981 resultados para Spectral Characterization
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Raman microscopy, based upon the inelastic scattering (Raman) of light by molecular species, has been applied as a specific structural probe in a wide range of biomedical samples. The purpose of the present investigation was to assess the potential of the technique for spectral characterization of the porcine outer retina derived from the area centralis, which contains the highest proportion of cone:rod cell ratio in the pig retina. METHODS: Retinal cross-sections, immersion-fixed in 4% (w/v) PFA and cryoprotected, were placed on salinized slides and air-dried prior to direct Raman microscopic analysis at three excitation wavelengths, 785 nm, 633 nm, and 514 nm. RESULTS: Raman spectra of each of the photoreceptor inner and outer segments (PIS, POS) and of the outer nuclear layer (ONL) of the retina acquired at 785 nm were dominated by vibrational features characteristic of proteins and lipids. There was a clear difference between the inner and outer domains in the spectroscopic regions, amide I and III, known to be sensitive to protein conformation. The spectra recorded with 633 nm excitation mirrored those observed at 785 nm excitation for the amide I region, but with an additional pattern of bands in the spectra of the PIS region, attributed to cytochrome c. The same features were even more enhanced in spectra recorded with 514 nm excitation. A significant nucleotide contribution was observed in the spectra recorded for the ONL at all three excitation wavelengths. A Raman map was constructed of the major spectral components found in the retinal outer segments, as predicted by principal component analysis of the data acquired using 633 nm excitation. Comparison of the Raman map with its histological counterpart revealed a strong correlation between the two images. CONCLUSIONS: It has been demonstrated that Raman spectroscopy offers a unique insight into the biochemical composition of the light-sensing cells of the retina following the application of standard histological protocols. The present study points to the considerable promise of Raman microscopy as a component-specific probe of retinal tissue.
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Nesta tese são estabelecidas novas propriedades espectrais de grafos com estruturas específicas, como sejam os grafos separados em cliques e independentes e grafos duplamente separados em independentes, ou ainda grafos com conjuntos (κ,τ)-regulares. Alguns invariantes dos grafos separados em cliques e independentes são estudados, tendo como objectivo limitar o maior valor próprio do espectro Laplaciano sem sinal. A técnica do valor próprio é aplicada para obter alguns majorantes e minorantes do índice do espectro Laplaciano sem sinal dos grafos separados em cliques e independentes bem como sobre o índice dos grafos duplamente separados em independentes. São fornecidos alguns resultados computacionais de modo a obter uma melhor percepção da qualidade desses mesmos extremos. Estudamos igualmente os grafos com um conjunto (κ,τ)-regular que induz uma estrela complementar para um valor próprio não-principal $. Além disso, é mostrado que $=κ-τ. Usando uma abordagem baseada nos grafos estrela complementares construímos, em alguns casos, os respectivos grafos maximais. Uma caracterização dos grafos separados em cliques e independentes que envolve o índice e as entradas do vector principal é apresentada tal como um majorante do número da estabilidade dum grafo conexo.
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In the present work 2-formylpyridine-para-chloro-phenyl hydrazone (H2FopCIPh) and 2-formylpyridine-para-nitro-phenyl hydrazone (H2FopNO(2)Ph) were obtained, as well as their copper(II) and zinc(II) complexes [Cu(H2FopClPh)Cl(2)] (1), [Cu(2FopNO(2)Ph)Cl] (2), [Zn(H2FopClPh)Cl(2)] (3) and [Zn(H2FopNO(2)Ph)Cl(2)] (4). Upon re-crystallization in DMSO:acetone conversion of 2 into [Cu(2FopNO(2)Ph)Cl(DMSO)] (2a) and of 4 into [Zn(2FopNO(2)Ph)Cl(DMSO)] (4a) occurred. The crystal structures of 1, 2a, 3 and 4a were determined. (C) 2009 Elsevier Ltd. All rights reserved.
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2-Benzoylpyridine-methyl hydrazone (HBzMe) has been obtained as well as its copper(II) [Cu(HBzMe)Cl(2)] (1) and zinc(II) [Zn(HBzMe)Cl(2)] (2) complexes. Upon re-crystallization in 1 - 9 DMSO:acetone conversion of I into dimeric [Cu(BzMe)Cl](2) (1a) occurred. The crystal structures of HBzMe, 1, 1a, and 2 were determined. HBzMe adopts the ZE conformation in the solid. In all complexes the hydrazone adopts the E configuration to attach to the metal through the N(py)-N2-O chelating system. In 1 and 2 a neutral hydrazone coordinates to the metal center while in 1a deprotonation occurs with coordination of an anionic ligand. la presents a dimeric structure. having two copper(II) ions per asymmetric unit. Two chlorides are also present in the copper coordination sphere, which act as bridging ligands and connect the copper centers to each other. (C) 2008 Elsevier B.V. All rights reserved.
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In mammalian membranes, cholesterol is concentrated in lipid rafts. The generation of cholesterol hydroperoxides (ChOOHs) and their decomposition products induces various types of cell damage. The decomposition of some organic hydroperoxides into peroxyl radicals is known to be a potential source of singlet molecular oxygen [O(2) ((1)Delta(g))] in biological systems. We report herein on evidence of the generation of O(2) ((1)Delta(g)) from ChOOH isomers in solution or in liposomes containing ChOOHs, which involves a cyclic mechanism from a linear tetraoxide intermediate originally proposed by Russell. Characteristic light emission at 1270 nm, corresponding to O(2) ((1)Delta(g)) monomolecular decay, was observed for each ChOOH isomer or in liposomes containing ChOOHs. Moreover, the presence of O(2) ((1)Delta(g)) was unequivocally demonstrated using the direct spectral characterization of near-infrared light emission. Using (18)O-labeled cholesterol hydroperoxide (Ch(18)O(18)OH), we observed the formation of (18)O-labeled O(2) ((1)Delta(g)) [(18)O(2) ((1)Delta(g))] by the chemical trapping of (18)O(2) ((1)Delta(g)) with 9,10-diphenylanthracene (DPA) and detected the corresponding (18)O-labeled DPA endoperoxide (DPA(18)O(18)O) and the (18)O-labeled products of the Russell mechanism using high-performance liquid chromatography coupled to tandem mass spectrometry. Photoemission properties and chemical trapping clearly demonstrate that the decomposition of Ch(18)O(18)OH generates (18)O(2) ((1)Delta(g)), which is consistent with the Russell mechanism and points to the involvement of O(2) ((1)Delta(g)) in cholesterol hydroperoxide-mediated cytotoxicity.
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The current accessibility to hyperspectral images of Hyperion/EO1 orbital sensor has brought new perspectives for studies of aquatic environments for allowing the remote estimative of several optically active constituents (OACs) in water body. The changes in the composition and concentration of OACs cause different patterns of absorption and scattering of electromagnetic radiation, likely to be detected using hyperspectral data. Therefore, an investigation was conducted taking into account the spectral characterization of water of a reservoir intended for public supply (Itupararanga Reservoir), from Hyperion/EO1 images and derivative analysis technique applied to spectral curves generated. Simultaneously to the acquisition of a Hyperion/EO1 image, a field campaign was carried out to collect limnological data in situ in georeferenced points. After radiometric correction of the image, reflectance curves of pixels were extracted for each station and the curves obtained were subjected to the technique of derivative analysis, which revealed features of absorption and scattering mainly associated to the presence of algal pigments. The results obtained show the presence of phytoplankton and algal activity, matching the field observation.
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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This thesis reports on the experimental realization, characterization and application of a novel microresonator design. The so-called “bottle microresonator” sustains whispering-gallery modes in which light fields are confined near the surface of the micron-sized silica structure by continuous total internal reflection. While whispering-gallery mode resonators in general exhibit outstanding properties in terms of both temporal and spatial confinement of light fields, their monolithic design makes tuning of their resonance frequency difficult. This impedes their use, e.g., in cavity quantum electrodynamics (CQED) experiments, which investigate the interaction of single quantum mechanical emitters of predetermined resonance frequency with a cavity mode. In contrast, the highly prolate shape of the bottle microresonators gives rise to a customizable mode structure, enabling full tunability. The thesis is organized as follows: In chapter I, I give a brief overview of different types of optical microresonators. Important quantities, such as the quality factor Q and the mode volume V, which characterize the temporal and spatial confinement of the light field are introduced. In chapter II, a wave equation calculation of the modes of a bottle microresonator is presented. The intensity distribution of different bottle modes is derived and their mode volume is calculated. A brief description of light propagation in ultra-thin optical fibers, which are used to couple light into and out of bottle modes, is given as well. The chapter concludes with a presentation of the fabrication techniques of both structures. Chapter III presents experimental results on highly efficient, nearly lossless coupling of light into bottle modes as well as their spatial and spectral characterization. Ultra-high intrinsic quality factors exceeding 360 million as well as full tunability are demonstrated. In chapter IV, the bottle microresonator in add-drop configuration, i.e., with two ultra-thin fibers coupled to one bottle mode, is discussed. The highly efficient, nearly lossless coupling characteristics of each fiber combined with the resonator's high intrinsic quality factor, enable resonant power transfers between both fibers with efficiencies exceeding 90%. Moreover, the favorable ratio of absorption and the nonlinear refractive index of silica yields optical Kerr bistability at record low powers on the order of 50 µW. Combined with the add-drop configuration, this allows one to route optical signals between the outputs of both ultra-thin fibers, simply by varying the input power, thereby enabling applications in all-optical signal processing. Finally, in chapter V, I discuss the potential of the bottle microresonator for CQED experiments with single atoms. Its Q/V-ratio, which determines the ratio of the atom-cavity coupling rate to the dissipative rates of the subsystems, aligns with the values obtained for state-of-the-art CQED microresonators. In combination with its full tunability and the possibility of highly efficient light transfer to and from the bottle mode, this makes the bottle microresonator a unique tool for quantum optics applications.
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Towards the goal of investigating the possible Twisted Intramolecular Charge Transfer (TICT) state mechanism of fluorescence emission, two aromatic dicyanovinyl compounds, 2-(naphthalene-2-ylmethylene) malononitrile (DCN) and a rigidified analogue, 3,4-dihydrophenanthren-1(2H)-ylidene)malononitrile (RDCN) were synthesized and their absorption and steady-state fluorescence emission spectra characterized. The spectral characterization was divided into two studies: first, DCN and RDCN were characterized in liquid solvents of increasing polarity; second, DCN and RDCN were characterized in viscous solvents and rigid glass media. The absorption spectra for both DCN and RDCN in all solvents demonstrated little to no solvatochromism. Emission results for DCN and RDCN in liquid solvents of increasing polarity showed DCN possessing strong solvatochromism while RDCN showed much less solvatochromism. Using the Lippert-Mataga equation, the difference between the ground and excited state dipole moment for DCN was estimated to be 8.4 + 0.4 Debye and between ~3.0 to 5.0 Debye for RDCN. Quantum yield measurements for DCN and RDCN in hexane, diethyl ether and acetonitrile were less than 0.01 and independent of polarity for both both solvents, with DCN generally possessing a quantum yield 3-4 times greater than RDCN. Experiments in glass media for DCN and RDCN showed a lessening of their solvatochromic character in both polar and non-polar glasses. These data provide strong evidence for a link between molecular flexibility and solvatochromism. However, while these data are consistent with a TICT state hypothesis for the emission mechanism, an alternative mechanism proposed by Maroncelli et al.10 involving rotation about the dicyanovinyl double bond in the excited state remains a possibility as well.
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So far, no experimental data of the infrared and Raman spectra of 13C isotopologue of dimethyl ether are available. With the aim of providing some clues of its low-lying vibrational bands and with the hope of contributing in a next spectral analysis, a number of vibrational transition frequencies below 300 cm−1 of the infrared spectrum and around 400 cm−1 of the Raman spectrum have been predicted and their assignments were proposed. Calculations were carried out through an ab initio three dimensional potential energy surface based on a previously reported one for the most abundant dimethyl ether isotopologue (M. Villa et al., J. Phys. Chem. A 115 (2011) 13573). The potential function was vibrationally corrected and computed with a highly correlated CCSD(T) method involving the COC bending angle and the two large amplitude CH3 internal rotation degrees of freedom. Also, the Hamiltonian parameters could represent a support for the spectral characterization of this species. Although the computed vibrational term values are expected to be very accurate, an empirical adjustment of the Hamiltonian has been performed with the purpose of anticipating some workable corrections to any possible divergence of the vibrational frequencies. Also, the symmetry breaking derived from the isotopic substitution of 13C in the dimethyl ether was taken into account when the symmetrization procedure was applied.
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La determinación del origen de un material utilizado por el hombre en la prehistoria es de suma importancia en el ámbito de la arqueología. En los últimos años, los estudios de procedencia han utilizado técnicas que suelen ser muy precisas pero con el inconveniente de ser metodologías de carácter destructivo. El fenómeno de la minería a gran escala es una de las características que acompaña al Neolítico, de ahí que la revolución correspondiente a este periodo sea una de las etapas más importantes para la humanidad. El yacimiento arqueológico de Casa Montero es una mina de sílex neolítica ubicada en la Península Ibérica, de gran importancia por su antigüedad y su escala productiva. Este sitio arqueológico corresponde a una cantera de explotación de rocas silícicas desarrollada en el periodo neolítico en la que solamente se han encontrado los desechos de la extracción minera, lo cual incrementa la variabilidad de las muestras analizadas, de las que se desconoce su contexto económico, social y cultural. Es de gran interés arqueológico saber por qué esos grupos neolíticos explotaban de forma tan intensiva determinados tipos de material y cuál era el destino de la cadena productiva del sílex. Además, por ser una excavación de rescate, que ha tenido que procesar varias toneladas de material, en un tiempo relativamente corto, requiere de métodos expeditivos de clasificación y manejo de dicho material. Sin embargo,la implementación de cualquier método de clasificación debe evitar la alteración o modificación de la muestra,ya que,estudios previos sobre caracterización de rocas silícicas tienen el inconveniente de alterar parcialmente el objeto de estudio. Por lo que el objetivo de esta investigación fue la modelización del registro y procesamiento de datos espectrales adquiridos de rocas silícicas del yacimiento arqueológico de Casa Montero. Se implementó la metodología para el registro y procesamiento de datos espectrales de materiales líticos dentro del contexto arqueológico. Lo anterior se ha conseguido con la aplicación de modelos de análisis espectral, algoritmos de suavizado de firmas espectrales, reducción de la dimensionalidad de las características y la aplicación de métodos de clasificación, tanto de carácter vectorial como raster. Para la mayoría de los procedimientos se ha desarrollado una aplicación informática validada tanto por los propios resultados obtenidos como comparativamente con otras aplicaciones. Los ensayos de evaluación de la metodología propuesta han permitido comprobar la eficacia de los métodos. Por lo que se concluye que la metodología propuesta no solo es útil para materiales silícicos, sino que se puede generalizar en aquellos procesos donde la caracterización espectral puede ser relevante para la clasificación de materiales que no deban ser alterados, además, permite aplicarla a gran escala, dado que los costes de ejecución son mínimos si se comparan con los de métodos convencionales. Así mismo, es de destacar que los métodos propuestos, representan la variabilidad del material y permiten relacionarla con el estado del yacimiento, según su contenido respecto de las tipologías de la cadena operativa. ABSTRACT: The determination of the origin of a material used by man in prehistory is very important in the field of archaeology. In recent years the provenance studies have used techniques that tend to be very precise but with the drawback of being destructive methodologies. The phenomenon of mining on a large scale is a feature that accompanies the Neolithic period; the Neolithic revolution is one of the most important periods of humanity. The archaeological site of Casa Montero is a Neolithic flint mine located in the Iberian Peninsula of great importance for its antiquity and its scale. This archaeological site corresponds to a quarry exploitation of silicic rocks developed in the Neolithic period, in which only found debris from mining, which increases the variability of the samples analyzed, including their economic, social and cultural context is unknown. It is of great archaeological interest to know why these Neolithic groups exploited as intensive certain types of material and what the final destination of flint was in the productive chain. In addition, being an excavation of rescue that had to process several tons of material in a relatively short time requires expeditious methods of classification and handling of the material. However, the implementation of any method of classification should avoid the alteration or modification of the sample, since previous studies on characterization of silicic rocks have the disadvantage of destroying or partially modify the object of study. So the objective of this research wasthe modeling of the registration and processing of acquired spectral data of silicic rocks of the archaeological site of Casa Montero. The methodology implemented for modeling the registration and processing of existing spectral data of lithic materials within the archaeological context, was presented as an alternative to the conventional classification methods (methods destructive and expensive) or subjective methods that depend on the experience of the expert. The above has been achieved with the implementation of spectral analysis models, smoothing of spectral signatures and the dimensionality reduction algorithms. Trials of validation of the proposed methodology allowed testing the effectiveness of the methods in what refers to the spectral characterization of siliceous materials of Casa Montero. Is remarkable the algorithmic contribution of the signal filtering, improve of quality and reduction of the dimensionality, as well the proposal of using raster structures for efficient storage and analysis of spectral information. For which it is concluded that the proposed methodology is not only useful for siliceous materials, but it can be generalized in those processes where spectral characterization may be relevant to the classification of materials that must not be altered, also allows to apply it on a large scale, given that the implementation costs are minimal when compared with conventional methods.
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Este proyecto tiene como objetivo ampliar, mediante la caracterización espectral y multitemporal por técnicas de teledetección y medidas in situ, el estudio del corredor fluvial para el río Tinguiririca en Chile. Consiste en estudiar la cobertura del terreno, evaluar su dinámica de cambio e identificar zonas de acumulación de materiales de alteración hidrotermal arcillosos y óxidos de hierro, presentes en la cuenca durante las últimas tres décadas que puedan explicar su evolución temporal. Se pretenden obtener nuevas variables geoespaciales que ayuden a comprender las posibles causas de variación del cauce, elaborando cartografía para una posterior fase de investigación mediante modelización hidráulica que vaya dirigida a paliar el impacto de las riadas periódicas. Para ello, se han empleado, tratado y explotado imágenes de los sensores remotos TM, ETM+, OLI y TIRS tomadas en un período comprendido entre 1993 y 2014, que se han contrastado con perfiles batimétricos, datos GPS, supervisión y muestreo tomados sobre el terreno. Se ha realizado así mismo, un estudio prospectivo de caso sobre cómo afectarían las variables obtenidas por teledetección a la modelización hidráulica, en particular, la rugosidad, proponiendo un marco metodológico global de integración de las tres técnicas: sistemas de información geográfica, teledetección y modelización hidráulica. ABSTRACT This project aims to develop the study of Tinguiririca River corridor in Chile, through spectral characterization and multitemporal remote sensing and other measurements. This involves studying the land cover, its dynamic changes and identifies clayey materials and iron oxides accumulations of hydrothermal alteration, present in the basin during the last three decades to explain their evolution. It aims to obtain new geospatial variables in order to understand the possible causes of channel variation, developing mapping to a later research stage using hydraulic modeling so as to mitigate the impact of periodic floods. In this way, it has used processed and exploited images of TM, ETM +, OLI and TIRS remote sensing, taken in a period between 1993 and 2014 which it has been compared with bathymetric profiles, GPS, monitoring and sampling data collected in the field . It has done a prospective study about the variables obtained condition on hydraulic modeling, roughness in particular, proposing IX a complete methodological framework about the integration of the three techniques: geographic information systems, remote sensing and modeling hydraulics