The emergence of advanced computational techniques and artificial intelligence has strongly impacted the materials discovery and optimization. This study focuses on applying computational methods to extract information from complex spectral systems. Three distinct tiers of information extraction from hyperspectral data are explored: integrating light data treatment with computational modeling, employing convolutional neural networks for signal reconstruction, and advancing quantification using probabilistic machine learning. In the first tier, utilizing electron energy loss spectroscopy (EELS) in conjunction with boundary element method modeling, we uncovered the broadband plasmonic properties in wrinkled gold structures and their origin. We demonstrated the link between broadband plasmonic characteristics and surface nano-features, offering insights into property tunability. To benefit the broader microscopy community, in the second tier, we developed EELSpecNet, a Python script based on convolutional neural networks. EELSpecNet reconstructs signals to retrieve details that were obscured by various signal artifacts. EELSpecNet was benchmarked for near-zero-loss EELS, a challenging signal that contains crucial phononic and plasmonic information. The results clearly show that this neural network approach surpasses conventional Bayesian methods in deconvolution, particularly in terms of information retrieval, signal fidelity, and noise reduction. The final tier of this research introduces an innovative approach to spectral analysis and quantification using probabilistic machine learning methods. By employing the Markov Chain Monte Carlo sampling and Gaussian Process Regression models, this tool facilitates spectral quantifications, provides comprehensive uncertainty analysis, reduces human biases in the decision-making and model selection processes. This tool is particularly useful for in-operando X-ray diffraction data analysis, a key technique for examining battery materials. This method effectively disentangles overlapping peaks, quantifies each peak, and tracks their evolution. Tested on both synthetic and real experimental data, the tool demonstrated its efficacy and versatility. Given its broad adaptability, this method is suitable for a variety of spectroscopy techniques. / Thesis / Doctor of Science (PhD)

O principal objetivo deste estudo foi avaliar a refletância e sua influência no comportamento térmico de tintas refletivas e tintas convencionais aplicadas em telhas de fibrocimento para cobertura de habitações brasileiras. Foram realizados ensaios em laboratório de determinação de cor e de brilho por medida instrumental e determinação da refletância por análise espectrofotométrica em películas. Para o estudo do comportamento térmico foram realizados ensaios de simulação em laboratório com corpos-de-prova expostos à radiação infravermelha emitida por lâmpadas e de exposição à radiação solar em campo através de protótipos com monitorização da temperatura durante as exposições. Os resultados dos ensaios de determinação de cor e de brilho mostraram que as pinturas refletivas e convencionais realmente apresentaram cores correspondentes. Os resultados de refletância mostraram que as pinturas refletivas apresentaram valores de refletância superiores em relação às tintas convencionais, o que foi comprovado pela temperatura medida nos ensaios de exposição à radiação infravermelha e radiação solar. A conclusão do estudo é que as tintas refletivas têm potencial para redução da temperatura superficial da telha de fibrocimento e que é necessária uma continuidade do estudo de durabilidade e do desempenho térmico de tintas refletivas coloridas. / The main purpose of this study was to investigate the effect of reflective colored paints and conventional colored paints applied on fiber cement corrugated roofing sheets, proving whether both type of paints can present different reflection characteristics in the infrared solar radiation and high thermal performance. Color and gloss were measured by instrumental methods and reflectivity (reflection coefficient) was measured using spectrophotometers equipped with integrating spheres in free paint films. In order to investigate the thermal performance of reflective and conventional paints, simulation tests were performed in laboratory by IR lamps using fiber cement specimens and in field by exposure solar radiation using prototypes with temperature monitoring. The results showed that the reflective paints present higher reflectivity and better thermal performance than the conventional paint, independently of the color. The results showed that the reflective paints present potential to reduce superficial temperature of fiber cement corrugated roofing sheets. It is necessary to continue the reflective colored paints study on durability and thermal performance by exposure tests.

Among the three common gas hydrate structures, structure-H (sH) hydrate has been regarded as forming only in the laboratory since it was first reported in 1987. However, natural gas hydrate samples obtained from the Cascadia margin showed that sH hydrate can form naturally. Not only was the sH hydrate found in natural samples, but it was also discovered that n-alkanes such as n-pentane and n-hexane, considered to have too large molecular size to be sH hydrate formers, can act as co-guests of sH hydrates in mixtures with other sH hydrate formers. In this study, thermodynamic measurements and spectroscopic analysis of powder X-ray diffraction and 13C solid-state NMR methods, were performed for synthetic hydrate samples in order to identify the accommodation of n-alkanes with five or more carbon atoms. In addition, some new hydrate guests were found to form sH hydrates. From the present results, it is clear that, so far, our understanding of gas hydrates and guest enclathration needs to be revised and expanded in order to explain new findings.

O principal objetivo deste estudo foi avaliar a refletância e sua influência no comportamento térmico de tintas refletivas e tintas convencionais aplicadas em telhas de fibrocimento para cobertura de habitações brasileiras. Foram realizados ensaios em laboratório de determinação de cor e de brilho por medida instrumental e determinação da refletância por análise espectrofotométrica em películas. Para o estudo do comportamento térmico foram realizados ensaios de simulação em laboratório com corpos-de-prova expostos à radiação infravermelha emitida por lâmpadas e de exposição à radiação solar em campo através de protótipos com monitorização da temperatura durante as exposições. Os resultados dos ensaios de determinação de cor e de brilho mostraram que as pinturas refletivas e convencionais realmente apresentaram cores correspondentes. Os resultados de refletância mostraram que as pinturas refletivas apresentaram valores de refletância superiores em relação às tintas convencionais, o que foi comprovado pela temperatura medida nos ensaios de exposição à radiação infravermelha e radiação solar. A conclusão do estudo é que as tintas refletivas têm potencial para redução da temperatura superficial da telha de fibrocimento e que é necessária uma continuidade do estudo de durabilidade e do desempenho térmico de tintas refletivas coloridas. / The main purpose of this study was to investigate the effect of reflective colored paints and conventional colored paints applied on fiber cement corrugated roofing sheets, proving whether both type of paints can present different reflection characteristics in the infrared solar radiation and high thermal performance. Color and gloss were measured by instrumental methods and reflectivity (reflection coefficient) was measured using spectrophotometers equipped with integrating spheres in free paint films. In order to investigate the thermal performance of reflective and conventional paints, simulation tests were performed in laboratory by IR lamps using fiber cement specimens and in field by exposure solar radiation using prototypes with temperature monitoring. The results showed that the reflective paints present higher reflectivity and better thermal performance than the conventional paint, independently of the color. The results showed that the reflective paints present potential to reduce superficial temperature of fiber cement corrugated roofing sheets. It is necessary to continue the reflective colored paints study on durability and thermal performance by exposure tests.

L’utilisation d’adhésifs polyépoxy et plus particulièrement de pâte de calage dans l’aéronautique est chose très courante. L’augmentation des cadences de production des aéronefs poussent les fournisseurs à adapter les temps technologiques de ces produits (temps d’application et de complète polymérisation) : ainsi, la cinétique de réticulation des adhésifs de demain devra être lente à température ambiante et pouvant être accélérée à tout moment. Pour cela, la piste envisagée pour ces tra-vaux est la polymérisation sous rayonnement infrarouge. La cinétique de ré-action a été évaluée par analyse thermique (DSC) ou par analyse spectrosco-pique (MIR ou PIR). Les résultats obtenus ont mis en évidence un effet thermique et non thermique du rayonnement infrarouge. Grâce à plusieurs expérimentations, les résultats montrent que le rayonnement infrarouge interagit avec les groupe-ments époxydes dont l’énergie d’activation de la réaction avec les amines primaires diminue. Par ailleurs, l’utilisation d’un plan d’expérience a permis de montrer que l’adhérence et les propriétés mécaniques de ces adhésifs augmentaient suite à l’utilisation du rayonnement infrarouge. / The use of polyepoxy adhesives and more particularly of liquid shim in aero-nautics is very common. The increase in aircraft production rates is pushing suppli-ers to adapt the technological times of these sort of products (application and complete curing times): thus, the curing kinetics of tomorrow's adhesives must be slow at room temperature and can be accelerated at any time. For this purpose, this work paves the way of an infrared curing. The reaction kinetics were evalu-ated by thermal analysis (DSC) or spectroscopic analysis (MIR or NIR). The results obtained showed a thermal and non-thermal effects of infrared radiation. Thanks to several experiments, the results show that infrared radiation interacts with epoxide groups whose activation energy with primary amines reaction decreas-es. In addition, by the use of Design of Experiment (DoE) showed that the ad-hesion and mechanical properties of these adhesives increased as a result of the use of infrared radiation.

Made available in DSpace on 2017-07-21T18:53:10Z (GMT). No. of bitstreams: 1 Resultados.pdf: 1211314 bytes, checksum: 38baa9c0e58df7dddd94d9184303e7b7 (MD5) Previous issue date: 2008-04-14 / Photo and thermal oxidation effects on the stability of refined soybean, corn, canola and sunflower oils was evaluated by spectroscopy and titration methods in this work. Oils samples were submitted to oven test (63°C – 45 days) and photoxidation (room temperature – 4000 lux – 60 days). The antioxidants addition effects was evaluated on the oil protection during photoxidation. The results showed that the canola oil is more resistant to thermal and photoxidation while the sunflower oil shows less resistance. Good correlations between peroxide values and ultraviolet and 1H NMR data were found (correlation coefficients 0.962 to 0.996). The ultraviolet data indicated that the antioxidants effectiveness on the photoxidation oil protection was: propyl gallate (PG) > tert-butyl hydroquinone (TBHQ) > butilated hydroxytoluene (BHT) > butilated hydroxyanisole (BHA) > citric acid. The results showed that UV and NMR are efficient techniques to monitoring antioxidants effects, oxidative changes and vegetable oil quality control under thermal or photochemical stress. / Neste trabalho foram avaliados os efeitos da fotoxidação e termoxidação na estabilidade dos óleos de soja, milho, canola e girassol, por técnicas titulométricas e espectroscópicas. As amostras foram submetidas ao oven test (63°C – 45 dias) e à fotoxidação (temperatura ambiente – 4000 lux – 60 dias). Foram avaliados também os efeitos da adição de antioxidantes na proteção dos óleos durante a fotoxidação. Os resultados indicaram que o óleo de canola é o mais resistente à oxidação térmica e fotoxidativa enquanto o óleo de girassol é o menos resistente. Foram obtidas excelentes correlações entre o índice de peróxidos e os dados de ultravioleta e RMN de 1H, cujos coeficientes de regressão variaram de 0,962 a 0,996. Os dados de ultravioleta indicaram que a eficiência dos antioxidantes na proteção de óleos vegetais sob estresse fotoxidativo foi: propil galato (PG) > terc-butil-hidroquinona (TBHQ) > butil-hidroxitolueno (BHT) > butilhidroxianisol (BHA) > ácido cítrico. Os resultados mostraram que a espectroscopia de ultravioleta e RMN de 1H são técnicas eficientes para monitorar os efeitos de antioxidantes, alterações oxidativas e controle de qualidade de óleos vegetais sob estresse térmico ou fotoquímico.

Aerosols affect climate change, the energy balance of the atmosphere, and public health due to their variable chemical composition, size, and shape. Aerosols from natural and anthropogenic sources can be primary organic aerosols (POA), which are directly emitted to the atmosphere, or secondary organic aerosols (SOA) that are formed from chemical reactions of gas-phase precursors. At variance with the well investigated formation of SOA from gas phase precursors, the chemistry of aqueous SOAs that contribute to the total SOA budget remains unknown. Field measurements have revealed that carboxylic, dicarboxylic and oxocarboxylic acids are abundant species present in SOAs. This thesis explores the fate of two such acids, pyruvic (PA) and glyoxylic (GA) acids surrogates of the oxocarboxylic acids in the atmosphere, in their cross reaction under solar irradiation and dark thermal aging. Mixtures of complex photoproducts are identified by ion chromatography (IC) with conductivity and electrospray (ESI) mass spectrometry (MS) detection, direct ESI-MS analysis in the negative ion mode, and nuclear magnetic resonance spectroscopy (NMR) analysis including one-dimensional (1H- and 13C-NMR) and two-dimensional techniques such as gradient correlation spectroscopy (gCOSY) and heteronuclear single quantum correlation (HSQC). A reaction mechanism for the cross reaction is provided based on all experimental observations.

Indiana University-Purdue University Indianapolis (IUPUI) / Protein-protein interactions play a crucial role in a wide range of biological processes. Research on the design and synthesis of small molecules to modulate these proteinprotein interactions can lead to new targets and drugs to modulate their function. In Chapter one, we discuss the design and synthesis of small molecules to probe a proteinprotein interaction in a voltage-gated Ca2+ channel. Virtual screening identified a compound (BTT-3) that contained a 3,4-dihydro-3,4’-pyrazole core. This compound had modest biological activity when tested in a fluorescence polarization (FP) assay. The synthetic route to BTT-3 consisted of six steps. In addition, analogs of BTT-3 were made for a structure-activity study to establish the importance of a carboxylate moiety. We also synthesized a biotinylated benzophenone photo-affinity probe and linked it to BTT-3 to identify additional protein targets of the compound. In Chapter two, small-molecule antagonists targeting uPA-uPAR protein-protein interaction are presented. A total of 500 commercially-available compounds were previously identified by virtual screening and tested by a FP assay. Three classes of compounds were found with biological activity. The first class of compounds contains pyrrolidone core structures represented by IPR- 1110, the second class has a novel pyrrolo[3,4-c]pyrazole ring system, represented by xv IPR-1283 and the last series had compounds with a 1,2-disubstituted 1,2- dihydropyrrolo[3,4-b]indol-3(4H)-one core structure, represented by IPR-540. Each of these three compounds were synthesized and assessed by FP and ELISA assays. A binding mode of IPR-1110 with uPA was subsequently proposed. Based on this binding mode, another 61 IPR-1110 derivatives were synthesized by us to illustrate the SAR activity. Analogs of the other two series were also synthesized.

Indiana University-Purdue University Indianapolis (IUPUI) / Toner analysis has become an area of increased interest due to the wide availability of laser printers and photocopiers. Toner is most often encountered on paper in questioned document analysis. Because of this, it is important to develop methods that limit the interference of paper without damaging or destroying the document. Previous research using Fourier transform infrared spectroscopy (FTIR) has differentiated toners based on their polymer resin components. However, Raman spectroscopy and chemometric analysis are not typically used for the examination of this material. Raman spectroscopy is a popular tool for the chemical analysis of pigmented samples and was used to characterize cyan, yellow, and magenta toners. Analyses were performed using a dispersive micro-Raman spectrometer equipped with a 785nm diode laser, a CCD detector, and an objective at 20X magnification. One hundred samples of each color toner were collected. Three different and separate methods were developed for cyan, yellow, and magenta toners on paper to optimize results. Further analysis of the magenta toners was excluded due to a weak signal and significant paper interference. The data collected from the analyses of the blue and yellow toners was then processed using a combination of statistical procedures, including principal component analysis (PCA), agglomerative hierarchal clustering (AHC), and discriminative analysis (DA). Ninety-six blue toners were analyzed by PCA and three classes of spectra were suggested. Discriminant analysis showed that the three classes were well-differentiated with a cross-validation accuracy of 100% for the training set and 100% cross-validation accuracy for the external validation set. Eighty-eight yellow toners were analyzed by AHC and four classes of spectra were suggested. Discriminant analysis showed good differentiation between the classes with a cross-validation accuracy of 95.45% for the training set, but showed poor differentiation for the external validation set with a cross-validation accuracy of 72%. While these toners were able to be discriminated, no correlation could be made between the manufacturer, printer make and model, and the toner sample.