Relative changes are detectable in the blood of end-stage renal disease (ESRD) patients during hemodialysis (HD) treatment using optical spectroscopy. However, the potential impacts of several confounding factors that could affect the detection of these changes have not been evaluated. The objectives of this thesis were to: 1) investigate how the variations and/or changes in acid-base and oxygen parameters during HD treatment can affect the optical signature of whole blood of ESRD patients, 2) to investigate the effect of heparin on the optical properties of whole blood and its impact on our method. Blood samples were drawn from 23 ESRD patients at 5 time points during a 4 hour HD treatment and sent for blood gas and blood spectroscopy analyses. No significant correlations were found between the changes in the blood transmittance spectra and acid-base and oxygen parameters. This indicates that the perturbations in these parameters due to HD procedures do not confound the detection of changes in the blood transmittance spectra of ESRD patients during HD treatment. Additionally, the effect of heparin in modifying the optical properties of whole blood does not confound the detection of changes in the blood of ESRD patients due to HD treatment using whole blood-based optical spectroscopy. ANOVA revealed significant (P<0.05) measurable changes in the blood transmittance spectra of ESRD patients during HD treatment. Significant spectral differences (P<0.05) were found between ESRD patients. The lack of uniform spectral characteristics across patients is

Optical spectroscopy combined with mass spectrometry provides a unique opportunity to probe the intrinsic properties of biologically-relevant ions in the gas phase, free from the interfering effects of solvent interactions in the condensed phase. Electrospray ionization allows large biomolecules to be transferred intact into the gas phase for mass analysis. Modern mass spectrometers provide excellent sensitivity, mass-resolution and can efficiently isolate a single ionic species from a complex mixture. However, the extent to which biomolecules retain their solution-phase conformations in the gas phase is largely unknown. Therefore, there is considerable interest in applying spectroscopic methods to biological ions in vacuuo. Due to the low number densities of ions in storage devices, traditional absorption measurements are not feasible, requiring more sensitive analytical methods. Two such techniques are laser-inducedfluorescence (LIF) and photo-dissociation (PD) action spectroscopy, both of which measure the consequence of absorption. The work in this dissertation describes applications of optical spectroscopic methods to interrogate mass-selected ions using a variety of ion storage apparatus including a Fourier transform ion cyclotron resonance mass spectrometer, a quadrupole ion trap and an electrostatic ion storage ring. First, the conformations of small cationized arginine complexes have been investigated using infrared multiple-photon dissociation (IRMPD) action spectroscopy in the IR fingerprint region of the spectrum (200-1800 cm-1). Second, an apparatus incorporating a quadrupole ion trap has been constructed in our laboratory to perform LIF and PD-action spectroscopy. The gas-phase fluorescence and photodissociation properties of three Rhodamine dyes have been investigated including fluorescence excitation and dispersed fluorescence spectra. Finally, the latter chapters describe the use of electronic action spectroscopy to investigate a model chromophore of the green fluorescent protein (GFP), p-hydroxybenzylidene-2,3-dimethylimidazolone (HBDI). The body of work in this dissertation highlights the integration of gas-phase spectroscopy and mass spectrometry to elucidate the fundamental photophysical properties of biological and related ions.

Successful integration of daylighting systems requires the ability to predict their performance for given climates. In this dissertation, a bottom-up approach is applied to evaluate the optical performance of a selection of daylighting systems. The evaluations are based on the optical properties of the included materials, and part of the dissertation focuses on developing new optical characterization methods. The work on characterization techniques uses an integrating sphere method to characterize the transmittance of light scattering samples more accurately. The method's principle is to reduce the discrepancy in light distribution between the reference and the sample scans by using an entry port beam diffuser. For samples exhibiting distinct light scattering patterns, the benefits of improved uniformity outweigh the errors introduced by the diffusing material. The method is applicable to any integrating sphere instrument, and its simplicity makes it suitable for standard measurements. In addition to normal-hemispherical properties, many daylighting applications require knowledge of the system's spatial light distribution. This dissertation presents a method combining experimental techniques and ray tracing simulations to assess the light distribution from a Venetian blind system. The method indicates that ray tracing based on simplified optical data is inadequate to predict the light distribution for slat materials exhibiting both specular and diffuse properties. Ray tracing is a promising complement to experimental methods used to characterize light guiding or light redirecting systems. Here, spectrophotometric measurements of a scaled mirror light pipe validate a ray tracing model. The model shows excellent agreement with experimental results for both direct and diffuse incident light. The spectral evaluation shows no dramatic color changes for the transmitted light. The ray tracing model is used to evaluate four daylighting systems for a selection of Swedish locations. The percentage of occupied time when the studied systems achieve full design illuminance is relatively low, but the systems provide a valuable contribution to the required illuminance. Additionally, this dissertation provides an overview of available energy efficient windows and illustrates the importance of including the solar energy transmittance when evaluating window energy performance. Overall, this dissertation presents optical characterization techniques for improved performance evaluations of daylighting systems.

Ce travail de doctorat est dédié à l’étude des mécanismes régissant l’interaction lumière-matière dans des dispositifs optoélectroniques à base d’alliages (Al,Ga,In,)N. Diverses compositions de ces alliages sont assemblées en structures multicouches de matériaux d’épaisseurs nanométriques afin d’obtenir une émission à plus grande longueur d’onde que le bleu, couleur pour laquelle la technologie est mature depuis plus de vingt ans. Il s’agit de réaliser des émetteurs efficaces de lumière jaune, verte ou blanche (avec une approche alternative au pompage optique de luminophore par une diode bleue). Les solutions solides assemblées pour obtenir des émissions à grandes longueur d’onde sont à base de GaN et de Ga0.8In0.2N, matériaux pour lesquels les mailles cristallographiques sont désaccordées. Lorsqu’elles sont déposées sur un substrat ou un pseudo-substrat de GaN, matériau pour lequel les dopages n et p sont maitrisés et permettent l’injection électrique des porteurs, les tranches de Ga0.8In0.2N subissent de très fortes compressions dans leur plan de croissance et l’énergie élastique est relaxée par la formation de défauts délétères pour le rendement lumineux. Nous avons construit des hétéro-structures plus complexes en intercalant une couche complémentaire d’Al0.2Ga0.8N afin de réduire la densité d’énergie élastique globale. L’insertion de telles couches améliore la qualité cristalline et augmente leur rendement optique. Nous avons mesuré le rendement quantique interne en utilisant la spectroscopie de photoluminescence résolue en temps et une analyse des temps de déclins par une approche de type Lotka-Volterra des équations de recombinaison pour obtenir les taux de recombinaisons radiatifs et non-radiatifs. Nous avons montré quantitativement comment les champs électriques internes résultant du contraste de polarisation électrique aux interfaces et les recombinaisons non-radiatives de type Schockley-Read-Hall contribuent à définir le rendement quantique à faible densité d’excitations (optique ou électrique). L’objectif est l’obtention d’une émission spontanée intense pour une densité d’excitation modérée. Nous avons donc conduit une campagne d’expériences en variant l’intensité d’injection. Nous avons montré que l’effet Auger est le facteur dominant régissant la chute du rendement quantique interne sous fortes densités d’injection. Nous avons étudié diverses architectures à simple puits quantique ou à puits quantiques multiples émettant à des longueurs d’onde identiques pour quantifier l’influence spécifique de l’effet Stark confiné quantique. Nous avons corrélé l’apparition d’un seuil d’excitation au-delà duquel domine la recombinaison non-radiative de type Auger avec l’augmentation du temps de recombinaison radiative et de l’énergie de localisation des porteurs dans l’alliage inhomogène. Nous arrivons à la conclusion que la localisation des porteurs produite par le champ électrique aux interfaces et les fluctuations de la composition chimique de Ga0.8In0.2N contribuent de concert, facilitant l’interaction répulsive électron-électron et la recombinaison non-radiative Auger nnp. Nous avons montré que le modèle ABC permet de bien décrire la physique du phénomène si ses trois paramètres tiennent compte des effets d’écrantages sous injections modérées et des effets de remplissage de l’espace des phases sous fortes injections. Enfin, nous nous sommes écartés de l’étude des structures traditionnellement épitaxiées selon le plan polaire (0001) pour choisir des plans d’épitaxie semi-polaire (11-22). Dans ces conditions, il a été nécessaire de fabriquer des puits quantiques en Ga0.65In0.35N. Nous avons montré que la quasi-absence d’effet Stark confiné quantique augmente de manière très significative le seuil d’excitation au-delà duquel domine la recombinaison non-radiative de type Auger. Cette amélioration par rapport aux échantillons épitaxiés selon le plan (0001) est d’autant plus marquée que la longueur d’onde émise est grande. / Non renseigné

Nous avons utilisé une nouvelle méthode de photochimie laser pour la fabrication de microstructure 3D à base de nanofils métalliques. Les nanofils sont obtenus par photoréduction laser de sels métalliques dissous dans une matrice polymère. La réaction chimique est initiée par absorption à deux photons de photoréducteurs uniquement au point focal du laser. La géométrie des microstructures est obtenue en déplaçant le point focal du laser selon des trajectoires adaptées. Dans cette thèse nous avons étudié les propriétés optiques de structures à base de nanofils d'argent. Un nanofil qui occulte une onde plane crée un champ diffracté qui présente des trajectoires paraboliques de maximas et minimas d'intensité. Les calculs de Rayleigh-Sommerfeld montre que cette figure de diffraction typique correspond à l'inférence entre l'onde plane incidente et les ondes sphériques qui sont générées par diffraction sur les deux bords du nanofil. Lorsque les nanofils sont organisés en ensemble de nanofils parallèles distants de quelques microns, les champs diffractés donne des distributions d'intensité qui sont similaires à celles de microlentilles cylindriques. Dans ce cas l'interférence entre l'onde incidente et les ondes sphériques diffractées par les nanofils créée une distribution de phase quadratique qui est à l'origine de la focalisation. La fabrication de réseaux 2D de nanofils permet d'obtenir des réseaux de microlentilles très denses (10000x10000 DPI, dots per inch) qui ne sont pas réalisable avec des microlentilles réfractives. La possibilité de fabriquer des géométries 3D permet de manipuler les trajectoires des maxima et minima d'intensité pour obtenir de nouvelles fonctions diffractives à l'échelle microscopique. Par exemple, la fabrication de nanofils décalés dans l'espace nous a permis de développer un nouveau type de microdisposif optique qui permet la séparation spatiale des couleurs rouge, vert et bleu à l'échelle microscopique. / We used a novel method of laser photochemistry to fabricate 3D microstructures based on metallic nanowires. Nanowires are obtained by laser photoreduction of metallic salt dissolved in a polymer matrix. The chemical reaction is initiated by the two-photon absorption of a photoreductor only at laser focal point. The geometry of microstructures is obtained by moving laser focal point according to suitable trajectories. In this thesis, we have studied the optical properties of of structures based on silver nanowires. A nanowire that stops a plane wave creates a diffracted field which shows parabolic trajectories of maxima and minima intensities. Calculations based on Rayleigh-Sommerfeld diffraction show that this typical figure corresponds to interferences between the incident plane wave and spherical waves generated at the two nanowire edges. When nanowires are arranged into set of parallel nanowires, spaced by a few microns, their diffracted fields generate intensity distributions similar to those of cylindrical refractive microlenses. In that case interference between the incident wave and the diffracted wave leads to a quadrative phase which is the at origin of focalisation. Manufacturing 2D arrays of nanowires allow to achieve very dense arrays of microlenses (10000x10000 DPI, dots per inch), which are impossible to make with refractive microlenses. The possibility to make 3D geometry permit to manipulate maxima and minima intensity trajectories for new diffractive functions at the microscopic scale. For instance manufacturing nanowires shifted in space leads to a new type of optical microdevice that allows the spatial separation of colors red, green and blue at microscopic scale.

Estudamos as propriedades de absorção e emissão de aglomerados Yb2+/CN- em haletos de potássio (KCl, KBr e KI) e estamos propondo um modelo para a estrutura geométrica do aglomerado. Neste modelo o itérbio divalente e o íon cianeto substituem um cátion e um ânion vizinhos, respectivamente, com o eixo que une os dois íons na direção . O acoplamento entre os dois impede o movimento rotacional do cianeto, mesmo à temperatura ambiente, como pode ser comprovado pela presença de linhas estreitas no espectro de absorção infravermelha. Os espectros de absorção visível e ultravioleta são compatíveis com as transições 4&#40214&#8594 4&#40213 5d do itérbio em simetria C4v. A absorção vibracional indica a presença não intencional de OCN- que pode formar aglomerados com os íons cianeto. À temperatura do nitrogênio líquido, observa-se a influência do itérbio sobre os estados rotacionais do cianeto, uma indicação da interação entre centros vizinhos. A excitação sobre as bandas de absorção ultravioleta e visível produz intensa emissão em que podem ser identificadas três regiões (450&#8594;500 nm, 500&#8594;600 nm e acima de 600 nm) com comportamentos distintos quanto à variação da temperatura e excitação. Os tempos de vida variam de 50&#181s à temperatura ambiente até 20 ms à temperatura do hélio líquido. Simultaneamente à emissão visível, observa-se a emissão vibracional-rotacional dos íons cianeto, com indicações de transferência de energia entre os íons cianeto acoplados ao itérbio e os isolados / We have studied the absorption and emission properties of the Yb2+/CN- in potassium halides (KCl, KBr and KI) and it was proposed a structural model for this system. In this model the divalent ytterbium and the cyanide ion substitute a neighboured cation and an anion along a direction. The rotational motion of the cyanide ion is constrained by the coupling with the ytterbium, which is by the presence of narrow lines in the infrared absorption spectra, even at room temperature. The UV and visible absorption spectra are compatibles with the 4&#40214&#8594 4&#40213 5d ytterbium transitions under C4v symmetry. The vibrational absorption reveals the unintentional presence of OCN- that can form clusters with cyanide ions. The influence of the ytterbium over the rotational states of cyanide can be observed at liquid nitrogen temperature, revealing the interaction between both impurities. The optical excitation if the absorption bands shows a broad and strong emission in three regions (450&#8594;500 nm, 500&#8594;600 nm and above 600 nm) with different behaviors under temperature and excitation pump changes. Lifetimes between &#181s at room temperature and 20 ms at liquid heliurn temperature can be observed. Simultaneously to the visible emission, it was observed the vibrational-rotational emission of CN- ions with evidences of energy transfer between coupled Yb<sup<2+/CN- pairs and isolated CN- ions

Este trabalho apresenta o estudo de propriedades espectroscópicas de Vidros Oxifluoroboratos de Chumbo, 40PbO-10PbF2-50B2O3 dopados com diferentes concentrações de Dy3+: 1, 3, 5 e 7 mol%. Para tanto foram empregadas as técnicas de Difração de Raios-X, Espalhamento Raman, Absorção Óptica e Fotoluminescência. Parâmetros como temperatura de transição vítrea, índice de refração e densidade também foram determinados. O comportamento do índice de refração, da densidade, e da temperatura de transição vítrea, Tg, indicaram uma possível mudança estrutural provocada pela adição de dopante, o que foi confirmado pela Espectroscopia Raman. Com as medidas de absorção óptica foram calculados os parâmetros fenomenológicos de Judd-Ofelt, &#937&#955 (&#955 = 2, 4, 6), com os quais se calculou as probabilidades de transição radiativa do íon, bem como se verificou o caráter covalente das ligações presentes na matriz. As medidas de Fotoluminescência mostraram que o aumento da concentração de dopante diminui a intensidade da emissão, e que a diminuição da temperatura provoca um aumento da intensidade das mesmas bem como promove o estreitamento das bandas de emissão. Além disto, foi possível verificar a dependência da intensidade da emissão com a energia de excitação utilizada. Para as medidas de Fotoluminescência em baixas temperaturas foi desenvolvido um sistema alternativo baseado numa sonda de fibra óptica cuja utilização mostrou-se mais simples que a tradicional montagem com criostato. / This work presentes the study of the spectroscopic properties of Lead Oxifluroborate Glasses, 40PbO-10PbF2-50B2O3 doped with four different concentrations of Dy3+: 1, 3, 5 e 7 mol%. In order to achieve this, X-ray diffraction, Raman scaterring, Optical absorption, and Photoluminescence techniques were applied. Important parameters like the glass transition temperature, the index of refraction, and the density were also obtained. The behavior of these parameters suggested a possible structural change induced by adding Dy3+: which was confirmed by Raman scattering. The Judd-Ofelt phenomenological parameters, &#937&#955 (&#955 = 2, 4, 6), were calculated from the optical absorption results. From these values the ion radioactive transition probability were obtained and the covalent character of the bonds in the matrix was established. The photoluminescence measurements showed that an increase of Dy3+: concentration diminishes the emission intensity. The opposite happens decreasing the temperature, which also narrows the emission bands. Additionally, the emission intensity dependence with the excitation energy was verified. In order to study photoluminescence in the low temperatures range it was developed an alternative system based on an optical fiber probe. This device revealed to be more simple to operate than cryostat traditional system.

Os nitretos do grupo III (AlN, GaN, InN) sao semicondutores extremamente importantes na atualidade principalmente por suas aplicacoes em dispositivos emissores de luz de alta eficiência no visível e no ultravioleta. Neste trabalho foram estudados filmes finos de nitreto de gálio cubico (c-GaN, zincblende) crescidos sobre substratos de carbeto de silício cubico (3C-SiC) por epitaxia de feixe molecular assistida por plasma (PA-MBE). Inicialmente analisou-se o processo de implantação iônica através de técnicas de simulação computacional. Tendo em vista os resultados obtidos pelas simulações, as amostras foram submetidas a processo de implantação iônica com energia de feixe de 200 keV e diferentes íons implantados (Fe, Mn e Cu) nas doses de 1.2 e 2.4 × 1016 cm2. Com a implantação de íons magnéticos buscou-se a criação de um semicondutor com resposta ferromagnética acima da temperatura ambiente, enquanto que com a implantação do íons não magnéticos buscou-se, principalmente, um maior entendimento sobre a influencia de defeitos da rede cristalina sobre o magnetismo do material. Posteriormente as implantações e com o intuito de recuperar a rede cristalina das amostras danificada pelo processo, as amostras foram submetidas a tratamento térmico. Apos cada um destes processos as amostras foram caracterizadas estruturalmente, através de medidas de difração de raios x, espectroscopia de fotoluminescência e espectroscopia Raman e também magneticamente utilizando-se um SQUID. Conseguiu-se a caracterizacao quantitativa das transformações da rede cristalina pre e pós tratamento térmico com as diferentes técnicas. Foi observado comportamento ferromagnético a temperatura ambiente em amostras dopadas com os diversos íons e notou-se uma grande influencia da dose implantada, tanto nas propriedades estruturais quanto magnéticas das amostras. / Group-III nitrides (AlN, GaN, InN) are presently very important semiconductors mainly because of applications in high-efficiency, visible and ultraviolet, light-emitting devices. In this work, thin films of cubic gallium nitride (c-GaN, zincblende), grown over cubic silicon carbide (3C-SiC) by plasmaassisted molecular beam epitaxy (PA-MBE) were studied. Initially the process of ion implantation was investigated with the aid of computer simulation software. Following the simulations results, the samples were implanted with a 200 keV ion-beam of three different ions (Fe, Mn and Cu) with doses of 1.2 and 2.4 × 1016 cm2. With the implantation of magnetic ions the formation of a semiconductor with room-temperature ferromagnetic response was expected, whereas the implantation of non-magnetic ions (Cu) was performed seeking a better understanding on the influence of lattice defects on the subsequent magnetism. After the implantation the samples were annealed to recover some of the crystallinity lost due to the implantation process. After each process the samples were structurally characterized through x-ray diffraction, photoluminescence and Raman spectroscopies, and magnetically characterized through SQUID magnetometry. A quantitative measure of the transformations of the crystal lattices was obtained before and after annealing with the different techniques. Room-temperature ferromagnetic behavior was observed in the samples doped with different ions and a large influence of implanted dose was noted, in the structural properties and also in the magnetic properties.

Orientador: Rickson Coelho Mesquita / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-25T21:15:48Z (GMT). No. of bitstreams: 1 CanoRodriguez_Reember_M.pdf: 7820145 bytes, checksum: a3b06ecbe442d6ecf0266b22a280fb76 (MD5) Previous issue date: 2014 / Resumo: A capacidade de observar a fisiologia funcional do tecido humano tem crescido rapidamente nos últimos anos. Entre outras técnicas, destaca-se a espectroscopia óptica de difusão (DOS), uma técnica emergente que utiliza os princípios da difusão de fótons e permite o monitoramento do tecido biológico de forma continua e portátil. A partir da luz (~ 700 - 900 nm) espalhada pelo tecido é possível determinar variações relativas do seu coeficiente de absorção, que estão relacionadas com as concentrações de oxi-hemoglobina (HbO2) e deoxi-hemoglobina (HbR) presentes no sangue. Neste trabalho, utilizamos a técnica de DOS no domínio da frequência, e a informação da defasagem da onda espalhada (em relação _a onda incidida) para determinação das propriedades ópticas absolutas do tecido biológico e, consequentemente, da sua fisiologia. Em particular, comparamos diferentes modelos de propagação da luz no tecido (semi-infinito e duas camadas) e as propriedades ópticas derivadas destes modelos. Além disso, investigamos métodos de calibração do sinal óptico no tecido, do ponto de vista teórico e experimental, mostrando sua aplicabilidade em experimentos com humanos, no estado de repouso e em intervenções cirúrgicas / Abstract: The ability to observe the functional physiology of human tissue has grown rapidly in recent years. Among other techniques, we highlight diffuse optical spectroscopy (DOS), an emerging technique that utilizes the principles of diffusion of photons and allows monitoring of biological tissue continuously and portable way. From the light (~700 - 900 nm) scattered by tissue it is possible to determine the relative changes in the absorption coefficient, which are related to the concentrations of oxyhemoglobin (HbO2), and deoxyhemoglobin (HbR) in the blood. In this study, we used the technique DOS in the frequency domain, and the phase information of the scattered wave (related to incident wave) for determining the absolute optical properties of biological tissue and, consequently, the physiology. In particular, we compared different models of propagation of light (semi-infinite and two-layer) and the optical properties of tissue derived from these models. Furthermore, we investigated methods of calibration of the optical signal on the tissue from both the experimental and theoretical perspectives, demostrating its applicability in experiments with humans in the resting state and in surgical interventions / Mestrado / Física / Mestre em Física

Relative changes are detectable in the blood of end-stage renal disease (ESRD) patients during hemodialysis (HD) treatment using optical spectroscopy. However, the potential impacts of several confounding factors that could affect the detection of these changes have not been evaluated. The objectives of this thesis were to: 1) investigate how the variations and/or changes in acid-base and oxygen parameters during HD treatment can affect the optical signature of whole blood of ESRD patients, 2) to investigate the effect of heparin on the optical properties of whole blood and its impact on our method. Blood samples were drawn from 23 ESRD patients at 5 time points during a 4 hour HD treatment and sent for blood gas and blood spectroscopy analyses. No significant correlations were found between the changes in the blood transmittance spectra and acid-base and oxygen parameters. This indicates that the perturbations in these parameters due to HD procedures do not confound the detection of changes in the blood transmittance spectra of ESRD patients during HD treatment. Additionally, the effect of heparin in modifying the optical properties of whole blood does not confound the detection of changes in the blood of ESRD patients due to HD treatment using whole blood-based optical spectroscopy. ANOVA revealed significant (P<0.05) measurable changes in the blood transmittance spectra of ESRD patients during HD treatment. Significant spectral differences (P<0.05) were found between ESRD patients. The lack of uniform spectral characteristics across patients is