a key means to better understand past drivers, and hence to predicting future seasonal and inter-annual variability in carbon fixation in coastal ecosystems. An 8-year time series of primary production from 2003 to 2010, estimated using a recently developed absorption-based algorithm, was used to determine the nature and extent of change in primary production at a coastal station (L4) in the Western English Channel (WEC). Analysis of the seasonal and inter-annual variability in production demonstrated that on average, nano- and pico-phytoplankton account for 48% of the total carbon fixation and micro-phytoplankton for 52%. A recent decline in the primary production of nano- and pico-phytoplankton from 2005 to 2010 was observed, corresponding with a decrease in winter nutrient concentrations and a decrease in the biomass of Phaeocystis sp. Micro-phytoplankton primary production (PPM) remained relatively constant over the time series and was enhanced in summer during periods of high precipitation. Increases in sea surface temperature, and decreases in wind speeds and salinity were associated with later spring maxima in PPM. Together these trends indicate that predicted increases in temperature and decrease in wind speeds in future would drive later spring production whilst predicted increases in precipitation would also continue these blooms throughout the summer at this site.

Intrinsic dielectric response in ferroelectric nano-capacitors

Measurements on 'free-standing' single-crystal barium titanate capacitors with thickness down to 75 nm show a dielectric response typical of large single crystals, rather than conventional thin films. There is a notable absence of any broadening or temperature shift of the dielectric peak or loss tangent. Peak dielectric constants of similar to25 000 are observed, and Curie-Weiss analysis demonstrates first order transformation behaviour. This is in dramatic contrast to results on conventionally deposited thin film capacitor heterostructures, which show large dielectric peak broadening and temperature shifts (e.g. Parker et al 2002 Appl. Phys. Lett. 81 340), as well as an apparent change in the nature-of the paraelectric-ferroelectric transition from first to second order. Our data are compatible with a recent model by Bratkovsky and Levanyuk (2004 Preprint cond-mat/0402100), which attributes dielectric peak broadening to gradient terms that will exist in any thin film capacitor heterostructure. The observed recovery of first order transformation behaviour is consistent with the absence of significant substrate clamping in our experiment, as modelled by Pertsev et al (1998,Phys. Rev. Lett. 80 1988), and illustrates that the second order behaviour seen in conventionally deposited thin films cannot be attributed to the effects of reduced dimensionality in the system, nor to the influence of an intrinsic universal interfacial capacitance associated with the electrode- ferroelectric interface.

Liquid source misted chemical deposition process of three-dimensional nano-ferroelectrics with substrate heating

A modification of liquid source misted chemical deposition process (LSMCD) with heating mist and substrate has developed, and this enabled to control mist penetrability and fluidity on sidewalls of three-dimensional structures and ensure step coverage. A modified LSMCD process allowed a combinatorial approach of Pb(Zr,Ti)O-3 (PZT) thin films and carbon nanotubes (CNTs) toward ultrahigh integration density of ferroelectric random access memories (FeRAMs). The CNTs templates were survived during the crystallization process of deposited PZT film onto CNTs annealed at 650 degrees C in oxygen ambient due to a matter of minute process, so that the thermal budget is quite small. The modified LSMCD process opens up the possibility to realize the nanoscale capacitor structure of ferroelectric PZT film with CNTs electrodes toward ultrahigh integration density FeRAMs.