948 resultados para Physical and Theoretical Chemistry
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The flow of Bingham liquids through porous media has been studied. Experiments have been performed to determine the flow rate / pressure drop relationship for the flow of a grease of Binghamian rheological behavior through an array of rods of circular cross section. The yield stress and plastic viscosity of the grease have been determined with the aid of a controlled stress rotational rheometer. To investigate a wider range of the flow parameters, the mass and momentum conservation equations have been solved numerically, in conjunction with the generalized Newtonian constitutive law and the bi-viscosity model. The finite volume method has been employed to obtain the numerical solution. These numerical results also yielded a flow rate / pressure drop relationship, which is in very good agreement with the experimental results. A capillaric theory has been developed to determine an analytical relationship between the flow rate and pressure drop for flows of Bingham liquids through porous media. It is shown that the predictions of this theory are in good agreement with the experimental and numerical results.
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A study was conducted to evaluate the sorption and desorption of 14C herbicide saflufenacil (pyrimidinedione) in two soils in the State of São Paulo, classified as Red Yellow Latosol with clayey texture (LVA-1) and medium texture (LVA-2), using the batch method through isotherms. The soils were air dried and sieved a 2 mm mesh. The radioactivity was determined by liquid scintillation spectrometry in acclimatized room (25 ± 2 °C). Sorption isotherms were conducted for 5 concentrations of saflufenacil (5.0; 2.5; 1.0; 0.5 and 0.05 μg mL-1) and the results were adjusted to the Freundlich equation, thus obtaining the parameters of sorption followed by two extractions with 0.01 M CaCl2 to determine desorption parameters similarly to sorption. The results showed that saflufenacil sorption was low for both soils studied, being greater for the LVA with higher organic matter content. The desorption coefficients were greater than their sorption coefficients, suggesting the occurrence of hysteresis. The sorption and desorption isotherms (classified as type C isotherms), hysteresis and the t-test between the angular coefficient of the respective isotherms showed that both the sorption and desorption occur with equal intensity.
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The main purpose of the present doctoral thesis is to investigate subjective experiences and cognitive processes in four different types of altered states of consciousness: naturally occurring dreaming, cognitively induced hypnosis, pharmacologically induced sedation, and pathological psychosis. Both empirical and theoretical research is carried out, resulting in four empirical and four theoretical studies. The thesis begins with a review of the main concepts used in consciousness research, the most influential philosophical and neurobiological theories of subjective experience, the classification of altered states of consciousness, and the main empirical methods used to study consciousness alterations. Next, findings of the original studies are discussed, as follows. Phenomenal consciousness is found to be dissociable from responsiveness, as subjective experiences do occur in unresponsive states, including anaesthetic-induced sedation and natural sleep, as demonstrated by post-awakening subjective reports. Two new tools for the content analysis of subjective experiences and dreams are presented, focusing on the diversity, complexity and dynamics of phenomenal consciousness. In addition, a new experimental paradigm of serial awakenings from non-rapid eye movement sleep is introduced, which enables more rapid sampling of dream reports than has been available in previous studies. It is also suggested that lucid dreaming can be studied using transcranial brain stimulation techniques and systematic analysis of pre-lucid dreaming. For blind judges, dreams of psychotic patients appear to be indistinguishable from waking mentation reports collected from the same patients, which indicates a close resemblance of these states of mind. However, despite phenomenological similarities, dreaming should not be treated as a uniform research model of psychotic or intact consciousness. Contrary to this, there seems to be a multiplicity of routes of how different states of consciousness can be associated. For instance, seemingly identical time perception distortions in different alterations of consciousness may have diverse underlying causes for these distortions. It is also shown that altered states do not necessarily exhibit impaired cognitive processing compared to a baseline waking state of consciousness: a case study of time perception in a hypnotic virtuoso indicates a more consistent perceptual timing under hypnosis than in a waking state. The thesis ends with a brief discussion of the most promising new perspectives for the study of alterations of consciousness.
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Iron is one of the most common elements in the earth’s crust and thus its availability and economic viability far exceed that of metals commonly used in catalysis. Also the toxicity of iron is miniscule, compared to the likes of platinum and nickel, making it very desirable as a catalyst. Despite this, prior to the 21st century, the applicability of iron in catalysis was not thoroughly investigated, as it was considered to be inefficient and unselective in desired transformations. In this doctoral thesis, the application of iron catalysis in combination with organosilicon reagents for transformations of carbonyl compounds has been investigated together with insights into iron catalyzed chlorination of silanes and silanols. In the first part of the thesis, the synthetic application of iron(III)-catalyzed chlorination of silanes (Si-H) and the monochlorination of silanes (SiH2) using acetyl chloride as the chlorine source is described. The reactions proceed under ambient conditions, although some compounds need to be protected from excess moisture. In addition, the mechanism and kinetics of the chlorination reaction are briefly adressed. In the second part of this thesis a versatile methodology for transformation of carbonyl compounds into three different compound classes by changing the conditions and amounts of reagents is discussed. One pot reductive benzylation, reductive halogenation and reductive etherification of ketones and aldehydes using silanes as the reducing agent, halide source or cocatalyst, were investigated. Also the reaction kinetics and mechanism of the reductive halogenation of acetophenone are briefly discussed.
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"Panela" is a natural sweetener obtained by concentrating sugar cane juice and handmade in small factories. In the study carried out, the physical and chemical properties of two commercial brands of artisanal granulated panelas and of one made on an experimental level were determined. Three lots of each sample were analyzed. The parameters measured were moisture, a w, protein, ash, minerals, reducing sugars, sucrose, pH, color (L, a and b), insoluble solids (IS), transmittance a 720 nm and filterability. In addition, a qualitative test to detect sulphur dioxide was performed. The parameters with higher variability were moisture (1.66-4.36 g.100 g-1), a w (0.51-0.69), reducing sugars (4.58-11.48 g.100 g-1), pH (5.58-6.90), and color. Potassium was the most abundant mineral (229.52-1027.18 mg.100 g-1). An inverse relationship between IS and transmittance at 720 nm (R² = 0.96) and a direct relationship between IS and ash (R² = 0.94) were found. The sulphur dioxide test was negative for all the samples.
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The aim of this study was to evaluate the physicochemical properties of avocado pulp of four different varieties (Avocado, Guatemala, Dickinson, and Butter pear) and to identify which has the greatest potential for oil extraction. Fresh avocado pulp was characterized by moisture, protein, fat, ash, carbohydrates and energy contents were determined. The carotenoids and chlorophyll contents were determined by the organic solvent extraction method. The results showed significant differences in the composition of the fruit when varieties are compared. However, the striking feature in all varieties is high lipid content; Avocado and Dickinson are the most suitable varieties for oil extraction, taking into account moisture content and the levels of lipids in the pulp. Moreover, it could be said that the variety Dickinson is the most affected by the parameters evaluated in terms of overall quality. Chlorophyll and carotenoids, fat-soluble pigments, showed a negative correlation with respect to lipids since it could be related to its function in the fruit. The varieties Avocado and Dickinson are an alternative to oil extraction having great commercial potential to be exploited thus avoiding waste and increasing farmers income.
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The objective of this study was to evaluate the effect of harvest at different times of day on the chemical and physical characteristics of vegetable-type soybean BRS 267 cultivar, harvested at the R6 stage (seed development) and to compare it with that on the grains harvested at the R8 stage (maturation). The pods of the BRS 267 cultivar were harvested at the R6 stage (at 8:00 AM, 12:00 AM, and 6:00 PM), the color parameters were evaluated, and the grains were analyzed for chemical composition, activity inhibitor trypsin, phytic acid content, starch, sugars, fatty acids, and isoflavones. No differences were observed among the different harvest times in terms of the chemical constituents of vegetable-type soybean BRS 267 cultivar harvested at the R6 stage. Isoflavones content did not change with different harvest times, and the aglycone forms (daidzein, glycitein, and genistein) were found in smaller quantities at the R6 stage compared to the R8 stage. The color of the pods of soybean BRS 267 cultivar, harvested at the R6 stage did not change with different harvest times. The grains harvested at the R6 stage had lower protein content, phytic acid, and sucrose and higher levels of lipids, carbohydrates, starch, glucose, fructose, stachyose, and linolenic acids than those collected at the R8 stage. The different times of harvest did not affect the quality of the vegetable-type soybean BRS 267 cultivar harvested at stage R6. Nevertheless, it is recommended to harvest in the morning, when the temperature is milder, like other vegetables, to facilitate and optimize its marketing and in natura consumption.
Soymilk plain beverages: correlation between acceptability and physical and chemical characteristics
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The objective of the research was to relate the physical and chemical characteristics of soymilk plain beverages to its sensory acceptance. Five commercial products and a new product formulated based on the less accepted sample were used. The overall acceptance was evaluated by 102 assessors using a 10-point hybrid hedonic scale. The hedonic scores ranged from 3.8 (sample E) to 7.0 (A). Most assessors (55%) preferred sample A, which was viscous (26.6 cp), dark (L* = 77.7), and slightly acidic (pH = 6.6). Sample C, which had lower solid content and higher acidity, was preferred by 29% of the assessors. These two beverages showed the greatest commercial potential of the products analyzed. The least-accepted sample (E), preferred by 8% of the assessors, had a lighter color (L* = 96.8), lower viscosity (13.5 cp), higher lipid content (2.2 g/100 g), and less protein (1.68 g/100 g) than the other products evaluated. A reformulation of the least preferred product (E) with the addition of maltodextrin and also vanilla and milk flavors increased its acceptance, yielding an average score of 7.2. Overall, it was observed that a soymilk plain beverage with higher viscosity, darker color, and higher protein content best meets consumer expectations.
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Gelatin was extracted from the skin of tilapia (Oreochromis urolepis hornorum) and characterized according to its physical and chemical properties. It had pH 4.66, which is slightly higher than the values reported for gelatins processed by acid solubilization. In general, the ionic content was low, and the average yield of the process was 5.10 g/100 g. The proximal composition of the gelatin was similar to that of the commercial gelatins, with slightly higher moisture content. The tilapia skin gelatin had whitish-yellow color and average turbidity of 67 NTU.
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AbstractThe Atlantic Forest has species of native fruits, consumed fresh and processed, which have an important contribution to food sovereignty of families that consume it. This study examined the physical and physicochemical characteristics, proximate composition, concentration of carotenoids, vitamin C, vitamin E and minerals in the pulp and kernels of fruits of licuri (Syagrus coronata (Mart.) Becc.). Titratable acidity was analyzed by volumetric neutralization, soluble solids by refractometry, proteins by the micro-Kjeldahl method, lipids by gravimetry using soxhlet, dietary fiber by non-enzymatic gravimetry, carotenoids and vitamin C by HPLC-DAD, vitamin E by HPLC-fluorescence, and minerals by ICP-AES. Pulp were a source of Zn (0.95 mg 100–1), a good source of fiber (6.15 g 100–1), excellent source of provitamin A (758.75 RAE 100–1), Cu (0.69 mg 100–1), Fe (3.81 mg 100–1), Mn (3.40 mg 100–1) and Mo (0.06 mg 100–1). The kernel were a source of Fe (3.36 mg 100–1) and excellent source of Mn (6.14 mg 100–1), Cu (0.97 mg 100–1) and Mo (0.07 mg 100–1). The nutritional value and wide availability of licuri fruit make it an important resource for reducing food insecurity and improving nutrition of the rural population and other individuals who have access to it.
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The prlmaiy objective of this study was to Identify and describe the physical and psychological stress factors that elementary school teachers experience and how teachers cope with stress. A secondary objective was to offer boards and teachers potential coping strategies counteracting stress and the effects of stress. The sample consisted of 120 elementaiy teachers from southern Ontario. Ten elementaiy schools were randomly chosen. The Teacher Stress Inventory questionnaire (Flmian, 1989) was used. Data were analyzed using a variety of statistics. Test norms and interpretations were performed based on standard results obtained from the author of the questionnaire (Flmian, 1988). Overall, the results indicated that work-related stressors were the main factor for teacher stress. This Included such factors as caseload/class is too big, too much administrative paperwork, and having little time to prepare lessons. Implications for further research and practical suggestions for further reseairch are discussed. Also a variety of recommendations to boards and for individual use are discussed. Some recommendations are having counselling available for teachers, workshops on how to handle stress, and learning how to breathe and using calm visualization.
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The synthesis and studies of two classes of poly dentate ligands are presented as two projects. In project 1, four new carboxamide ligands have been synthesised via the condensation of 2,2',6,6'-tetrachloroformyl-4,4'-bipyridine or 2,6-dichloroformyl pyridine together with heterocyclic amines containing pyridine or pyrazole substituents. The coordination chemistry of these ligands has been investigated and studies have shown that with a Cu(II) salt, two carboxamide ligands LJ and L2 afford large clusters with stoichiometries [Cu8(L1)4Cl16].CHCl3.5H2O.7CH3OH (I) and [Cu9(L2)6Cl6].CH3OH.5H2O.(C2H5)3N (II) respectively. [molecular diagram availabel in pdf]. X-ray diffraction studies of cluster (I) reveal that it has approximate S4 symmetry and is comprised of four ligands and eight copper (II) centers. Here, coordination takes place via amide 0 atoms, and pyrazole nitrogens. This complex is the first reported example of an octanuclear copper cluster with a saddle-shaped structure. The second cluster comprises nine copper ions that are arranged in a cyclic array. Each ligand coordinates three copper centers and each copper ion shares two ligands to connect six ligands with nine copper ions. The amide nitrogens are completely deprotonated and both amide Nand 0 atoms coordinate the metal centres. The cluster has three-fold symmetry. There are six chloride ions, three of which are bridging two neighbouring Cu(II) centres. Magnetic studies of (I) and (II) reveal that both clusters display weak antiferromagnetic interactions between neighbouring Cu(II) centers at low temperature. In the second project, three complexes with stoichiometries [Fe[N302](SCN)2]2 (III), R,R-[Fe[N3O2](SCN)2 (IV) and R,R-]Fe[N3O2](CN)2] (V) were prepared and characterized, where [N302] is a pentadentate macrocycle. Complex (III) was prepared via the metal templated Schiff-base condensation of 2,2',6,6'-tetraacetyl-4,4'-bipyridine together with 3,6-dioxaoctane-I,8-diamine and comprises of a dimeric macro cycle where the two Fe(II) centres are in a pentagonal-bipyramidal environment with the [N302] ligands occupying the equatorial plane and two axial NCS ligands. Complexes (IV) and (V) were prepared via the condensation of 2,6-diacetylpyridine together with a chiral diamine in the presence of FeCh. The synthetic strategy for the preparation of the chiral diamine (4R,5R)-4,5-diphenyl-3,6-dioxa-I,8-octane-diamine was elucidated. The chirality of both macrocycles (IV) and (V) was probed by circular dichroism spectroscopy. The crystal structure of (IV) at 200 K contains two independent molecules in the unit cell, both of which contain a hepta-coordinated Fe(II) and axial NCS ligands. Variable temperature magnetic susceptibility and structural studies are consistent with a high spin Fe(II) complex and show no evidence of any spin crossover behaviour. In contrast, the bis cyanide derivative (V) crystallizes with two independent molecules in the unit cell, both of which have different coordination geometries consistent with different spin states for the two Fe(II) centres. At 250 K, the molecular structure of (V) shows the presence of both 7- and a 6-coordinate Fe(II) complexes in the crystal lattice. As the temperature is lowered, the molecules undergo a structural change and at 100 K the structural data is consistent with a 6- and 5-coordinate Fe(II) complex in the unit cell. Magnetic studies confirm that this complex undergoes a gradual, thermal, spin crossover transition in the solid state. Photomagnetic measurements indicate this is the first chiral Fe (II) sea complex to exhibit a LIESST.
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This study was an investigation into whether strong teacher-student rapport relates to the drop-out rates of students in grade 9 and 10 health and physical education (HPE). In the study, One hundred and thirty-six grade 9 students from five high schools in Ontario participated in this study. Findings of whether or not rapport related to students’ decision to take an additional HPE credit beyond grade 9 did not prove conclusive. A significant multivariate interaction effect was not found; however, tests of between-subject effects on sex and grade 10 dropouts showed some interesting trends. More research is needed to further illuminate the link between teacher-student rapport and students’ enrollment in optional HPE classes.
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Ce mémoire utilise des données qualitatives provenant d’entretiens semi-structurés pour examiner les ressources qu’utilisent les individus qui font face à l’insécurité alimentaire sous l’angle du capital culturel de Pierre Bourdieu. Les participants étaient choisis parmi les usagers des organismes alternatifs qui œuvrent en sécurité alimentaire à Montréal. Tous étaient en situation d’insécurité alimentaire. Des analyses inductives et déductives étaient exécutées. Seize indicateurs de la forme du capital culturel incorporée, et trois indicateurs de chacune des formes institutionnalisées et objectivées ont été trouvés à être reliés aux stratégies qu’utilisaient les répondants pour améliorer leur situation alimentaire. Cette recherche nous indique que le capital culturel individuel joue un rôle dans les stratégies utilisées, incluant la participation dans les organismes communautaires. De plus, un manque de capital approprié peut servir comme barrière à la participation dans certaines stratégies ce qui pourra avancer des réflexions sur la justesse et l’efficacité des stratégies actuelles.