994 resultados para Krulwich, Sara


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The effectiveness of using thermally activated hydrotalcite materials has been investigated for the removal of arsenate, vanadate, and molybdate in individual and mixed solutions. Results show that increasing the Mg,Al ratio to 4:1 causes an increase in the percentage of anions removed from solution. The order of affinity of the three anions analysed in this investigation is arsenate, vanadate, and molybdate. By comparisons with several synthetic hydrotalcite materials, the hydrotalcite structure in the seawater neutralised red mud (SWN-RM) has been determined to consist of magnesium and aluminium with a ratio between 3.5:1 and 4:1. Thermally activated seawater neutralised red mud removes at least twice the concentration of anionic species than thermally activated red mud alone, due to the formation of 40 to 60 % Bayer hydrotalcite during the neutralisation process.

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Raman and infrared spectroscopies were used to characterise two samples of triclinic ejkaite Na4[UO2(CO3)3] and its synthetic trigonal analogue. The v3 (UO2)2+ mode is not Raman active, whereas both the v3 and v1 (UO2)2+ modes are infrared active. U--O bond lengths in uranyls were calculated from the spectra obtained and compared with bond lengths derived from crystal structure analyses. From the higher number of bands related to the uranyl and carbonate vibrations, the presence of symmetrically distinct (UO2)2+ and (CO3)2- units in both structures is proposed.

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Bayer hydrotalcites prepared using the seawater neutralisation (SWN) process of Bayer liquors are characterised using X-ray diffraction and thermal analysis techniques. The Bayer hydrotalcites are synthesised at four different temperatures (0, 25, 55, 75 °C) to determine the effect on the thermal stability of the hydrotalcite structure, and to identify other precipitates that form at these temperatures. The interlayer distance increased with increasing synthesis temperature, up to 55 °C, and then decreased by 0.14 Å for Bayer hydrotalcites prepared at 75 °C. The three mineralogical phases identified in this investigation are; 1) Bayer hydrotalcite, 2), calcium carbonate species, and 3) hydromagnesite. The DTG curve can be separated into four decomposition steps; 1) the removal of adsorbed water and free interlayer water in hydrotalcite (30 – 230 °C), 2) the dehydroxylation of hydrotalcite and the decarbonation of hydrotalcite (250 – 400 °C), 3) the decarbonation of hydromagnesite (400 – 550 °C), and 4) the decarbonation of aragonite (550 – 650 °C).

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The mineral reevesite and the cobalt substituted reevesite have been synthesised. The d(003) spacings of the minerals ranged from 7.54 to 7.95 Å. The maximum d(003) value occurred at around Ni:Co 0.4:0.6. This maximum in interlayer distance is proposed to be due to a greater number of carbonate anions and water molecules intercalated into the structure. The stability of the reevesite and cobalt doped reevesite was determined by thermogravimetric analysis. The maximum temperature of the reevesite occurs for the unsubstituted reevesite and is around 220°C. The effect of cobalt substitution results in a decrease in thermal stability of the reevesites. Four thermal decomposition steps are observed and are attributed to dehydration, dehydroxylation and decarbonation, decomposition of the formed carbonate and oxygen loss at ~807 °C. A mechanism for the thermal decomposition of the reevesite and the cobalt substituted reevesite is proposed.

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The hydrotalcite based upon manganese known as charmarite Mn4Al2(OH)12CO3•3H2O has been synthesised with different Mn/Al ratios from 4:1 to 2:1. Impurities of manganese oxide, rhodochrosite and bayerite at low concentrations were also produced during the synthesis. The thermal stability of charmarite was investigated using thermogravimetry. The manganese hydrotalcite decomposed in stages with mass loss steps at 211, 305 and 793°C. The product of the thermal decomposition was amorphous material mixed with manganese oxide. A comparison is made with the thermal decomposition of the Mg/Al hydrotalcite. It is concluded that the synthetic charmarite is slightly less stable than hydrotalcite.

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Dynamic and controlled rate thermal analysis (CRTA) has been used to characterise alunites of formula [M(Al)3(SO4)2(OH)6 ] where M+ is the cations K+, Na+ or NH4+. Thermal decomposition occurs in a series of steps. (a) dehydration, (b) well defined dehydroxylation and (c) desulphation. CRTA offers a better resolution and a more detailed interpretation of water formation processes via approaching equilibrium conditions of decomposition through the elimination of the slow transfer of heat to the sample as a controlling parameter on the process of decomposition. Constant-rate decomposition processes of water formation reveal the subtle nature of dehydration and dehydroxylation.

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Raman spectroscopy has been used to study the arsenate minerals haidingerite Ca(AsO3OH)•H2O and brassite Mg(AsO3OH)•4H2O. Intense Raman bands in haidingerite spectrum observed at 745 and 855 cm-1 are assigned to the (AsO3OH)2- ν3 antisymmetric stretching and ν1 symmetric stretching vibrational modes. For brassite two similarly assigned intense bands are found at 809 and 862 cm-1. The observation of multiple Raman bands in the (AsO3OH)2- stretching and bending regions suggests that the arsenate tetrahedrons in the crystal structures of both minerals studied are strongly distorted. Broad Raman bands observed at 2842 cm-1 for haidingerite and 3035 cm-1 for brassite indicate strong hydrogen bonding of water molecules in the structure of these minerals. OH…O hydrogen bond lengths were calculated from the Raman spectra based on empiric relations.

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Background Colorectal cancer survivors may suffer from a range of ongoing psychosocial and physical problems that negatively impact on quality of life. This paper presents the study protocol for a novel telephone-delivered intervention to improve lifestyle factors and health outcomes for colorectal cancer survivors. Methods/Design Approximately 350 recently diagnosed colorectal cancer survivors will be recruited through the Queensland Cancer Registry and randomised to the intervention or control condition. The intervention focuses on symptom management, lifestyle and psychosocial support to assist participants to make improvements in lifestyle factors (physical activity, healthy diet, weight management, and smoking cessation) and health outcomes. Participants will receive up to 11 telephone-delivered sessions over a 6 month period from a qualified health professional or 'health coach'. Data collection will occur at baseline (Time 1), post-intervention or six months follow-up (Time 2), and at 12 months follow-up for longer term effects (Time 3). Primary outcome measures will include physical activity, cancer-related fatigue and quality of life. A cost-effective analysis of the costs and outcomes for survivors in the intervention and control conditions will be conducted from the perspective of health care costs to the government. Discussion The study will provide valuable information about an innovative intervention to improve lifestyle factors and health outcomes for colorectal cancer survivors.

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The kaolinite-like phyllosilicate minerals bismutoferrite BiFe3+2Si2O8(OH) and chapmanite SbFe3+2Si2O8(OH) have been studied by Raman spectroscopy and complemented with infrared spectra. Tentatively interpreted spectra were related to their molecular structure. The antisymmetric and symmetric stretching vibrations of the Si-O-Si bridges,  SiOSi and  OSiO bending vibrations,  (Si-Oterminal)- stretching vibrations,  OH stretching vibrations of hydroxyl ions, and  OH bending vibrations were attributed to observed bands. Infrared bands 3289-3470 cm-1 and Raman bands 1590-1667 cm-1 were assigned to adsorbed water. O-H...O hydrogen bond lengths were calculated from the Raman and infrared spectra.

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Insight into the unique structure of hydrotalcites has been obtained using Raman spectroscopy. Gallium containing hydrotalcites of formula Mg4Ga2(CO3)(OH)12•4H2O (2:1 Ga-HT) to Mg8Ga2(CO3)(OH)20•4H2O (4:1 Ga-HT) have been successfully synthesised and characterized by X-ray diffraction and Raman spectroscopy. The d(003) spacing varied from 7.83 Å for the 2:1 hydrotalcite to 8.15 Å for the 3:1 gallium containing hydrotalcite. Raman spectroscopy complemented with selected infrared data has been used to characterise the synthesised gallium containing hydrotalcites of formula Mg6Ga2(CO3)(OH)16•4H2O. Raman bands observed at around 1046, 1048 and 1058 cm-1 were attributed to the symmetric stretching modes of the (CO32-) units. Multiple ν3 CO32- antisymmetric stretching modes are found at around 1346, 1378, 1446, 1464 and 1494 cm-1. The splitting of this mode indicates the carbonate anion is in a perturbed state. Raman bands observed at 710 and 717 cm-1 assigned to the ν4 (CO32-) modes support the concept of multiple carbonate species in the interlayer.

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Insight into the unique structure of layered double hydroxides has been obtained using a combination of X-ray diffraction and thermal analysis. Indium containing hydrotalcites of formula Mg4In2(CO3)(OH)12•4H2O (2:1 In-LDH) through to Mg8In2(CO3)(OH)18•4H2O (4:1 In-LDH) with variation in the Mg:In ratio have been successfully synthesised. The d(003) spacing varied from 7.83 Å for the 2:1 LDH to 8.15 Å for the 3:1 indium containing layered double hydroxide. Distinct mass loss steps attributed to dehydration, dehydroxylation and decarbonation are observed for the indium containing hydrotalcite. Dehydration occurs over the temperature range ambient to 205 °C. Dehydroxylation takes place in a series of steps over the 238 to 277 °C temperature range. Decarbonation occurs between 763 and 795 °C. The dehydroxylation and decarbonation steps depend upon the Mg:In ratio. The formation of indium containing hydrotalcites and their thermal activation provides a method for the synthesis of indium oxide based catalysts.

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The removal of toxic anions has been achieved using hydrotalcite via two methods: (1) coprecipitation and (2) thermal activation. Hydrotalcite formed via the coprecipitation method, using solutions containing arsenate and vanadate up to pH 10, are able to remove more than 95% of the toxic anions (0.2 M) from solution. The removal of toxic anions in solutions with a pH of >10 reduces the removal uptake percentage to 75%. Raman spectroscopy observed multiple A1 stretching modes of V−O and As−O at 930 and 810 cm−1, assigned to vanadate and arsenate, respectively. Analysis of the intensity and position of the A1 stretching modes helped to identify the vanadate and arsenate specie intercalated into the hydrotalcite structure. It has been determined that 3:1 hydrotalcite structure predominantly intercalate anions into the interlayer region, while the 2:1 and 4:1 hydrotalcite structures shows a large portion of anions being removed from solution by adsorption processes. Treatment of carbonate solutions (0.2 M) containing arsenate and vanadate (0.2 M) three times with thermally activated hydrotalcite has been shown to remove 76% and 81% of the toxic anions, respectively. Thermally activated hydrotalcite with a Mg:Al ratio of 2:1, 3:1, and 4:1 have all been shown to remove 95% of arsenate and vanadate (25 ppm). At increased concentrations of arsenate and vanadate, the removal uptake percentage decreased significantly, except for the 4:1 thermally activated hydrotalcite. Thermally activated Bayer hydrotalcite has also been shown to be highly effective in the removal of arsenate and vanadate. The thermal activation of the solid residue component (red mud) removes 30% of anions from solution (100 ppm of both anions), while seawater-neutralized red mud removes 70%. The formation of hydrotalcite during the seawater neutralization process removes anions via two mechanisms, rather than one observed for thermally activated red mud.

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Developmental progression and differentiation of distinct cell types depend on the regulation of gene expression in space and time. Tools that allow spatial and temporal control of gene expression are crucial for the accurate elucidation of gene function. Most systems to manipulate gene expression allow control of only one factor, space or time, and currently available systems that control both temporal and spatial expression of genes have their limitations. We have developed a versatile two-component system that overcomes these limitations, providing reliable, conditional gene activation in restricted tissues or cell types. This system allows conditional tissue-specific ectopic gene expression and provides a tool for conditional cell type- or tissue-specific complementation of mutants. The chimeric transcription factor XVE, in conjunction with Gateway recombination cloning technology, was used to generate a tractable system that can efficiently and faithfully activate target genes in a variety of cell types. Six promoters/enhancers, each with different tissue specificities (including vascular tissue, trichomes, root, and reproductive cell types), were used in activation constructs to generate different expression patterns of XVE. Conditional transactivation of reporter genes was achieved in a predictable, tissue-specific pattern of expression, following the insertion of the activator or the responder T-DNA in a wide variety of positions in the genome. Expression patterns were faithfully replicated in independent transgenic plant lines. Results demonstrate that we can also induce mutant phenotypes using conditional ectopic gene expression. One of these mutant phenotypes could not have been identified using noninducible ectopic gene expression approaches.