Functionalised zinc oxide nanowire gas sensors : enhanced NO2 gas sensor response by chemical modification of nanowire surfaces

Surface coating with an organic self-assembled monolayer (SAM) can enhance surface reactions or the absorption of specific gases and hence improve the response of a metal oxide (MOx) sensor toward particular target gases in the environment. In this study the effect of an adsorbed organic layer on the dynamic response of zinc oxide nanowire gas sensors was investigated. The effect of ZnO surface functionalisation by two different organic molecules, tris(hydroxymethyl)aminomethane (THMA) and dodecanethiol (DT), was studied. The response towards ammonia, nitrous oxide and nitrogen dioxide was investigated for three sensor configurations, namely pure ZnO nanowires, organic-coated ZnO nanowires and ZnO nanowires covered with a sparse layer of organic-coated ZnO nanoparticles. Exposure of the nanowire sensors to the oxidising gas NO2 produced a significant and reproducible response. ZnO and THMA-coated ZnO nanowire sensors both readily detected NO2 down to a concentration in the very low ppm range. Notably, the THMA-coated nanowires consistently displayed a small, enhanced response to NO2 compared to uncoated ZnO nanowire sensors. At the lower concentration levels tested, ZnO nanowire sensors that were coated with THMA-capped ZnO nanoparticles were found to exhibit the greatest enhanced response. ΔR/R was two times greater than that for the as-prepared ZnO nanowire sensors. It is proposed that the ΔR/R enhancement in this case originates from the changes induced in the depletion-layer width of the ZnO nanoparticles that bridge ZnO nanowires resulting from THMA ligand binding to the surface of the particle coating. The heightened response and selectivity to the NO2 target are positive results arising from the coating of these ZnO nanowire sensors with organic-SAM-functionalised ZnO nanoparticles.

Real-time detection of concealed chemical hazards under ambient light conditions using Raman spectroscopy

Current concerns regarding terrorism and international crime highlight the need for new techniques for detecting unknown and hazardous substances. A novel Raman spectroscopy-based technique, spatially offset Raman spectroscopy (SORS), was recently devised for non-invasively probing the contents of diffusely scattering and opaque containers. Here, we demonstrate a modified portable SORS sensor for detecting concealed substances in-field under different background lighting conditions. Samples including explosive precursors, drugs and an organophosphate insecticide (chemical warfare agent surrogate) were concealed inside diffusely scattering packaging including plastic, paper and cloth. Measurements were carried out under incandescent and fluorescent light as well as under daylight to assess the suitability of the probe for different real-life conditions. In each case, it was possible to identify the substances against their reference Raman spectra in less than one minute. The developed sensor has potential for rapid detection of concealed hazardous substances in airports, mail distribution centers and customs checkpoints.

Preliminary results on the chemical composition of outdoor airborne particles at urban schools and possible implications for the air quality in classrooms

Vehicle emissions are a significant source of fine particles (Dp < 2.5 µm) in an urban environment. These fine particles have been shown to have detrimental health effects, with children thought to be more susceptible. Vehicle emissions are mainly carbonaceous in nature, and carbonaceous aerosols can be defined as either elemental carbon (EC) or organic carbon (OC). EC is a soot-like material emitted from primary sources while OC fraction is a complex mixture of hundreds of organic compounds from either primary or secondary sources (Cao et al., 2006). Therefore the ratio of OC/EC can aid in the identification of source. The purpose of this paper is to use the concentration of OC and EC in fine particles to determine the levels of vehicle emissions in schools. It is expected that this will improve the understanding of the potential exposure of children in a school environment to vehicle emissions.

Lignocellulosics as a renewable feedstock for chemical industry : chemical hydrolysis and pretreatment processes

Lignocellulosic materials including agricultural, municipal and forestry residues, and dedicated bioenergy crops offer significant potential as a renewable feedstock for the production of fuels and chemicals. These products can be chemically or functionally equivalent to existing products that are produced from fossil-based feedstocks. To unlock the potential of lignocellulosic materials, it is necessary to pretreat or fractionate the biomass to make it amenable to downstream processing. This chapter explores current and developing technologies for the pretreatment and fractionation of lignocellulosic biomass for the production of chemicals and fuels.

Value added products from modified kaolins : new chemical routes to new markets

Chemical treatments of kaolins to produce nanocrystalline or "X-ray amorphous", stable aluminosilicates with variable - but reproducible - types of micro- and meso-porosity have been developed. These materials show cation exchange capacities and surface area values significantly higher (ranging from 10x to 100x) than kaolin and show good acid resistance to pH~3.0. The combination of these properties offers strong potential for many new applications of kaolin-derived materials in large worldwide markets such as environmental remediation and catalysis. Kaolin amorphous derivative (KAD) is well-suited to removal of many toxic metals down to ppb range from acid mine drainage. Engineering development trials of the KAD manufacturing process and the utilisation of KAD in polluted waters such as acid mine drainage indicates that scale-up from bench-scale is not a barrier to market entry.

A multi-scaled approach for simulating chemical reaction systems

In this paper we give an overview of some very recent work, as well as presenting a new approach, on the stochastic simulation of multi-scaled systems involving chemical reactions. In many biological systems (such as genetic regulation and cellular dynamics) there is a mix between small numbers of key regulatory proteins, and medium and large numbers of molecules. In addition, it is important to be able to follow the trajectories of individual molecules by taking proper account of the randomness inherent in such a system. We describe different types of simulation techniques (including the stochastic simulation algorithm, Poisson Runge-Kutta methods and the balanced Euler method) for treating simulations in the three different reaction regimes: slow, medium and fast. We then review some recent techniques on the treatment of coupled slow and fast reactions for stochastic chemical kinetics and present a new approach which couples the three regimes mentioned above. We then apply this approach to a biologically inspired problem involving the expression and activity of LacZ and LacY proteins in E coli, and conclude with a discussion on the significance of this work. (C) 2004 Elsevier Ltd. All rights reserved.

A new database compilation of whole-rock chemical and geochronological data of igneous rocks in Queensland : a new resource for HDR geothermal resource exploration

The Geothermal industry in Australia and Queensland is in its infancy and for hot dry rock (HDR) geothermal energy, it is very much in the target identification and resource definition stages. As a key effort to assist the geothermal industry and exploration for HDR in Queensland, we are developing a comprehensive and new integrated geochemical and geochronological database on igneous rocks. To date, around 18,000 igneous rocks have been analysed across Queensland for chemical and/or age information. However, these data currently reside in a number of disparate datasets (e.g., Ozchron, Champion et al., 2007, Geological Survey of Queensland, journal publications, and unpublished university theses). The goal of this project is to collate and integrate these data on Queensland igneous rocks to improve our understanding of high heat producing granites in Queensland, in terms of their distribution (particularly in the subsurface), dimensions, ages, and controlling factors in their genesis.

Sources of ultrafine particles and chemical species along a traffic corridor : comparison of the results from two receptor models

Particulate matter is common in our environment and has been linked to human health problems particularly in the ultrafine size range. A range of chemical species have been associated with particulate matter and of special concern are the hazardous chemicals that can accentuate health problems. If the sources of such particles can be identified then strategies can be developed for the reduction of air pollution and consequently, the improvement of the quality of life. In this investigation, particle number size distribution data and the concentrations of chemical species were obtained at two sites in Brisbane, Australia. Source apportionment was used to determine the sources (or factors) responsible for the particle size distribution data. The apportionment was performed by Positive Matrix Factorisation (PMF) and Principal Component Analysis/Absolute Principal Component Scores (PCA/APCS), and the results were compared with information from the gaseous chemical composition analysis. Although PCA/APCS resolved more sources, the results of the PMF analysis appear to be more reliable. Six common sources identified by both methods include: traffic 1, traffic 2, local traffic, biomass burning, and two unassigned factors. Thus motor vehicle related activities had the most impact on the data with the average contribution from nearly all sources to the measured concentrations higher during peak traffic hours and weekdays. Further analyses incorporated the meteorological measurements into the PMF results to determine the direction of the sources relative to the measurement sites, and this indicated that traffic on the nearby road and intersection was responsible for most of the factors. The described methodology which utilised a combination of three types of data related to particulate matter to determine the sources could assist future development of particle emission control and reduction strategies.

Preparing nanocomposite fibrous scaffolds of P3HB/nHA for bone tissue engineering

Nanocomposites are recently known to be among the most successful materials in biomedical applications. In this work we sought to fabricate fibrous scaffolds which can mimic the extra cellular matrix of cartilaginous connective tissue not only to a structural extent but with a mechanical and biological analogy. Poly(3-hydroxybutyrate) (P3HB) matrices were reinforced with 5, 10 and 15 %wt hydroxyapatite (HA) nanoparticles and electrospun into nanocomposite fibrous scaffolds. Mechanical properties of each case were compared with that of a P3HB scaffold produced in the same processing condition. Spectroscopic and morphological observations were used for detecting the interaction quality between the constituents. Nanoparticles rested deep within the fibers of 1 μm in diameter. Chemical interactions of hydrogen bonds linked the constituents through the interface. Maximum elastic modulus and mechanical strength was obtained with the presence of 5%wt hydroxyapatite nanoparticles. Above 10%wt, nanoparticles tended to agglomerate and caused the entity to lose its mechanical performance; however, viscoelasticity interfered at this concentration and lead to a delayed failure. In other words, higher elongation at break and a massive work of rupture was observed at 10%wt.

Aerosol mass spectrometric analysis of the chemical composition of non- refractory PM1 samples from school environments in Brisbane, Australia

Long term exposure to vehicle emissions has been associated with harmful health effects. Children are amongst the most susceptible group and schools represent an environment where they can experience significant exposure to vehicle emissions. However, there are limited studies on children’s exposure to vehicle emissions in schools. The aim of this study was to quantify the concentration of organic aerosol and in particular, vehicle emissions that children are exposed to during school hours. Therefore an Aerodyne compact time-of-flight aerosol mass spectrometer (TOF-AMS) was deployed at five urban schools in Brisbane, Australia. The TOF-AMS enabled the chemical composition of the non- refractory (NR-PM1) to be analysed with a high temporal resolution to assess the concentration of vehicle emissions and other organic aerosols during school hours. At each school the organic fraction comprised the majority of NR-PM1 with secondary organic aerosols as the main constitute. At two of the schools, a significant source of the organic aerosol (OA) was slightly aged vehicle emissions from nearby highways. More aged and oxidised OA was observed at the other three schools, which also recorded strong biomass burning influences. Primary emissions were found to dominate the OA at only one school which had an O:C ratio of 0.17, due to fuel powered gardening equipment used near the TOF-AMS. The diurnal cycle of OA concentration varied between schools and was found to be at a minimum during school hours. The major organic component that school children were exposed to during school hours was secondary OA. Peak exposure of school children to HOA occurred during school drop off and pick up times. Unless a school is located near major roads, children are exposed predominately to regional secondary OA as opposed to local emissions during schools hours in urban environments.

Deformation with coupled chemical diffusion

The deformation of rocks is commonly intimately associated with metamorphic reactions. This paper is a step towards understanding the behaviour of fully coupled, deforming, chemically reacting systems by considering a simple example of the problem comprising a single layer system with elastic-power law viscous constitutive behaviour where the deformation is controlled by the diffusion of a single chemical component that is produced during a metamorphic reaction. Analysis of the problem using the principles of non-equilibrium thermodynamics allows the energy dissipated by the chemical reaction-diffusion processes to be coupled with the energy dissipated during deformation of the layers. This leads to strain-rate softening behaviour and the resultant development of localised deformation which in turn nucleates buckles in the layer. All such diffusion processes, in leading to Herring-Nabarro, Coble or “pressure solution” behaviour, are capable of producing mechanical weakening through the development of a “chemical viscosity”, with the potential for instability in the deformation. For geologically realistic strain rates these chemical feed-back instabilities occur at the centimetre to micron scales, and so produce structures at these scales, as opposed to thermal feed-back instabilities that become important at the 100–1000 m scales.

Physico-chemical/biological properties of tripolyphosphate cross-linked chitosan based

In this study, chitosan-PEO blend, prepared in a 15 M acetic acid, was electrospun into nanofibers (~ 78 nm diameter) with bead free morphology. While investigating physico-chemical parameters of blend solutions, effect of yield stress on chitosan based nanofiber fabrication was clearly evidenced. Architectural stability of nanofiber mat in aqueous medium was achieved by ionotropic cross-linking of chitosan by tripolyphosphate (TPP) ions. The TPP cross-linked nanofiber mat showed swelling up to ~ 300 % in 1h and ~ 40 % degradation during 30 d study period. 3T3 fibroblast cells showed good attachment, proliferation and viability on TPP treated chitosan based nanofiber mats. The results indicate non-toxic nature of TPP cross-linked chitosan based nanofibers and their potential to be explored as a tissue engineering matrix.

Chitosan-collagen scaffolds with nano/microfibrous architecture for skin tissue engineering

In this study, a hierarchical nano/microfibrous chitosan/collagen scaffold that approximates structural and functional attributes of native extracellular matrix (ECM), has been developed for applicability in skin tissue engineering. Scaffolds were produced by electrospinning of chitosan followed by imbibing of collagen solution, freeze-drying and subsequent cross-linking of two polymers. Scanning electron microscopy showed formation of layered scaffolds with nano/microfibrous architechture. Physico-chemical properties of scaffolds including tensile strength, swelling behavior and biodegradability were found satisfactory for intended application. 3T3 fibroblasts and HaCaT keratinocytes showed good in vitro cellular response on scaffolds thereby indicating the matrices′ cytocompatible nature. Scaffolds tested in an ex vivo human skin equivalent (HSE) wound model, as a preliminary alternative to animal testing, showed keratinocyte migration and wound re-epithelization — a pre-requisite for healing and regeneration. Taken together, the herein proposed chitosan/collagen scaffold, shows good potential for skin tissue engineering.