585 resultados para Controlled synthesis


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This paper begins by providing an overview of bike share programs, followed by a critical examination of the growing body of literature on these programs. This synthesis of previous works, both peer-reviewed and grey, includes an identification of the current gaps in knowledge related to the impacts of bike sharing programs. This synthesis represents a critically needed evaluation of the current state of global bike share research, in order to better understand, and maximize the effectiveness of current and future programs. Several consistent themes have emerged within the growing body of research on bike share programs. Firstly, the importance bike share members place on convenience and value for money appears paramount in their motivation to sign up and use these programs. Secondly, and somewhat counter intuitively, scheme members are more likely to own and use private bicycles than non-members. Thirdly, users demonstrate a greater reluctance to wear helmets than private bicycle riders and helmets have acted as a deterrent in jurisdictions in which helmets are mandatory. Finally, and perhaps most importantly from a sustainable transport perspective, the majority of scheme users are substituting from sustainable modes of transport rather than the car.

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The optimum parameters for synthesis of zeolite NaA based on metakaolin were investigated according to results of cation exchange capacity and static water adsorption of all synthesis products and selected X-ray diffraction (XRD). Magnetic zeolite NaA was synthesized by adding Fe3O4 in the precursor of zeolite. Zeolite NaA and magnetic zeolite NaA were characterized with scanning electron microscopy (SEM) and XRD. Magnetic zeolite NaA with different Fe3O4 loadings was prepared and used for removal of heavy metals (Cu2+, Pb2+). The results show the optimum parameters for synthesis zeolite NaA are SiO2/Al2O3 = 2.3, Na2O/SiO2 = 1.4, H2O/Na2O = 50, crystallization time 8 h, crystallization temperature 95 �C. The addition of Fe3O4 makes the NaA zeolite with good magnetic susceptibility and good magnetic stability regardless of the Fe3O4 loading, confirming the considerable separation efficiency. Additionally, Fe3O4 loading had a little effect on removal of heavy metal by magnetic zeolite, however, the adsorption capacity still reaches 2.3 mmol g�1 for Cu2+, Pb2+ with a removal efficiency of over 95% in spite of 4.7% Fe3O4 loading. This indicates magnetic zeolite can be used to remove metal heavy at least Cu2+, Pb2+ from water with metallic contaminants and can be separated easily after a magnetic process.

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The robust and diversely useful isoindoline nitroxide, 5-carboxy-1,1,3,3-tetramethylisoindolin-2-yloxyl (1; CTMIO), has previously been synthesised in low-to-moderate yields from phthalic anhydride (3). Recent interest in its biological potential as a potent antioxidant and in other areas has seen an increased demand for its production. Herein, three new synthetic routes to CTMIO are presented and their efficiencies assessed. Two routes, via the nitrile 9 and the formyl compound 11, derive from 5-bromo-1,1,3,3-tetramethylisoindoline (6). The third approach starts from the readily accessible starting material, 4-methylphthalic anhydride (12), and proceeds by a methylarene oxidation with potassium permanganate. The three new approaches yield CTMIO in comparable overall yields (16–18 %); however, the synthetic efficiency is most improved when employing the nitrile intermediate 9.

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Boron–nitrogen containing compounds with high hydrogen contents as represented by ammonia borane (NH3BH3) have recently attracted intense interest for potential hydrogen storage applications. One such compound is [(NH3)2BH2]B3H8 with a capacity of 18.2 wt% H. Two safe and efficient synthetic routes to [(NH3)2BH2]B3H8 have been developed for the first time since it was discovered 50 years ago. The new synthetic routes avoid a dangerous starting chemical, tetraborane (B4H10), and afford a high yield. Single crystal X-ray diffraction analysis reveals N–Hδ+Hδ−–B dihydrogen interactions in the [(NH3)2BH2]B3H8·18-crown-6 adduct. Extended strong dihydrogen bonds were observed in pure [(NH3)2BH2]B3H8 through crystal structure solution based upon powder X-ray analysis. Pyrolysis of [(NH3)2BH2]B3H8 leads to the formation of hydrogen gas together with appreciable amounts of volatile boranes below 160 °C.

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The microwave synthesis of MnC2O4·2H2O nanoparticles was performed through the thermal double decomposition of oxalic acid dihydrate (C2H2O4·2H2O) and Mn(OAc)2·4H2O solutions using a CATA-2R microwave reactor. Structural characterization was performed using X-ray diffraction (XRD), particle size and shape were analyzed using transmission electron microscopy (TEM). The chemical in the structures was investigated using electron paramagnetic resonance (EPR) as well as optical absorption spectra and near-infrared (NIR) spectroscopies. The nanocrystals produced with this method were pure and had a distorted rhombic octahedral structure.

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Amphiphilic poly(ethylene glycol)-block-pol (dimethylsiloxane)-block-poly(ethylene glycol)(PEG-block-PDMS block-PEG) triblock copolymers have been successfully prepared via hydrosilylation using discrete and polydisperse PEG of various chain lengths. Facile synthesis of discrete PEG (dPEG) is achieved via systematic tosylation and etherification of lower glycols. Amphiphilicity of the dPEG block-PDMS-block-dPEG triblock copolymer is illustrated by dynamic light scattering (DLS) and measurement of the critical micelle concentration (CMC).

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A nanocomposite of Mn3O4 wrapped in graphene sheets (GSs) was successfully synthesized via a facile, effective, energy-saving, and scalable microwave hydrothermal technique. The morphology and microstructures of the fabricated GS–Mn3O4 nanocomposite were characterized using various techniques. The results indicate that the particle size of the Mn3O4 particles in the nanocomposite markedly decreased to nearly 20 nm, significantly smaller than that for the bare Mn3O4. Electrochemical measurements demonstrated a high specific capacity of more than 900 mA h g−1 at 40 mA g−1, and excellent cycling stability with no capacity decay can be observed up to 50 cycles. All of these properties are also interpreted by experimental studies and theoretical calculations.

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Controlled drug delivery is a key topic in modern pharmacotherapy, where controlled drug delivery devices are required to prolong the period of release, maintain a constant release rate, or release the drug with a predetermined release profile. In the pharmaceutical industry, the development process of a controlled drug delivery device may be facilitated enormously by the mathematical modelling of drug release mechanisms, directly decreasing the number of necessary experiments. Such mathematical modelling is difficult because several mechanisms are involved during the drug release process. The main drug release mechanisms of a controlled release device are based on the device’s physiochemical properties, and include diffusion, swelling and erosion. In this thesis, four controlled drug delivery models are investigated. These four models selectively involve the solvent penetration into the polymeric device, the swelling of the polymer, the polymer erosion and the drug diffusion out of the device but all share two common key features. The first is that the solvent penetration into the polymer causes the transition of the polymer from a glassy state into a rubbery state. The interface between the two states of the polymer is modelled as a moving boundary and the speed of this interface is governed by a kinetic law. The second feature is that drug diffusion only happens in the rubbery region of the polymer, with a nonlinear diffusion coefficient which is dependent on the concentration of solvent. These models are analysed by using both formal asymptotics and numerical computation, where front-fixing methods and the method of lines with finite difference approximations are used to solve these models numerically. This numerical scheme is conservative, accurate and easily implemented to the moving boundary problems and is thoroughly explained in Section 3.2. From the small time asymptotic analysis in Sections 5.3.1, 6.3.1 and 7.2.1, these models exhibit the non-Fickian behaviour referred to as Case II diffusion, and an initial constant rate of drug release which is appealing to the pharmaceutical industry because this indicates zeroorder release. The numerical results of the models qualitatively confirms the experimental behaviour identified in the literature. The knowledge obtained from investigating these models can help to develop more complex multi-layered drug delivery devices in order to achieve sophisticated drug release profiles. A multi-layer matrix tablet, which consists of a number of polymer layers designed to provide sustainable and constant drug release or bimodal drug release, is also discussed in this research. The moving boundary problem describing the solvent penetration into the polymer also arises in melting and freezing problems which have been modelled as the classical onephase Stefan problem. The classical one-phase Stefan problem has unrealistic singularities existed in the problem at the complete melting time. Hence we investigate the effect of including the kinetic undercooling to the melting problem and this problem is called the one-phase Stefan problem with kinetic undercooling. Interestingly we discover the unrealistic singularities existed in the classical one-phase Stefan problem at the complete melting time are regularised and also find out the small time behaviour of the one-phase Stefan problem with kinetic undercooling is different to the classical one-phase Stefan problem from the small time asymptotic analysis in Section 3.3. In the case of melting very small particles, it is known that surface tension effects are important. The effect of including the surface tension to the melting problem for nanoparticles (no kinetic undercooling) has been investigated in the past, however the one-phase Stefan problem with surface tension exhibits finite-time blow-up. Therefore we investigate the effect of including both the surface tension and kinetic undercooling to the melting problem for nanoparticles and find out the the solution continues to exist until complete melting. The investigation of including kinetic undercooling and surface tension to the melting problems reveals more insight into the regularisations of unphysical singularities in the classical one-phase Stefan problem. This investigation gives a better understanding of melting a particle, and contributes to the current body of knowledge related to melting and freezing due to heat conduction.

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Adolescent injury remains a significant public health concern and is often the result of at-risk transport related behaviours. When a person is injured actions taken by bystanders are of crucial importance and timely first aid appears to reduce the severity of some injuries (Hussain & Redmond, 1994). Accordingly, researchers have suggested that first aid training should be more widely available as a potential strategy to reduce injury (Lynch et al., 2006). Further research has identified schools as an ideal setting for learning first aid skills as a means of injury prevention (Maitra, 1997). The current research examines the implications of school based first aid training for young adolescents on injury prevention, particularly relating to transport injuries. First aid training was integrated with peer protection and school connectedness within the Skills for Preventing Injury in Youth (SPIY) program (Buckley & Sheehan, 2009) and evaluated to determine if there was a reduction in the likelihood of transport related injuries at six months post-intervention. In Queensland, Australia, 35 high schools were recruited and randomly assigned to intervention and control conditions in early April 2012. A total of 2,000 Year nine students (mean age 13.5 years, 39% male) completed surveys six months post-intervention in November 2012. Analyses will compare the intervention students with control group students who self-reported i) first aid training with a teacher, professional or other adult and ii) no first aid in the preceding six months. Using the Extended Adolescent Injury Checklist (E-AIC) (Chapman, Buckley & Sheehan, 2011) the transport related injury experiences included being injured while “riding as a passenger in a car”, “driving a car off road” and “riding a bicycle”. It is expected that students taught first aid within SPIY will report significantly fewer transport related injuries in the previous three months, compared to the control groups described above. Analyses will be conducted separately for sex and socio-economic class of schools. Findings from this study will provide insight into the value of first aid in adolescent injury prevention and provide evidence as to whether teaching first aid skills within a school based health education curriculum has traffic safety implications.

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Increasing concerns about the atmospheric CO2 concentration and its impact on the environment are motivating researchers to discover new materials and technologies for efficient CO2 capture and conversion. Here, we report a study of the adsorption of CO2, CH4, and H2 on boron nitride (BN) nanosheets and nanotubes (NTs) with different charge states. The results show that the process of CO2 capture/release can be simply controlled by switching on/off the charges carried by BN nanomaterials. CO2 molecules form weak interactions with uncharged BN nanomaterials and are weakly adsorbed. When extra electrons are introduced to these nanomaterials (i.e., when they are negatively charged), CO2 molecules become tightly bound and strongly adsorbed. Once the electrons are removed, CO2 molecules spontaneously desorb from BN absorbents. In addition, these negatively charged BN nanosorbents show high selectivity for separating CO2 from its mixtures with CH4 and/or H2. Our study demonstrates that BN nanomaterials are excellent absorbents for controllable, highly selective, and reversible capture and release of CO2. In addition, the charge density applied in this study is of the order of 1013 cm–2 of BN nanomaterials and can be easily realized experimentally.

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Several randomized trials have found behavior change programs delivered via text messaging to be efficacious to improve preventive health behaviors such as physical activity and stopping smoking; however few have assessed its value in skin cancer prevention or early detection. The HealthyTexts study enrolled 678 participants 18–42 years, and assigned them to receive 21 text messages about skin cancer prevention, skin self-examination or physical activity(attention control) over the course of one year. Baseline data have been collected and outcomes will be assessed at three months and twelve months post intervention. The trial aims to increase the mean overall sun protection habits index score from 2.3 to 2.7 with a standard deviation of 0.5 (effect size of 0.5) and the proportion of people who conduct a whole-body skin self-examination by an absolute 10%. This paper describes the study design and participants' baseline characteristics. In addition, participants' goals for their health, and strategies they apply to achieve those goals are summarized.

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Sol-gel synthesis in varied gravity is only a relatively new topic in the literature and further investigation is required to explore its full potential as a method to synthesise novel materials. Although trialled for systems such as silica, the specific application of varied gravity synthesis to other sol-gel systems such as titanium has not previously been undertaken. Current literature methods for the synthesis of sol-gel material in reduced gravity could not be applied to titanium sol-gel processing, thus a new strategy had to be developed in this study. To successfully conduct experiments in varied gravity a refined titanium sol-gel chemical precursor had to be developed which allowed the single solution precursor to remain un-reactive at temperatures up to 50oC and only begin to react when exposed to a pressure decrease from a vacuum. Due to the new nature of this precursor, a thorough characterisation of the reaction precursors was subsequently undertaken with the use of techniques such as Nuclear Magnetic Resonance, Infra-red and UV-Vis spectroscopy in order to achieve sufficient understanding of precursor chemistry and kinetic stability. This understanding was then used to propose gelation reaction mechanisms under varied gravity conditions. Two unique reactor systems were designed and built with the specific purpose to allow the effects of varied gravity (high, normal, reduced) during synthesis of titanium sol-gels to be studied. The first system was a centrifuge capable of providing high gravity environments of up to 70 g’s for extended periods, whilst applying a 100 mbar vacuum and a temperature of 40-50oC to the reaction chambers. The second system to be used in the QUT Microgravity Drop Tower Facility was also required to provide the same thermal and vacuum conditions used in the centrifuge, but had to operate autonomously during free fall. Through the use of post synthesis characterisation techniques such as Raman Spectroscopy, X-Ray diffraction (XRD) and N2 adsorption, it was found that increased gravity levels during synthesis, had the greatest effect on the final products. Samples produced in reduced and normal gravity appeared to form amorphous gels containing very small particles with moderate surface areas. Whereas crystalline anatase (TiO2), was found to form in samples synthesised above 5 g with significant increases in crystallinity, particle size and surface area observed when samples were produced at gravity levels up to 70 g. It is proposed that for samples produced in higher gravity, an increased concentration gradient of water is forms at the bottom of the reacting film due to forced convection. The particles formed in higher gravity diffuse downward towards this excess of water, which favours the condensation reaction of remaining sol gel precursors with the particles promoting increased particle growth. Due to the removal of downward convection in reduced gravity, particle growth due to condensation reaction processes are physically hindered hydrolysis reactions favoured instead. Another significant finding from this work was that anatase could be produced at relatively low temperatures of 40-50oC instead of the conventional method of calcination above 450oC solely through sol-gel synthesis at higher gravity levels. It is hoped that the outcomes of this research will lead to an increased understanding of the effects of gravity on chemical synthesis of titanium sol-gel, potentially leading to the development of improved products suitable for diverse applications such as semiconductor or catalyst materials as well as significantly reducing production and energy costs through manufacturing these materials at significantly lower temperatures.

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Background Falls are one of the most frequently occurring adverse events that impact upon the recovery of older hospital inpatients. Falls can threaten both immediate and longer-term health and independence. There is need to identify cost-effective means for preventing falls in hospitals. Hospital-based falls prevention interventions tested in randomized trials have not yet been subjected to economic evaluation. Methods Incremental cost-effectiveness analysis was undertaken from the health service provider perspective, over the period of hospitalization (time horizon) using the Australian Dollar (A$) at 2008 values. Analyses were based on data from a randomized trial among n = 1,206 acute and rehabilitation inpatients. Decision tree modeling with three-way sensitivity analyses were conducted using burden of disease estimates developed from trial data and previous research. The intervention was a multimedia patient education program provided with trained health professional follow-up shown to reduce falls among cognitively intact hospital patients. Results The short-term cost to a health service of one cognitively intact patient being a faller could be as high as A$14,591 (2008). The education program cost A$526 (2008) to prevent one cognitively intact patient becoming a faller and A$294 (2008) to prevent one fall based on primary trial data. These estimates were unstable due to high variability in the hospital costs accrued by individual patients involved in the trial. There was a 52% probability the complete program was both more effective and less costly (from the health service perspective) than providing usual care alone. Decision tree modeling sensitivity analyses identified that when provided in real life contexts, the program would be both more effective in preventing falls among cognitively intact inpatients and cost saving where the proportion of these patients who would otherwise fall under usual care conditions is at least 4.0%. Conclusions This economic evaluation was designed to assist health care providers decide in what circumstances this intervention should be provided. If the proportion of cognitively intact patients falling on a ward under usual care conditions is 4% or greater, then provision of the complete program in addition to usual care will likely both prevent falls and reduce costs for a health service.

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Temperate Australia sits between the heat engine of the tropics and the cold Southern Ocean, encompassing a range of rainfall regimes and falling under the influence of different climatic drivers. Despite this heterogeneity, broad-scale trends in climatic and environmental change are evident over the past 30 ka. During the early glacial period (∼30–22 ka) and the Last Glacial Maximum (∼22–18 ka), climate was relatively cool across the entire temperate zone and there was an expansion of grasslands and increased fluvial activity in regionally important Murray–Darling Basin. The temperate region at this time appears to be dominated by expanded sea ice in the Southern Ocean forcing a northerly shift in the position of the oceanic fronts and a concomitant influx of cold water along the southeast (including Tasmania) and southwest Australian coasts. The deglacial period (∼18–12 ka) was characterised by glacial recession and eventual disappearance resulting from an increase in temperature deduced from terrestrial records, while there is some evidence for climatic reversals (e.g. the Antarctic Cold Reversal) in high resolution marine sediment cores through this period. The high spatial density of Holocene terrestrial records reveals an overall expansion of sclerophyll woodland and rainforest taxa across the temperate region after ∼12 ka, presumably in response to increasing temperature, while hydrological records reveal spatially heterogeneous hydro-climatic trends. Patterns after ∼6 ka suggest higher frequency climatic variability that possibly reflects the onset of large scale climate variability caused by the El Niño/Southern Oscillation.

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In situ FT-IR spectroscopy allows the methanol synthesis reaction to be investigated under actual industrial conditions of 503 K and 10 MPa. On Cu/SiO2 catalyst formate species were initially formed which were subsequently hydrogenated to methanol. During the reaction a steady state concentration of formate species persisted on the copper. Additionally, a small quantity of gaseous methane was produced. In contrast, the reaction of CO2 and H2 on ZnO/SiO2 catalyst only resulted in the formation of zinc formate species: no methanol was detected. The interaction of CO2 and H2 with Cu/ZnO/SiO2 catalyst gave formate species on both copper and zinc oxide. Methanol was again formed by the hydrogenation of copper formate species. Steady-state concentrations of copper formate existed under actual industrial reaction conditions, and copper formate is the pivotal intermediate for methanol synthesis. Collation of these results with previous data on copper-based methanol synthesis catalysts allowed the formulation of a reaction mechanism