956 resultados para 1D and 2D NMR
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Analysis of river flow using hydraulic modelling and its implications in derived environ-mental applications are inextricably connected with the way in which the river boundary shape is represented. This relationship is scale-dependent upon the modelling resolution which in turn determines the importance of a subscale performance of the model and the way subscale (surface and flow) processes are parameterised. Commonly, the subscale behaviour of the model relies upon a roughness parameterisation whose meaning depends on the dimensionality of the hydraulic model and the resolution of the topographic represen¬tation scale. This latter is, in turn, dependent on the resolution of the computational mesh as well as on the detail of measured topographic data. Flow results are affected by this interactions between scale and subscale parameterisation according to the dimensionality approach. The aim of this dissertation is the evaluation of these interactions upon hy¬draulic modelling results. Current high resolution topographic source availability induce this research which is tackled using a suitable roughness approach according to each di¬mensionality with the purpose of the interaction assessment. A 1D HEC-RAS model, a 2D raster-based diffusion-wave model with a scale-dependent distributed roughness parame-terisation and a 3D finite volume scheme with a porosity algorithm approach to incorporate complex topography have been used. Different topographic sources are assessed using a 1D scheme. LiDAR data are used to isolate the mesh resolution from the topographic content of the DEM effects upon 2D and 3D flow results. A distributed roughness parameterisation, using a roughness height approach dependent upon both mesh resolution and topographic content is developed and evaluated for the 2D scheme. Grain-size data and fractal methods are used for the reconstruction of topography with microscale information, required for some applications but not easily available. Sensitivity of hydraulic parameters to this topographic parameterisation is evaluated in a 3D scheme at different mesh resolu¬tions. Finally, the structural variability of simulated flow is analysed and related to scale interactions. Model simulations demonstrate (i) the importance of the topographic source in a 1D models; (ii) the mesh resolution approach is dominant in 2D and 3D simulations whereas in a 1D model the topographic source and even the roughness parameterisation impacts are more critical; (iii) the increment of the sensitivity to roughness parameterisa-tion in 1D and 2D schemes with detailed topographic sources and finer mesh resolutions; and (iv) the topographic content and microtopography impact throughout the vertical profile of computed 3D velocity in a depth-dependent way, whereas 2D results are not affected by topographic content variations. Finally, the spatial analysis shows that the mesh resolution controls high resolution model scale results, roughness parameterisation control 2D simulation results for a constant mesh resolution; and topographic content and micro-topography variations impacts upon the organisation of flow results depth-dependently in a 3D scheme. Resumen La topografía juega un papel fundamental en la distribución del agua y la energía en los paisajes naturales (Beven and Kirkby 1979; Wood et al. 1997). La simulación hidráulica combinada con métodos de medición del terreno por teledetección constituyen una poderosa herramienta de investigación en la comprensión del comportamiento de los flujos de agua debido a la variabilidad de la superficie sobre la que fluye. La representación e incorporación de la topografía en el esquema hidráulico tiene una importancia crucial en los resultados y determinan el desarrollo de sus aplicaciones al campo medioambiental. Cualquier simulación es una simplificación de un proceso del mundo real, y por tanto el grado de simplificación determinará el significado de los resultados simulados. Este razonamiento es particularmente difícil de trasladar a la simulación hidráulica donde aspectos de la escala tan diferentes como la escala de los procesos de flujo y de representación del contorno son considerados conjuntamente incluso en fases de parametrización (e.g. parametrización de la rugosidad). Por una parte, esto es debido a que las decisiones de escala vienen condicionadas entre ellas (e.g. la dimensionalidad del modelo condiciona la escala de representación del contorno) y por tanto interaccionan en sus resultados estrechamente. Y por otra parte, debido a los altos requerimientos numéricos y computacionales de una representación explícita de alta resolución de los procesos de flujo y discretización de la malla. Además, previo a la modelización hidráulica, la superficie del terreno sobre la que el agua fluye debe ser modelizada y por tanto presenta su propia escala de representación, que a su vez dependerá de la escala de los datos topográficos medidos con que se elabora el modelo. En última instancia, esta topografía es la que determina el comportamiento espacial del flujo. Por tanto, la escala de la topografía en sus fases de medición y modelización (resolución de los datos y representación topográfica) previas a su incorporación en el modelo hidráulico producirá a su vez un impacto que se acumulará al impacto global resultante debido a la escala computacional del modelo hidráulico y su dimensión. La comprensión de las interacciones entre las complejas geometrías del contorno y la estructura del flujo utilizando la modelización hidráulica depende de las escalas consideradas en la simplificación de los procesos hidráulicos y del terreno (dimensión del modelo, tamaño de escala computacional y escala de los datos topográficos). La naturaleza de la aplicación del modelo hidráulico (e.g. habitat físico, análisis de riesgo de inundaciones, transporte de sedimentos) determina en primer lugar la escala del estudio y por tanto el detalle de los procesos a simular en el modelo (i.e. la dimensionalidad) y, en consecuencia, la escala computacional a la que se realizarán los cálculos (i.e. resolución computacional). Esta última a su vez determina, el detalle geográfico con que deberá representarse el contorno acorde con la resolución de la malla computacional. La parametrización persigue incorporar en el modelo hidráulico la cuantificación de los procesos y condiciones físicas del sistema natural y por tanto debe incluir no solo aquellos procesos que tienen lugar a la escala de modelización, sino también aquellos que tienen lugar a un nivel subescalar y que deben ser definidos mediante relaciones de escalado con las variables modeladas explícitamente. Dicha parametrización se implementa en la práctica mediante la provisión de datos al modelo, por tanto la escala de los datos geográficos utilizados para parametrizar el modelo no sólo influirá en los resultados, sino también determinará la importancia del comportamiento subescalar del modelo y el modo en que estos procesos deban ser parametrizados (e.g. la variabilidad natural del terreno dentro de la celda de discretización o el flujo en las direcciones laterales y verticales en un modelo unidimensional). En esta tesis, se han utilizado el modelo unidimensional HEC-RAS, (HEC 1998b), un modelo ráster bidimensional de propagación de onda, (Yu 2005) y un esquema tridimensional de volúmenes finitos con un algoritmo de porosidad para incorporar la topografía, (Lane et al. 2004; Hardy et al. 2005). La geometría del contorno viene definida por la escala de representación topográfica (resolución de malla y contenido topográfico), la cual a su vez depende de la escala de la fuente cartográfica. Todos estos factores de escala interaccionan en la respuesta del modelo hidráulico a la topografía. En los últimos años, métodos como el análisis fractal y las técnicas geoestadísticas utilizadas para representar y analizar elementos geográficos (e.g. en la caracterización de superficies (Herzfeld and Overbeck 1999; Butler et al. 2001)), están promoviendo nuevos enfoques en la cuantificación de los efectos de escala (Lam et al. 2004; Atkinson and Tate 2000; Lam et al. 2006) por medio del análisis de la estructura espacial de la variable (e.g. Bishop et al. 2006; Ju et al. 2005; Myint et al. 2004; Weng 2002; Bian and Xie 2004; Southworth et al. 2006; Pozd-nyakova et al. 2005; Kyriakidis and Goodchild 2006). Estos métodos cuantifican tanto el rango de valores de la variable presentes a diferentes escalas como la homogeneidad o heterogeneidad de la variable espacialmente distribuida (Lam et al. 2004). En esta tesis, estas técnicas se han utilizado para analizar el impacto de la topografía sobre la estructura de los resultados hidráulicos simulados. Los datos de teledetección de alta resolución y técnicas GIS también están siendo utilizados para la mejor compresión de los efectos de escala en modelos medioambientales (Marceau 1999; Skidmore 2002; Goodchild 2003) y se utilizan en esta tesis. Esta tesis como corpus de investigación aborda las interacciones de esas escalas en la modelización hidráulica desde un punto de vista global e interrelacionado. Sin embargo, la estructura y el foco principal de los experimentos están relacionados con las nociones espaciales de la escala de representación en relación con una visión global de las interacciones entre escalas. En teoría, la representación topográfica debe caracterizar la superficie sobre la que corre el agua a una adecuada (conforme a la finalidad y dimensión del modelo) escala de discretización, de modo que refleje los procesos de interés. La parametrización de la rugosidad debe de reflejar los efectos de la variabilidad de la superficie a escalas de más detalle que aquellas representadas explícitamente en la malla topográfica (i.e. escala de discretización). Claramente, ambos conceptos están físicamente relacionados por un
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"[Presented by] Mr. Everett from the select committee appointed on the subject."-p.[1]
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Mode of access: Internet.
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"15 March 1990."
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Mode of access: Internet.
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Grafted GMA on EPR samples were prepared in a Thermo-Haake internal mixer by free radical melt grafting reactions in the absence (conventional system; EPR-g-GMA(CONV)) and presence of the reactive comonomer divinyl benzene, DVB (EPR-g-GMA(DVB)). The GMA-homopolymer (poly-GMA), a major side reaction product in the conventional system, was almost completely absent in the DVB-containing system, the latter also resulted in a much higher level of GMA grafting. A comprehensive microstructure analysis of the formed poly-GMA was performed based on one-dimensional H-1 and C-13 NMR spectroscopy and the complete spectral assignments were supported by two-dimensional NMR techniques based on long range two and three bond order carbon-proton couplings from HMBC (Heteronuclear Multiple Bond Coherence) and that of one bond carbon-proton couplings from HSQC (Heteronuclear Single Quantum Coherence), as well as the use of Distortionless Enhancement by Polarization Transfer (DEPT) NMR spectroscopy. The unambiguous analysis of the stereochemical configuration of poly-GMA was further used to help understand the microstructures of the GMA-grafts obtained in the two different free radical melt grafting reactions, the conventional and comonomer-containing systems. In the grafted GMA, in the conventional system (EPR-g-GMA(CONV)), the methylene protons of the GMA were found to be sensitive to tetrad configurational sequences and the results showed that 56% of the GMA sequence in the graft is in atactic configuration and 42% is in syndiotactic configuration whereas the poly-GMA was predominantly syndiotactic. The differences in the microstructures of the graft in the conventional EPR-g-GMA(CONV) and the DVB-containing (EPR-g-GMA(DVB)) systems is also reported (C) 2009 Elsevier Ltd. All rights reserved.
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Water-insoluble glucan was isolated from the baker’s yeast Saccharomyces cerevisiae. The yeast cells were treated with alkali and the residue then with acid. Chemical and NMR (1D and 2D) analyses showed that a linear (1→3)-β-glucan was purified that was not contaminated with other carbohydrates, proteins or phenolic compounds. The effects of the glucan on wound healing were assessed in human venous ulcers by histopathological analysis after 30 days of topical treatment. (1→3)-β-glucan enhanced ulcer healing and increased epithelial hyperplasia, as well as increased inflammatory cells, angiogenesis and fibroblast proliferation. In one patient who had an ulcer that would not heal for over 15 years, glucan treatment caused a 67.8% decrease in the area of the ulcer. This is the first study to investigate the effects of (1→3)-β-glucan on venous ulcer healing in humans; our findings suggest that this glucan is a potential natural biological response modifier in wound healing
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Water-insoluble glucan was isolated from the baker’s yeast Saccharomyces cerevisiae. The yeast cells were treated with alkali and the residue then with acid. Chemical and NMR (1D and 2D) analyses showed that a linear (1→3)-β-glucan was purified that was not contaminated with other carbohydrates, proteins or phenolic compounds. The effects of the glucan on wound healing were assessed in human venous ulcers by histopathological analysis after 30 days of topical treatment. (1→3)-β-glucan enhanced ulcer healing and increased epithelial hyperplasia, as well as increased inflammatory cells, angiogenesis and fibroblast proliferation. In one patient who had an ulcer that would not heal for over 15 years, glucan treatment caused a 67.8% decrease in the area of the ulcer. This is the first study to investigate the effects of (1→3)-β-glucan on venous ulcer healing in humans; our findings suggest that this glucan is a potential natural biological response modifier in wound healing
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Water-insoluble glucan was isolated from the baker’s yeast Saccharomyces cerevisiae. The yeast cells were treated with alkali and the residue then with acid. Chemical and NMR (1D and 2D) analyses showed that a linear (1→3)-β-glucan was purified that was not contaminated with other carbohydrates, proteins or phenolic compounds. The effects of the glucan on wound healing were assessed in human venous ulcers by histopathological analysis after 30 days of topical treatment. (1→3)-β-glucan enhanced ulcer healing and increased epithelial hyperplasia, as well as increased inflammatory cells, angiogenesis and fibroblast proliferation. In one patient who had an ulcer that would not heal for over 15 years, glucan treatment caused a 67.8% decrease in the area of the ulcer. This is the first study to investigate the effects of (1→3)-β-glucan on venous ulcer healing in humans; our findings suggest that this glucan is a potential natural biological response modifier in wound healing
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Water-insoluble glucan was isolated from the baker’s yeast Saccharomyces cerevisiae. The yeast cells were treated with alkali and the residue then with acid. Chemical and NMR (1D and 2D) analyses showed that a linear (1→3)-β-glucan was purified that was not contaminated with other carbohydrates, proteins or phenolic compounds. The effects of the glucan on wound healing were assessed in human venous ulcers by histopathological analysis after 30 days of topical treatment. (1→3)-β-glucan enhanced ulcer healing and increased epithelial hyperplasia, as well as increased inflammatory cells, angiogenesis and fibroblast proliferation. In one patient who had an ulcer that would not heal for over 15 years, glucan treatment caused a 67.8% decrease in the area of the ulcer. This is the first study to investigate the effects of (1→3)-β-glucan on venous ulcer healing in humans; our findings suggest that this glucan is a potential natural biological response modifier in wound healing
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We demonstrate numerically light-pulse combining and pulse compression using wave-collapse (self-focusing) energy-localization dynamics in a continuous-discrete nonlinear system, as implemented in a multicore fiber (MCF) using one-dimensional (1D) and 2D core distribution designs. Large-scale numerical simulations were performed to determine the conditions of the most efficient coherent combining and compression of pulses injected into the considered MCFs. We demonstrate the possibility of combining in a single core 90% of the total energy of pulses initially injected into all cores of a 7-core MCF with a hexagonal lattice. A pulse compression factor of about 720 can be obtained with a 19-core ring MCF.
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The aim of the present work is to gain new insights into the formation mechanism of CdTe magic-sized clusters (MSCs) at low temperatures, as well as on their evolution towards 1D and 2D nanostructures and assemblies thereof, under mild reaction conditions. The reaction system included toluene as solvent, octylamine as primary alkylamine, trioctylphosphine-Te as chalcogenide precursor and Cd(oleate)2 as metal precursor. UV-Vis absorption spectroscopy and transmission electron microscopy (TEM) were used to analyze samples containing concentrations of octylamine of 0.2, 0.8 and 2 M: well-defined, sharp absorption peaks were observed, with peaks maxima at 449, 417 and 373 nm respectively, and 1D structures with a string-like appearance were displayed in the TEM images. Investigating peaks growth, step-wise peaks shift to lower energies and reverse, step-wise peak shift to higher energies allowed to propose a model to describe the system, based on interconnected [CdTe]x cluster units originating an amine-capped, 1-dimensional, polymer-like structure, in which different degrees of electronic coupling between the clusters are held responsible for the different absorption transitions. The many parameters involved in the synthesis procedure were then investigated, starting from the Cd:Te ratio, the role of the amine, the use of different phosphine-Te and Cd precursors. The results allowed to gain important information of the reaction mechanism, as well as on the different behavior of the species featuring the sharp absorption peaks in each case. Using Cd(acetate)2 as metal precursor, 2D structures were found to evolve from the MSCs solutions over time, and their tendency to self-assemble was then analyzed employing two amines of different alkyl chain length, octylamine (C-8) and oleylamine (C-18). Their co-presence led to the formation of free-floating triangular nanosheets, which tend to readily aggregate if only octylamine is present in solution.
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A phytochemical investigation of the ethanolic extract of stalks of Senna martiana Benth. (Leguminoseae), native specie of northeast Brazil, resulted in the isolation and spectroscopic characterization of a new bianthrone glycoside, martianine 1 (10,10'-il-chrysophanol-10-oxi10,10'-bi-glucosyl). Its identification was established by HRMS, IR and 2D NMR experiments. The evaluation of martianine trypanocidal activity was carried out against gliceraldehyde 3-phosphate dehydrogenase enzyme from Trypanosoma cruzi. Its inhibitory constant (Ki) is in the low micromolar concentration and it was determined by isothermal titration calorimetry to be 27.3 ± 2.47 µmol L-1. The non-competitive mechanism is asserted to be putative of the mode of action martianine displays against T. cruzi GAPDH. Results show that martianine has a great potential to become new lead molecule by inhibiting this key enzyme and for the development of new drugs against Chagas disease.
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A new phenylpropanoid and two new diterpenes were isolated from the leaves of the plant Mikania laevigata Shultz Bip. ex Baker. The structures of these compounds were established by 1D- and 2D-nuclear magnetic resonance spectroscopic techniques and mass spectrometry data. Taraxerol, lupeol, coumarin, syringaldehyde, trans-melilotoside, cis-melilotoside, adenosine, patuletin 3-O-beta-D-glucopyranoside, kaempferol 3-O-beta-D-glucopyranoside, quercetin 3-O-beta-D-glucopyranoside, methyl 3,5-di-O-caffeoyl quinate, and 3,3`,5-trihydroxy-4`,6,7-trimethoxyflavone were isolated too. In addition, the compounds dihydrocoumarin, spathulenol, caryophyllene oxide, kaurenoic acid, beyerenoic acid, and lupeol acetate were identified by GC-MS. (C) 2010 Elsevier Ltd. All rights reserved.
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A novel labdane diterpene was isolated from the plant Acritopappus longifolius. The structure of this compound was established by 1D- and 2D-nuclear magnetic resonance spectroscopic techniques and mass spectrometry data. N-Methyl-4-hydroxy-trans-proline, stigmasterol-3-O-beta-D-glycoside. and the flavonoids quercetin, luteolin, kaempferol, and rutin were also isolated. (C) 2010 Elsevier Ltd. All rights reserved.