981 resultados para chemical shifts


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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.

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A pilot study has produced 31 groundwater samples from a coal seam gas (CSG) exploration well located in Maramarua, New Zealand. This paper describes sources of CSG water chemistry variations, and makes sampling and analytical recommendations to minimize these variations. The hydrochemical character of these samples is studied using factor analysis, geochemical modelling, and a sparging experiment. Factor analysis unveils carbon dioxide (CO2) degassing as the principal cause of sample variation (about 33%). Geochemical modelling corroborates these results and identifies minor precipitation of carbonate minerals with degassing. The sparging experiment confirms the effect of CO2 degassing by showing a steady rise in pH while maintaining constant alkalinity. Factor analysis correlates variations in the major ion composition (about 17%) to changes in the pumping regime and to aquifer chemistry variations due to cation exchange reactions with argillaceous minerals. An effective CSG water sampling program can be put into practice by measuring pH at the well head and alkalinity at the laboratory; these data can later be used to calculate the carbonate speciation at the time the sample was collected. In addition, TDS variations can be reduced considerably if a correct drying temperature of 180°C is consistently implemented.

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10.1 Histamine and cytokines 10.1.1 Actions of histamine 10.1.2 Drugs that modify the actions of histamine 10.1.3 Cytokines 10.2 Eicosanoids 10.2.1 Cyclooxygenase (COX) and lipooxygenase system 10.2.2 Actions of eicosanoids 10.2.3 Drugs that modify the actions of eicosanoids 10.2.3.1 Inhibit phospholipase A2 10.2.3.2 Non-selective cyclooxygenase inhibitors 10.2.3.3 Selective COX-2 inhibitors 10.2.3.4 Agonists at prostaglandin receptors 10.2.3.5 Leukotriene receptor antagonists 10.3. 5-Hydroxtryptamine (serotonin), nitric oxide, and endothelin 10.3.1 5-HT and migraine 10.3.2 5-HT and the gastrointestinal tract 10.3.3 Nitric oxide and angina 10.3.4 Nitric oxide and erectile dysfunction 10.3.5 Endothelin and pulmonary hypertension

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Purpose. The purpose of the study was to investigate the changes in axial length occurring with shifts in gaze direction. Methods. Axial length measurements were obtained from the left eye of 30 young adults (10 emmetropes, 10 low myopes, and 10 moderate myopes) through a rotating prism with 15° deviation, along the foveal axis, using a noncontact optical biometer in each of the nine different cardinal directions of gaze over 5 minutes. The subject's fellow eye fixated on an external distance (6 m) target to control accommodation, also with 15° deviation. Axial length measurements were also performed in 15° and 25° downward gaze with the biometer inclined on a tilting table, allowing gaze shifts to be achieved with either full head turn but no eye turn, or full eye turn with no head turn. Results. There was a significant influence of gaze angle and time on axial length (both P < 0.001), with the greatest axial elongation (+18 ± 8 μm) occurring with inferonasal gaze (P < 0.001) and a slight decrease in axial length in superior gaze (−12 ± 17 μm) compared with primary gaze (P < 0.001). In downward gaze, a significant axial elongation occurred when eye turn was used (P < 0.001), but not when head turn was used to shift gaze (P > 0.05). Conclusions. The angle of gaze has a small but significant short-term effect on axial length, with greatest elongation occurring in inferonasal gaze. The elongation of the eye appears to be due to the influence of the extraocular muscles, in particular the oblique muscles.

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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.

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Detailed analytical electron microscope (AEM) studies of yellow whiskers produced by chemical vapor deposition (CVD)1 show that two basic types of whiskers are produced at low temperatures (between 1200°C and 1400°C) and low boron to carbon gas ratios. Both whisker types show planar microstructures such as twin planes and stacking faults oriented parallel to, or at a rhombohedral angle to, the growth direction. For both whisker types, the presence of droplet-like terminations containing both Si and Ni indicate that the growth process during CVD is via a vapor-liquid-solid (VLS) mechanism.

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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.

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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.

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The influence of different electrolyte cations ((Li+, Na+, Mg2+, tetrabutyl ammonium (TBA+)) on the TiO2 conduction band energy (Ec) the effective electron lifetime (τn), and the effective electron diffusion coefficient (Dn) in dye-sensitized solar cells (DSCs) was studied quantitatively. The separation between Ec and the redox Fermi level, EF,redox, was found to decrease as the charge/radius ratio of the cations increased. Ec in the Mg2+ electrolyte was found to be 170 meV lower than that in the Na+ electrolyte and 400 meV lower than that in the TBA+ electrolyte. Comparison of Dn and τn in the different electrolytes was carried out by using the trapped electron concentration as a measure of the energy difference between Ec and the quasi-Fermi level, nEF, under different illumination levels. Plots of Dn as a function of the trapped electron density, nt, were found to be relatively insensitive to the electrolyte cation, indicating that the density and energetic distribution of electron traps in TiO2 are similar in all of the electrolytes studied. By contrast, plots of τn versus nt for the different cations showed that the rate of electron back reaction is more than an order of magnitude faster in the TBA+ electrolyte compared with the Na+ and Li+ electrolytes. The electron diffusion lengths in the different electrolytes followed the sequence of Na+ > Li+ > Mg2+ > TBA+. The trends observed in the AM 1.5 current–voltage characteristics of the DSCs are rationalized on the basis of the conduction band shifts and changes in electron lifetime.

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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.

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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.

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An investigation on hydrogen and methane sensing performance of hydrothermally formed niobium tungsten oxide nanorods employed in a Schottky diode structure is presented herein. By implementing tungsten into the surface of the niobium lattice, we create Nb5+ and W5+ oxide states and an abundant number of surface traps, which can collect and hold the adsorbate charge to reinforce a greater bending of the energy bands at the metal/oxide interface. We show experimentally, that extremely large voltage shifts can be achieved by these nanorods under exposure to gas at both room and high temperatures and attribute this to the strong accumulation of the dipolar charges at the interface via the surface traps. Thus, our results demonstrate that niobium tungsten oxide nanorods can be implemented for gas sensing applications, showing ultra-high sensitivities.

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A nanostructured Schottky diode was fabricated to sense hydrogen and propene gases in the concentration range of 0.06% to 1%. The ZnO sensitive layer was deposited on SiC substrate by pulse laser deposition technique. Scanning electron microscopy and X-ray diffraction characterisations revealed presence of wurtzite structured ZnO nanograins grown in the direction of (002) and (004). The nanostructured diode was investigated at optimum operating temperature of 260 °C. At a constant reverse current of 1 mA, the voltage shifts towards 1% hydrogen and 1% propene were measured as 173.3 mV and 191.8 mV, respectively.

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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.