Tout au long du procédé d’élaboration d’un vin, des réactions d’oxydation peuvent se produire y compris au cours du vieillissement en bouteilles. Depuis quelques années, la profession viti-vinicole est confrontée au problème de l’oxydation prématurée des vins blancs.. A ce jour, peu d’études ont pu apporter des explications d’ordre chimique à ce phénomène, et les mécanismes réactionnels intervenant restent peu connus.L’objectif de ce travail de thèse est d’apporter, au travers d’une analyse moléculaire non ciblée en spectrométrie de masse à transformée de Fourier et à résonance cyclotronique des ions (FT-ICR-MS) couplée à une étude chimiométrique, des réponses originales aux questions posées par la problématique actuelle d’oxydation prématurée des vins blancs. Nous avons montré suite à l’étude d’une série de vins oxydés prématurément non seulement la grande diversité chimique des vins, mais aussi la présence d’un ensemble de masses typiques associées à ce phénomène. Pour une meilleure compréhension de l’origine de cette problématique, nous avons considéré deux autres types d’oxydation : une oxydation relative exclusivement à un apport contrôlé en oxygène et une autre relative à l'évolution naturelle de vins en bouteilles. Cette dernière consiste en le suivi de l'évolution des espaces chimiques de séries verticales de vins blancs et rouges en fonction du temps. Sur la série verticale des vins blancs allant de 1979 à 2006, une charnière à l’année 1990 a été observée avec des groupes de masses typiques de chacun des vins jeunes (1979-1990) et des vieux vins (1991-2006).La comparaison entre les espaces chimiques discriminants chacun de ces trois types d’oxydation ne révèle la présence que de trois masses en commun, ce qui appuie l'hypothèse de causes multiparamétriques à l’oxydation prématurée des vins blancs, qui ne serait donc pas un phénomène du exclusivement à une exposition non contrôlée à l'oxygène.Des essais d’élucidation structurale en FT-ICR-MS/MS des masses discriminantes des vins oxydés et de la série verticale ont été effectués et des schémas de fragmentation pour certaines masses sont proposés / During winemaking processes, many oxidation reactions may occur especially during the aging period. Recently, white wines are characterized by a problem of premature oxidation for which few studies have provided chemical explanation. To date, the involved mechanisms in this phenomenon remain poorly understood.The aim of this thesis project is to provide, through an untargeted molecular analysis using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) coupled to chemometric analysis, original clue to understand the premature oxidation of white wines. Based on the study of a series of premature oxidized white wines, we were able to elucidate the high complexity and the chemical diversity of wine, and got out typical masses characterizing the oxidation state. In order to better understand the origin of this phenomenon, we considered two alternative possibilities of oxidation: the first one induced by oxygen, and the second through a natural evolution of wines in bottles. The latter included the monitoring of the chemical evolution of white and red wines as a function of time. A very interesting result was obtained on the vertical series of white wines from 1979 to 2006, where two groups were separated at the 1990 vintage to provide a group of old wines (1979-1990) and a group of new wines (1991-2006). Typical discriminant masses were found for each group.A comparison between the chemical spaces discriminating each of the three types of oxidation (premature oxidation, oxidation with oxygen and natural evolution of wine in bottle) revealed very few common masses that may indicate that the phenomenon of premature oxidation is indeed influenced by multiple factors.Finally, a structural elucidation of the typical masses of the groups of oxidized and aged wines were established using FT-ICR-MS/MS. Possible fragmentations schemes of some of these masses were proposed

Dans un objectif de valorisation des huiles d’olive tunisiennes, les huiles de huit variétés autochtones : Chemchali, Chemlali Sfax, Chemlali Zarzis, Chétoui, Oueslati, Sayali, Zalmati et Zarrazi ont été étudiées et caractérisées par des techniques spectroscopique et chromatographique en tenant compte de leurs composés mineurs (acides gras mineurs, squalène, phénols totaux et α-, β- et γ-tocophérols). Une banque de données à été créé à partir des analyses de la composition en acides gras et des spectres proche infrarouge de 516 échantillons d’huiles d’olive vierges. Quatre outils d’authentification de l’origine variétale, basés sur l’utilisation des approches statistiques et chimiométriques associées aux données chromatographiques et spectrales, ont été élaborés. / In order to valorize the Tunisian olive oil production, eight autochthonous oil varieties (Chemchali, Chemlali Sfax, Chemlali Zarzis, Chétoui, Oueslati, Sayali, Zalmati and Zarrazi) were characterized by chromatographic and vibrational spectroscopy approaches. Fatty acid, squalene and near infrared spectra were analyzed in 516 samples which were used to create the data bank. Four origin varietal authentication tools were established using statistic and chemometric fatty acid treatment, NIR Spectra and olive oil minor fraction (minor fatty acids, squalene, totals phenols and α, β and γ-tocopherols).

Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / The methodology developed in the present work, through chromatographic fingerprint by LC-DAD and Principal Component Analysis (PCA), was adequate for the chemical differentiation of Lippia alba (Mill) NE Brown accessions, considering the extraction method (infusion and maceration hydroalcoholic) and the collection season (summer and winter), allowing to evaluate the influence of these variables on the chemical composition of extracts obtained. In addition, all extracts were submitted to cytotoxic tests against two tumor cell lines, HL-60 (human leukemia) and HepG2 (human hepatocellular carcinoma), and to inhibition tests against the enzyme acetylcholinesterase (AChE) in order to evaluate the form of extraction and which access is the most promising from a pharmacological point of view. Among the extracts analyzed against tumor cells, eight of them, two from the infusion: 01IW and 02IW and six from the hydroalcoholic extraction: 02HW, 24HW, 39HW, 54HW, 01HS and 24HS, presented better cell inhibition performances against HL-60, with percentage of inhibition between 40.0 and 52.0%, suggesting that these extracts are potentially promising against this lineage. With respect to the anticholinesterase tests, all extracts studied had low AChE inhibitory effect when compared to galantamine (87.4%), highlighting only the samples 01HW (28.4%), 02HW (27.2%), 54HW (29.3%), 01HS (32.7%), 02HS (27.4%) and 24HS (30.3%). Through the analyzes performed by Nuclear Magnetic Resonance (NMR) it was possible to identify the structures of some compounds isolated from this species: flavone tricin and phenylpropanoid verbascoside/isoverbascoside. In addition, the classes of three other metabolites were proposed: two phenylpropanoid derivatives and one flavonoid diglucoside. / A metodologia desenvolvida no presente trabalho, utilizando fingerprint cromatográfico por CL-DAD e Análise de Componentes Principais (PCA), se mostrou adequado para a diferenciação química de acessos de Lippia alba (Mill) N. E. Brown, considerando o método de extração (infusão e maceração hidroalcoólica) e a época de coleta (verão e inverno), permitindo, ainda, avaliar a influência destas variáveis na composição química dos extratos obtidos. Adicionalmente, todos os extratos foram submetidos a testes citotóxicos frente a duas linhagens de células tumorais, HL-60 (leucemia humana) e HepG2 (carcinoma hepatocelular humano), e de inibição enzimática frente a acetilcolinesterase (AChE) com o intuito de avaliar qual a forma de extração e qual acesso é o mais promissor do ponto de vista farmacológico. Entre todos os extratos analisados frente as células tumorais, dois provenientes da infusão: 01II e 02II e seis da extração hidroalcoólica: 02HI, 24HI, 39HI, 54HI, 01HV e 24HV, apresentaram melhores desempenhos de inibição frente a HL-60, com percentual de inibição entre 40,0 e 52,0%, sugerindo que estes extratos são potencialmente promissores contra esta linhagem. Com relação aos testes anticolinesterásicos, todos os extratos estudados apresentaram baixo efeito inibidor da AChE quando comparados a galantamina (87,4%), com destaque para os extratos 01HI (28,4%), 02HI (27,2%), 54HI (29,3%), 01HV (32,7%), 02HV (27,4%) e 24HV (30,3%). Através das análises realizadas por Ressonância Magnética Nuclear (RMN) foi possível identificar as estruturas de alguns dos compostos isolados a partir desta espécie: a flavona tricina e o fenilpropanóide verbascosídeo/isoverbascosídeo. Além disso, foram propostas as classes de outros três metabólitos: dois derivados de fenilpropanóides e um flavonóide diglicosilado. / São Cristóvão, SE

<p>U ovoj doktorskoj disertaciji je radi fizičko-hemijske karakterizacije i ispitivanja potencijalne<br />biolo&scaron;ke aktivnosti sintetisano&nbsp; 40&nbsp; derivata mono(tio)karbohidrazona. Strukture dobijenih jedinjenja su potvrđene&nbsp; NMR&nbsp; i&nbsp; FT&ndash;IR&nbsp; spektroskopijom,&nbsp; elementalnom&nbsp; i&nbsp; rendgenskom&nbsp; strukturnom&nbsp; analizom. Uticaj&nbsp; rastvarača&nbsp; i&nbsp; prisutnog&nbsp; supstituenta&nbsp; na&nbsp; položaje apsorpcionih&nbsp; maksimuma&nbsp; ispitani&nbsp; su&nbsp; po principima LSER i LFER metoda. Teorijski proračuni za sintetisana jedinjenja izvedeni su&nbsp; primenom TD&ndash;DFT&nbsp; metode.&nbsp; Jonizacione&nbsp; konstante&nbsp; derivata&nbsp; mono(tio)karbohidrazona&nbsp; su&nbsp; određene potenciometrijskim&nbsp; titracijama.&nbsp; Antioksidativna&nbsp; aktivnost&nbsp; je&nbsp; određena&nbsp; primenom&nbsp; tri&nbsp; testa:&nbsp; DPPH, ABTS&nbsp; i&nbsp; FRAP&nbsp; testa.&nbsp; Antimikrobna&nbsp; aktivnost&nbsp; je&nbsp; ispitana&nbsp; mikrodilucionom&nbsp; metodom&nbsp; na&nbsp; dva&nbsp; soja bakterija:&nbsp; Staphylococcus&nbsp; aureus&nbsp; i&nbsp; Escherichia&nbsp; coli.&nbsp; Za&nbsp; jedinjenja&nbsp; koja&nbsp; su&nbsp; pokazali&nbsp; antimikrobnu aktivnost je&nbsp; ispitan procenat citotoksičnosti.&nbsp; Sveukupan&nbsp; zaključak o sličnosti i razlikama sintetisanih derivata izveden je na osnovu multivarijatnih metoda klaster analize i analize glavnih komponenti.</p> / <p>In this doctoral dissertation, 40 mono(thio)carbohydrazone derivatives were synthesized for the purpose of physico-chemical characterization and examination of potential biological activity. The structures of the obtained compounds were confirmed by NMR and FT &ndash;IR spectroscopy, elemental analysis&nbsp; and&nbsp; X-ray&nbsp; structural&nbsp; analysis.&nbsp; The&nbsp; influence&nbsp; of&nbsp; solvent&nbsp; and&nbsp; substituent&nbsp; present&nbsp; on&nbsp; the positions&nbsp; of&nbsp; absorption maxima&nbsp; was&nbsp; examined&nbsp; according&nbsp; to&nbsp; the&nbsp; principles&nbsp; of&nbsp; LSER&nbsp; and&nbsp; LFER methods.&nbsp; Theoretical&nbsp; calculations&nbsp; for&nbsp; the&nbsp; synthesized&nbsp; compounds&nbsp; were&nbsp; performed&nbsp; by&nbsp; the&nbsp; TD&ndash;DFT method.&nbsp; The&nbsp; acid&nbsp; constants&nbsp; of&nbsp; mono(thio)carbohydrazone&nbsp; derivatives&nbsp; were&nbsp; determined&nbsp; by potentiometric&nbsp; titrations.&nbsp; Antioxidant&nbsp; activity&nbsp; was&nbsp; determined&nbsp; using&nbsp; three&nbsp; tests:&nbsp; DPPH,&nbsp; ABTS&nbsp; and FRAP test. Antimicrobial activity was examined by microdilution method on two strains of bacteria: Staphylococcus&nbsp; aureus&nbsp; and&nbsp; Escherichia&nbsp; coli.&nbsp; The&nbsp; percentage&nbsp; of&nbsp; cytotoxicity&nbsp; was&nbsp; examined&nbsp; for compounds&nbsp; that&nbsp; showed&nbsp; antimicrobial&nbsp; activity.&nbsp; Overall&nbsp; conclusion&nbsp; about&nbsp; the&nbsp; similarities&nbsp; and differences of the synthesized&nbsp; derivatives was studied by multivariate&nbsp; methods of cluster analysis and analysis of principal components.</p>

Este trabalho de pesquisa descreve três estudos de utilização de métodos quimiométricos para a classificação e caracterização de óleos comestíveis vegetais e seus parâmetros de qualidade através das técnicas de espectrometria de absorção molecular no infravermelho médio com transformada de Fourier e de espectrometria no infravermelho próximo, e o monitoramento da qualidade e estabilidade oxidativa do iogurte usando espectrometria de fluorescência molecular. O primeiro e segundo estudos visam à classificação e caracterização de parâmetros de qualidade de óleos comestíveis vegetais utilizando espectrometria no infravermelho médio com transformada de Fourier (FT-MIR) e no infravermelho próximo (NIR). O algoritmo de Kennard-Stone foi usado para a seleção do conjunto de validação após análise de componentes principais (PCA). A discriminação entre os óleos de canola, girassol, milho e soja foi investigada usando SVM-DA, SIMCA e PLS-DA. A predição dos parâmetros de qualidade, índice de refração e densidade relativa dos óleos, foi investigada usando os métodos de calibração multivariada dos mínimos quadrados parciais (PLS), iPLS e SVM para os dados de FT-MIR e NIR. Vários tipos de pré-processamentos, primeira derivada, correção do sinal multiplicativo (MSC), dados centrados na média, correção do sinal ortogonal (OSC) e variação normal padrão (SNV) foram utilizados, usando a raiz quadrada do erro médio quadrático de validação cruzada (RMSECV) e de predição (RMSEP) como parâmetros de avaliação. A metodologia desenvolvida para determinação de índice de refração e densidade relativa e classificação dos óleos vegetais é rápida e direta. O terceiro estudo visa à avaliação da estabilidade oxidativa e qualidade do iogurte armazenado a 4C submetido à luz direta e mantido no escuro, usando a análise dos fatores paralelos (PARAFAC) na luminescência exibida por três fluoróforos presentes no iogurte, onde pelo menos um deles está fortemente relacionado com as condições de armazenamento. O sinal fluorescente foi identificado pelo espectro de emissão e excitação das substâncias fluorescentes puras, que foram sugeridas serem vitamina A, triptofano e riboflavina. Modelos de regressão baseados nos escores do PARAFAC para a riboflavina foram desenvolvidos usando os escores obtidos no primeiro dia como variável dependente e os escores obtidos durante o armazenamento como variável independente. Foi visível o decaimento da curva analítica com o decurso do tempo da experimentação. Portanto, o teor de riboflavina pode ser considerado um bom indicador para a estabilidade do iogurte. Assim, é possível concluir que a espectroscopia de fluorescência combinada com métodos quimiométricos é um método rápido para monitorar a estabilidade oxidativa e a qualidade do iogurte / This research work describes three studies of chemometric methods employed for the classification and characterization of edible oils and its quality parameters through Fourier Transform mid infrared spectroscopy and near infrared spectroscopy, and for the monitoring the oxidative stability and quality of yogurt using fluorescence spectroscopy . The first and second studies aimed the classification and characterization of edible oil and its quality parameters using Fourier Transform mid infrared spectroscopy (FT-MIR) and near infrared spectroscopy (NIR) measurements, respectively. Kennard-Stone algorithm was used for selecting the training set, after a principal component analysis (PCA) was applied. The discrimination of canola oils from sunflower, corn and soybean was investigated using SVM-DA, SIMCA and PLS-DA. The quality parameters refraction index and relative density of edible oil was investigated using partial least squares (PLS), iPLS, LS- SVM multivariate calibration of FT-MIR and NIR data were evaluated. Several preprocessing alternatives (first derivative, multiplicative scatter correction, mean centering, orthogonal signal correction and standard normal variate) were investigated by using the root mean square error of validation cross validation (RMSECV) and prediction (RMSEP), as control parameters. In fact, the methodology developed is proposed for direct relative density and refraction index in edible oils and their classification, requiring a few minutes per sample without any previous treatment. The third study aimed to evaluate the oxidative stability and quality of yogurt stored at 40C with light or dark using the combined parallel factor (PARAFAC) analysis and fluorescence spectroscopy. PARAFAC analysis of the fluorescence landscapes exhibited three fluorophores present in the yogurt, where, at least one of them was strongly related to the storage conditions. The fluorescence signal was resolved into excitation and emission profiles of the pure fluorescent compounds, which are suggested to be vitamin A, tryptophan and riboflavin. Regression model based on PARAFAC scores for riboflavin were built using the scores obtained in the first day as dependent variable and the scores obtained during the storage as independent variable. It was clear demonstrated that the slope of the analytical curve has become smaller throughout the experiment. Therefore, riboflavin level could be considered a good indicator for the yogurt stability. Thus, it is concluded that fluorescence spectroscopy in combination with chemometrics has a potential as a fast method for monitoring the oxidative stability and quality of yogurt

Este trabalho de pesquisa descreve três estudos de utilização de métodos quimiométricos para a classificação e caracterização de óleos comestíveis vegetais e seus parâmetros de qualidade através das técnicas de espectrometria de absorção molecular no infravermelho médio com transformada de Fourier e de espectrometria no infravermelho próximo, e o monitoramento da qualidade e estabilidade oxidativa do iogurte usando espectrometria de fluorescência molecular. O primeiro e segundo estudos visam à classificação e caracterização de parâmetros de qualidade de óleos comestíveis vegetais utilizando espectrometria no infravermelho médio com transformada de Fourier (FT-MIR) e no infravermelho próximo (NIR). O algoritmo de Kennard-Stone foi usado para a seleção do conjunto de validação após análise de componentes principais (PCA). A discriminação entre os óleos de canola, girassol, milho e soja foi investigada usando SVM-DA, SIMCA e PLS-DA. A predição dos parâmetros de qualidade, índice de refração e densidade relativa dos óleos, foi investigada usando os métodos de calibração multivariada dos mínimos quadrados parciais (PLS), iPLS e SVM para os dados de FT-MIR e NIR. Vários tipos de pré-processamentos, primeira derivada, correção do sinal multiplicativo (MSC), dados centrados na média, correção do sinal ortogonal (OSC) e variação normal padrão (SNV) foram utilizados, usando a raiz quadrada do erro médio quadrático de validação cruzada (RMSECV) e de predição (RMSEP) como parâmetros de avaliação. A metodologia desenvolvida para determinação de índice de refração e densidade relativa e classificação dos óleos vegetais é rápida e direta. O terceiro estudo visa à avaliação da estabilidade oxidativa e qualidade do iogurte armazenado a 4C submetido à luz direta e mantido no escuro, usando a análise dos fatores paralelos (PARAFAC) na luminescência exibida por três fluoróforos presentes no iogurte, onde pelo menos um deles está fortemente relacionado com as condições de armazenamento. O sinal fluorescente foi identificado pelo espectro de emissão e excitação das substâncias fluorescentes puras, que foram sugeridas serem vitamina A, triptofano e riboflavina. Modelos de regressão baseados nos escores do PARAFAC para a riboflavina foram desenvolvidos usando os escores obtidos no primeiro dia como variável dependente e os escores obtidos durante o armazenamento como variável independente. Foi visível o decaimento da curva analítica com o decurso do tempo da experimentação. Portanto, o teor de riboflavina pode ser considerado um bom indicador para a estabilidade do iogurte. Assim, é possível concluir que a espectroscopia de fluorescência combinada com métodos quimiométricos é um método rápido para monitorar a estabilidade oxidativa e a qualidade do iogurte / This research work describes three studies of chemometric methods employed for the classification and characterization of edible oils and its quality parameters through Fourier Transform mid infrared spectroscopy and near infrared spectroscopy, and for the monitoring the oxidative stability and quality of yogurt using fluorescence spectroscopy . The first and second studies aimed the classification and characterization of edible oil and its quality parameters using Fourier Transform mid infrared spectroscopy (FT-MIR) and near infrared spectroscopy (NIR) measurements, respectively. Kennard-Stone algorithm was used for selecting the training set, after a principal component analysis (PCA) was applied. The discrimination of canola oils from sunflower, corn and soybean was investigated using SVM-DA, SIMCA and PLS-DA. The quality parameters refraction index and relative density of edible oil was investigated using partial least squares (PLS), iPLS, LS- SVM multivariate calibration of FT-MIR and NIR data were evaluated. Several preprocessing alternatives (first derivative, multiplicative scatter correction, mean centering, orthogonal signal correction and standard normal variate) were investigated by using the root mean square error of validation cross validation (RMSECV) and prediction (RMSEP), as control parameters. In fact, the methodology developed is proposed for direct relative density and refraction index in edible oils and their classification, requiring a few minutes per sample without any previous treatment. The third study aimed to evaluate the oxidative stability and quality of yogurt stored at 40C with light or dark using the combined parallel factor (PARAFAC) analysis and fluorescence spectroscopy. PARAFAC analysis of the fluorescence landscapes exhibited three fluorophores present in the yogurt, where, at least one of them was strongly related to the storage conditions. The fluorescence signal was resolved into excitation and emission profiles of the pure fluorescent compounds, which are suggested to be vitamin A, tryptophan and riboflavin. Regression model based on PARAFAC scores for riboflavin were built using the scores obtained in the first day as dependent variable and the scores obtained during the storage as independent variable. It was clear demonstrated that the slope of the analytical curve has become smaller throughout the experiment. Therefore, riboflavin level could be considered a good indicator for the yogurt stability. Thus, it is concluded that fluorescence spectroscopy in combination with chemometrics has a potential as a fast method for monitoring the oxidative stability and quality of yogurt

In forensic chemistry, a quicker and more accurate analysis of a sample is always being pursued. Speedy analyses allow the analyst to provide quick turn-around times and potentially decrease back-logs that are known to be a problem in the field. Accurate analyses are paramount with the futures and lives of the accused potentially on the line. One of the most common methods of analysis in forensic chemistry laboratories is gas chromatography, chosen for the relative speed and efficiency afforded by this method. Two major routes were attempted to further improve on gas chromatography applications in forensic chemistry.<br> The first route was to decrease separation times for analysis of ignitable liquid residues by using micro-bore wall coated open-tubular columns. Micro-bore columns are much shorter and have higher separation efficiencies than the standard columns used in forensic chemistry, allowing for faster analysis times while maintaining the expected peak separation. Typical separation times for fire debris samples are between thirty minutes and one hour, the micro-bore columns were able to achieve equivalent performance in three minutes. The reduction in analysis time was demonstrated by analysis of ignitable liquid residues from simulated fire debris exemplars.<br> The second route looked at a relatively new detector for gas chromatography known as a vacuum ultraviolet (VUV) spectrophotometer. The VUV detector uses traditional UV and far-ultraviolet light to probe the pi and sigma bonds of the gas phase analytes as well as Rydberg traditions to produce spectra that are nearly unique to a compound. Thus far, the only spectra that were not discernable were from enantiomers, otherwise even diastereomers have been differentiated. The specificity attained with the VUV detector has achieved differentiation of compounds that mass spectrometry, the most common detection method for chromatography in forensic chemistry labs, has difficulty distinguishing. This specificity has been demonstrated herein by analyzing various classes of drugs of abuse and applicability to “real world” samples has been demonstrated by analysis of de-identified seized samples.<br>

[pt] As partículas finas (PM2.5) são um dos principais poluentes atmosféricos associados a problemas de saúde. Estas partículas penetram no sistema respiratório, carreando desde metais traços a substâncias orgânicas. Apesar disso, a legislação ambiental brasileira ainda não tem estabelecido padrões para este poluente. Entretanto, Agencia Ambiental dos Estados Unidos (US.EPA) já tem adotado limites para exposições de curto (25 (micro)g m-3/diário) e longo (15 (micro)g m-3/anual) prazo. Esta tese teve quatro principais objetivos: (1) investigar a relação das condições meteorológicas, sazonalidade e bacias aéreas sobre as concentrações de PM2.5 na atmosfera; (2) avaliar modelos de previsão de qualidade do ar inovadores para estimar concentração de PM2.5 em locais com diferentes fontes de emissão; (3) validar método de extração e determinação pseudototal de metais traços presentes no material particulado, com espectrômetro de emissão ótica por plasma indutivamente acoplado (ICP-OES) de acordo com critérios estabelecidos pelo INMETRO; (4) quantificar carbono orgânico e metais traços presentes no material particulado fino para entender melhor como a atmosfera do estado do Rio de Janeiro tem sido afetada, devido aos vários tipos de emissão e condições meteorológicas. Amostradores de grandes volumes coletaram todas as amostras de PM2.5. Estes amostradores foram operados por 24 h, a cada seis dias, em locais com diferentes fontes de emissão (industrial, veicular, poeira do solo, etc.), no estado do Rio de Janeiro. As amostras foram coletadas pelo Instituto Estadual do Ambiente (INEA), no período de janeiro/11 até dezembro/13. Variáveis meteorológicas próximas (d(menor que)2 km) aos pontos de monitoramento de PM2.5 também foram obtidas na mesma frequência e período de amostragem. Em relação a este estudo, quatro resultados podem ser destacados. O primeiro, as concentrações médias diárias de PM2.5 variaram de 1-65 (micro)g m-3, ultrapassando em alguns pontos os limites adotados pela US.EPA. Estes resultados mostraram que concentrações de PM2.5 no RJ não é influenciada, em expressão, pela sazonalidade. Além disso, foi observado que as bacias aéreas definidas no Rio de Janeiro não têm sido confirmadas, e os locais mostraram uma semelhança de comportamento em função da sua fonte de emissão. O segundo, a aplicação do modelo Holt-Winters para previsão de PM2.5 simulou melhor a zona industrial, com RMSE (raiz do erro quadrático médio) entre 5,8-14,9 (micro)g m-3. Em contrapartida, a rede neural artificial associada a variáveis meteorológicas estimou melhor os resultados das zonas urbanas e rurais, com RMSE entre 4,2-9,3 (micro)g m-3. O terceiro, o método de extração e determinação pseudototal de metais por ICP-OES atendeu aos critérios de validação estabelecidos pelo INMETRO. Além disso, mostrou-se ser equivalente ao método US.EPA IO-3.1. Finalmente, as concentrações de carbono orgânico solúvel em água variaram de 0,8-4,9 (micro)g m-3. Os principais metais determinados foram: Na (5,8-13,6 (micro)g m-3), Al (1,6-6,7 (micro)g m-3) e Zn (1,9-6,6 (micro)g m-3). Foi verificado também que os fenômenos meteorológicos de superfície aumentam em 30 por cento a explicação da variância do modelo receptor (PCA), quando adicionados aos dados das substâncias químicas analisadas do PM2.5. Contudo, é crucial a aplicação de ferramentas quimiométricas para ajudar na caracterização e estimava das concentrações de poluentes atmosféricos. / [en] Fine particulate matters (PM2.5) are one of the primary air pollutants associated with health problems. These particles penetrate in the respiratory system, loading from trace metals to organic compounds. Neverthelere4ss, the Brazilian environmental legislation has not yet established standards for this pollutant. However, the US Environmental Agency (US.EPA) has already adopted limits for short-term (25 (micro)g m-3/daily) and long-term (15 (micro)g m-3/annual) exposures. This thesis had four main objectives: (1) to investigate the relation of weather conditions, seasonality and air basins on PM2.5 concentrations in the atmosphere; (2) to evaluate innovative air quality forecast models to estimate PM2.5 concentration in sites with different emission sources; (3) to validate method to extract and pseudo total determinate trace metals present in the particulate matter by inductively coupled plasma optical emission spectrometer (ICP-OES) according to criteria established by INMETRO; (4) to quantify organic carbon and trace metals present in fine particulate matter to better understand how the Rio de Janeiro State (RJ) atmosphere has been affected due to the various types of emission and weather conditions. High volumes samplers PM2.5 collected all PM2.5 samples. These samplers were operated for 24 h, every six days, in places with different emission sources (industrial, vehicular, soil dust, et caetera), in the Rio de Janeiro State. The samples were collected by the State Environmental Institute (INEA) during the period from January/2011 still December/2013. Meteorological variables nearby (d(less than)2 km) to PM2.5 monitoring points were also obtained at the same frequency and sampling period. Regarding this study, four results can be highlighted. The first one, the PM2.5 dailly concentrations average ranged from 1-65 (micro)g m-3, exceeding in some sites the limits adopted by US.EPA. These results showed that PM2.5 concentrations in RJ is not influenced, in expression, by the seasonality. In addition, it was observed that the defined RJ air basins have not been confirmed, and the local showed a similar performance according to their emission sources. The second one, the application of the Holt-Winters model for PM2.5 forecast simulated best industrial zone, with RMSE (root mean square error) between 5.8 to 14.9 (micro)g m-3. On the others hand, the artificial neural network associated with meteorological variables estimated best results from urban and rural areas, with RMSE between 4.2 to 9.3 (micro)g m-3. The third one, the method to extract and determine pseudo total metals by ICP-OES followed the validation criteria established by INMETRO. Furthermore, it was shown to be equivalent to US.EPA IO-3.1 method. Finally, the water-soluble organic carbon concentrations ranged from 0.8 to 4.9 (micro)g m-3. The principal metals determined were: Na (5.8-13.6 (micro)g m-3), Al (1.6-6.7 (micro)g m-3) and Zn (1.9-6.6 (micro)g m-3). It was also found that the surface meteorological phenomena increase at 30 percent the explicated variance of the receiver model (PCA) when added to PM2.5 chemical analysis data. Therefore, it is crucial the application of chemometric tools to help in the characterization and estimated air pollutant concentrations.

Indiana University-Purdue University Indianapolis (IUPUI) / Clear coats have been part of automotive field paint finishes for several decades. Originally a layer of paint with no pigment, they have evolved into a protective layer important to the appearance and longevity of the vehicle's finish. These clear coats have been studied previously using infrared spectroscopy and other spectroscopic techniques. Previous studies focused on either all the layers of an automobile finish or on chemometric analysis of clear coats using other analytical techniques. For this study, chemometric analysis was performed on preprocessed spectra averaged from five separate samples. Samples were analyzed on a Thermo-Nicolet Nexus 670 connected to a Continuμm™ FT-IR microscope. Two unsupervised chemometric techniques, Agglomerative Hierarchical Clustering (AHC) and Principal Component Analysis (PCA), were used to evaluate the data set. Discriminant analysis, a supervised technique, was evaluated using several known qualifiers; these included cluster group from AHC, make, model, and year. Although discriminant analysis confirmed the AHC and PCA results, no correlation to make, model, or year was indicated.