Nitrogen-doped graphene films from chemical vapor deposition of pyridine: Influence of process parameters on the electrical and optical properties

Graphene films were produced by chemical vapor deposition (CVD) of pyridine on copper substrates. Pyridine-CVD is expected to lead to doped graphene by the insertion of nitrogen atoms in the growing sp2 carbon lattice, possibly improving the properties of graphene as a transparent conductive film. We here report on the influence that the CVD parameters (i.e., temperature and gas flow) have on the morphology, transmittance, and electrical conductivity of the graphene films grown with pyridine. A temperature range between 930 and 1070 °C was explored and the results were compared to those of pristine graphene grown by ethanol-CVD under the same process conditions. The films were characterized by atomic force microscopy, Raman and X-ray photoemission spectroscopy. The optical transmittance and electrical conductivity of the films were measured to evaluate their performance as transparent conductive electrodes. Graphene films grown by pyridine reached an electrical conductivity of 14.3 × 105 S/m. Such a high conductivity seems to be associated with the electronic doping induced by substitutional nitrogen atoms. In particular, at 930 °C the nitrogen/carbon ratio of pyridine-grown graphene reaches 3%, and its electrical conductivity is 40% higher than that of pristine graphene grown from ethanol-CVD.

Biophysical response of living cells to boron nitride nanoparticles: Uptake mechanism and bio-mechanical characterization

Boron nitride nanomaterials have attracted significant interest due to their superior chemical and physical properties. Despite these novel properties, investigation on the interaction between boron nitride nanoparticle (BN NP) and living systems has been limited. In this study, BN NP (100–250 nm) is assessed as a promising biomaterial for medical applications. The toxicity of BN NP is evaluated by assessing the cells behaviours both biologically (MTT assay, ROS detection etc.) and physically (atomic force microscopy). The uptake mechanism of BN NP is studied by analysing the alternations in cellular morphology based on cell imaging techniques. The results demonstrate in vitro cytocompatibility of BN NP with immense potential for use as an effective nanoparticle for various bio-medical applications.

Evaluation of residence time on nitrogen oxides removal in non-thermal plasma reactor

Non-thermal plasma (NTP) has been introduced over the last few years as a promising after- treatment system for nitrogen oxides and particulate matter removal from diesel exhaust. NTP technology has not been commercialised as yet, due to its high rate of energy consumption. Therefore, it is important to seek out new methods to improve NTP performance. Residence time is a crucial parameter in engine exhaust emissions treatment. In this paper, different electrode shapes are analysed and the corresponding residence time and NOx removal efficiency are studied. An axisymmetric laminar model is used for obtaining residence time distribution numerically using FLUENT software. If the mean residence time in a NTP plasma reactor increases, there will be a corresponding increase in the reaction time and consequently the pollutant removal efficiency increases. Three different screw thread electrodes and a rod electrode are examined. The results show the advantage of screw thread electrodes in comparison with the rod electrode. Furthermore, between the screw thread electrodes, the electrode with the thread width of 1 mm has the highest NOx removal due to higher residence time and a greater number of micro-discharges. The results show that the residence time of the screw thread electrode with a thread width of 1 mm is 21% more than for the rod electrode.

DFT study of electronic and optical properties of anatase titanium dioxide tuned by nitrogen and lithium co-doping

The electronic and optical properties of anatase titanium dioxide (TiO2), co-doped by nitrogen (N) and lithium (Li), have been investigated by density functional theory plus Hubbard correction term U, namely DFT+U. It is found that Li-dopants can effectively balance the net charges brought by N-dopants and shift the local state to the top of valence band. Depending on the distribution of dopants, the adsorption edges of TiO2 may be red- or blue-shifted, being consistent with recent experimental observations.

Levels and predictors of exercise referral scheme uptake and adherence: A systematic review

Background The effectiveness of exercise referral schemes (ERS) is influenced by uptake and adherence to the scheme. The identification of factors influencing low uptake and adherence could lead to the refinement of schemes to optimise investment. Objectives To quantify the levels of ERS uptake and adherence and to identify factors predictive of uptake and adherence. Methods A systematic review and meta-analysis was undertaken. MEDLINE, EMBASE, PsycINFO, Cochrane Library, ISI WOS, SPORTDiscus and ongoing trial registries were searched (to October 2009) and included study references were checked. Included studies were required to report at least one of the following: (1) a numerical measure of ERS uptake or adherence and (2) an estimate of the statistical association between participant demographic or psychosocial factors (eg, level of motivation, self-efficacy) or programme factors and uptake or adherence to ERS. Results Twenty studies met the inclusion criteria, six randomised controlled trials (RCTs) and 14 observational studies. The pooled level of uptake in ERS was 66% (95% CI 57% to 75%) across the observational studies and 81% (95% CI 68% to 94%) across the RCTs. The pooled level of ERS adherence was 49% (95% CI 40% to 59%) across the observational studies and 43% (95% CI 32% to 54%) across the RCTs. Few studies considered anything other than gender and age. Women were more likely to begin an ERS but were less likely to adhere to it than men. Older people were more likely to begin and adhere to an ERS. Limitations Substantial heterogeneity was evident across the ERS studies. Without standardised definitions, the heterogeneity may have been reflective of differences in methods of defining uptake and adherence across studies. Conclusions To enhance our understanding of the variation in uptake and adherence across ERS and how these variations might affect physical activity outcomes, future trials need to use quantitative and qualitative methods.

Insights into PBDE uptake, body burden, and elimination gained from Australian age–Concentration trends observed shortly after peak exposure

Background Population pharmacokinetic models combined with multiple sets of age– concentration biomonitoring data facilitate back-calculation of chemical uptake rates from biomonitoring data. Objectives We back-calculated uptake rates of PBDEs for the Australian population from multiple biomonitoring surveys (top-down) and compared them with uptake rates calculated from dietary intake estimates of PBDEs and PBDE concentrations in dust (bottom-up). Methods Using three sets of PBDE elimination half-lives, we applied a population pharmacokinetic model to the PBDE biomonitoring data measured between 2002–2003 and 2010–2011 to derive the top-down uptake rates of four key PBDE congeners and six age groups. For the bottom-up approach, we used PBDE concentrations measured around 2005. Results Top-down uptake rates of Σ4BDE (the sum of BDEs 47, 99, 100, and 153) varied from 7.9 to 19 ng/kg/day for toddlers and from 1.2 to 3.0 ng/kg/day for adults; in most cases, they were—for all age groups—higher than the bottom-up uptake rates. The discrepancy was largest for toddlers with factors up to 7–15 depending on the congener. Despite different elimination half-lives of the four congeners, the age–concentration trends showed no increase in concentration with age and were similar for all congeners. Conclusions In the bottom-up approach, PBDE uptake is underestimated; currently known pathways are not sufficient to explain measured PBDE concentrations, especially in young children. Although PBDE exposure of toddlers has declined in the past years, pre- and postnatal exposure to PBDEs has remained almost constant because the mothers’ PBDE body burden has not yet decreased substantially.

Mathematical modelling of human corneal oxygenation and cell kinetics in corneal epithelial wound healing

Healthy transparent cornea depends upon the regulation of fluid, nutrient and oxygen transport through the tissue to sustain cell metabolism and other critical processes for normal functioning. This research considers the corneal geometry and investigates oxygen distribution using a two-dimensional Monod kinetic model, showing that previous studies make assumptions that lead to predictions of near-anoxic levels of oxygen tension in the limbal regions of the cornea. It also considers the comparison of experimental spatial and temporal data with the predictions of novel mathematical models with respect to distributed mitotic rates during corneal epithelial wound healing.

Dynamics of nitrate-nitrogen removal in experimental stormwater biofilters under intermittent wetting and drying

High concentrations of nitrate-nitrogen degrade the quality of aquatic environments. The primary mechanism by which nitrate-nitrogen is removed (denitrification) requires anoxic conditions and electron donors. While removal of total and ammonium-nitrogen is often high in stormwater biofilters, poor removal or even the release of nitrate-nitrogen in the outflow has often been observed. Five Perspex biofilter columns (94 mm internal diameter) were fabricated with a filter layer that contained 8% organic material. Columns were operated at 875  mm/h 875  mm/h and fed with simulated stormwater with different antecedent dry days (ADDs) and concentrations of nitrate-nitrogen. Samples were collected from the outflow at different time intervals between 2 and 150 min and were tested for nitrate-nitrogen. The removal of nitrate-nitrogen varied during an event from a high removal percentage (60–90%) in the initial outflow that gradually decreased in the first 30 min and settled at 0–15% removal thereafter. This remained consistent during all simulated events independent of the number of ADDs or inflow concentrations. ADDs and previous event feed concentrations affected the outflow nitrate-nitrogen concentration in the first 30 min of the current event. Therefore, from this study it is concluded that denitrification within stormwater biofilters occurs mainly during drying periods rather than wetting periods.

Factors influencing kinetic and equilibrium behaviour of sodium ion exchange with strong acid cation resin

This study reports an investigation of the ion exchange treatment of sodium chloride solutions in relation to use of resin technology for applications such as desalination of brackish water. In particular, a strong acid cation (SAC) resin (DOW Marathon C) was studied to determine its capacity for sodium uptake and to evaluate the fundamentals of the ion exchange process involved. Key questions to answer included: impact of resin identity; best models to simulate the kinetics and equilibrium exchange behaviour of sodium ions; difference between using linear least squares (LLS) and non-linear least squares (NLLS) methods for data interpretation; and, effect of changing the type of anion in solution which accompanied the sodium species. Kinetic studies suggested that the exchange process was best described by a pseudo first order rate expression based upon non-linear least squares analysis of the test data. Application of the Langmuir Vageler isotherm model was recommended as it allowed confirmation that experimental conditions were sufficient for maximum loading of sodium ions to occur. The Freundlich expression best fitted the equilibrium data when analysing the information by a NLLS approach. In contrast, LLS methods suggested that the Langmuir model was optimal for describing the equilibrium process. The Competitive Langmuir model which considered the stoichiometric nature of ion exchange process, estimated the maximum loading of sodium ions to be 64.7 g Na/kg resin. This latter value was comparable to sodium ion capacities for SAC resin published previously. Inherent discrepancies involved when using linearized versions of kinetic and isotherm equations were illustrated, and despite their widespread use, the value of this latter approach was questionable. The equilibrium behaviour of sodium ions form sodium fluoride solution revealed that the sodium ions were now more preferred by the resin compared to the situation with sodium chloride. The solution chemistry of hydrofluoric acid was suggested as promoting the affinity of the sodium ions to the resin.

Annual nitrogen dynamics and urea fertilizer recoveries from a dairy pasture using 15N; effect of nitrification inhibitor DMPP and reduced application rates

Direct nitrogen (N) losses from pastures contribute to the poor nitrogen use efficiency of the dairy industry, though the exact fate of applied N and the processes involved are largely unknown. Nitrification inhibitors such as DMPP can potentially increase fertilizer N use efficiency (NUE), though few studies globally have examined the effectiveness of DMPP coated urea in pastures. This study quantified the NUE of DMPP combined with reduced application rates, and the effect on N dynamics and plant–soil interactions over an annual ryegrass/kikuyu rotation in Queensland, Australia. Labeled 15N urea and DMPP was applied over 7 winter applications at standard farmer (45 kg N ha−1) and half (23 kg N ha−1) rates. Fertilizer recoveries and NUE were calculated over 13 harvests, and the contribution of fertilizer and soil N estimated. Up to 85% of the annual N harvested was from soil organic matter. DMPP at the lower rate increased annual yields by 31% compared to the equivalent urea treatment with no difference to the high N rates. Almost 40% of the N added at the conventional fertilizer application rate as urea was lost to the environment; 80 kg N ha−1 higher than the low DMPP. Combining the nitrification inhibitor DMPP with reduced fertilizer application rates shows substantial potential to reduce N losses to the environment while sustaining productivity in subtropical dairy pastures.

Non-linear response of soil N2O emissions to nitrogen fertiliser in a cotton-fallow rotation in sub-tropical Australia

Nitrogen fertiliser is a major source of atmospheric N2O and over recent years there is growing evidence for a non-linear, exponential relationship between N fertiliser application rate and N2O emissions. However, there is still high uncertainty around the relationship of N fertiliser rate and N2O emissions for many cropping systems. We conducted year-round measurements of N2O emission and lint yield in four N rate treatments (0, 90, 180 and 270 kg N ha-1) in a cotton-fallow rotation on a black vertosol in Australia. We observed a nonlinear exponential response of N2O emissions to increasing N fertiliser rates with cumulative annual N2O emissions of 0.55 kg N ha-1, 0.67kg N ha-1, 1.07 kg N ha-1 and 1.89 kg N ha-1 for the four respective N fertiliser rates while no N response to yield occurred above 180N. The N fertiliser induced annual N2O EF factors increased from 0.13% to 0.29% and 0.50% for the 90N, 180N and 270N treatments respectively, significantly lower than the IPCC Tier 1 default value (1.0 %). This non-linear response suggests that an exponential N2O emissions model may be more appropriate for use in estimating emission of N2O from soils cultivated to cotton in Australia. It also demonstrates that improved agricultural N management practices can be adopted in cotton to substantially reduce N2O emissions without affecting yield potential.

Behaviour of natural zeolites used for the treatment of simulated and actual coal seam gas water

Coal seam gas operations produce significant quantities of associated water which often require demineralization. Ion exchange with natural zeolites has been proposed as a possible approach. The interaction of natural zeolites with solutions of sodium chloride and sodium bicarbonate in addition to coal seam gas water is not clear. Hence, we investigated ion exchange kinetics, equilibrium, and column behaviour of an Australian natural zeolite. Kinetic tests suggested that the pseudo first order equation best simulated the data. Intraparticle diffusion was part of the rate limiting step and more than one diffusion process controlled the overall rate of sodium ion uptake. Using a constant mass of zeolite and variable concentration of either sodium chloride or sodium bicarbonate resulted in a convex isotherm which was fitted by a Langmuir model. However, using a variable mass of zeolite and constant concentration of sodium ions revealed that the exchange of sodium ions with the zeolite surface sites was in fact unfavourable. Sodium ion exchange from bicarbonate solutions (10.3 g Na/kg zeolite) was preferred relative to exchange from sodium chloride solutions (6.4 g Na/kg zeolite). The formation of calcium carbonate species was proposed to explain the observed behaviour. Column studies of coal seam gas water showed that natural zeolite had limited ability to reduce the concentration of sodium ions (loading 2.1 g Na/kg zeolite) with rapid breakthrough observed. It was concluded that natural zeolites may not be suitable for the removal of cations from coal seam gas water without improvement of their physical properties.

Molecular and biochemical characterisation of transgenic banana lines containing iron uptake and storage enhancing genes

This thesis investigated the basis for availability of iron (Fe) and zinc (Zn) content in different banana fruits grown in Uganda and Australia. Rather than micronutrient content levels in different banana cultivar, genotype and environment interactions explained much of the differences. Such information should provide important insights for future developments in the biofortification of banana. Bananas consumed in Uganda did not contain sufficient levels of Fe and Zn that meet the nutrient requirements for vulnerable groups.

Kinetics and mechanism of hot corrosion of γ-Y 2Si 2O 7 in thin-film Na 2SO 4 molten salt

γ-Y 2Si 2O 7 is a promising candidate material both for hightemperature structural applications and as an environmental/thermal barrier coating material due to its unique properties such as high melting point, machinability, thermal stability, low linear thermal expansion coefficient (3.9×10 -6/K, 200°-1300°C), and low thermal conductivity (<3.0 W/ṁK above 300°C). The hot corrosion behavior of γ-Y 2Si 2O 7 in thin-film molten Na 2SO 4 at 850°-1000°C for 20 h in flowing air was investigated using a thermogravimetric analyzer (TGA) and a mass spectrometer (MS). γ-Y 2Si 2O 7 exhibited good resistance against Na 2SO 4 molten salt. The kinetic curves were well fitted by a paralinear equation: the linear part was caused by the evaporation of Na2SO4 and the parabolic part came from gas products evolved from the hotcorrosion reaction. A thin silica film formed under the corrosion scale was the key factor for retarding the hot corrosion. The apparent activation energy for the corrosion of γ-Y 2Si 2O 7 in Na 2SO 4 molten salt with flowing air was evaluated to be 255 kJ/mol.