The aim of this study was to optimize the sample preparation and methods for analysis of oligosaccharides of hyaluronic acid with MALDI- TOF-MS. The analysis was carried out on an Autoflex speed MADLI-TOF- MS instrument with both linear and reflectron mode. Matrices used in this study were 2,5-DHB and Super-DHB and type of matrix was chosen depending on the size of the analyzed oligosaccharides. The application of sample and matrix on the target that gave the most homogenous crystallization was sandwich and the laser power in the MALDI was kept at 65 %. Since it is known that salts and buffers interfere with the analysis, sample clean-up such as solid phase extraction (SPE) in pipette tips and dialysis was performed. SPE worked best for low mass oligosaccharides and provided high intensity and little noise. With SPE a concentration of the analyte could be done which was the advantage over dialysis. Dialysis worked well for larger oligosaccharides and mixtures of different sized oligosaccharides. Another way of using MALDI for biomolecule analysis is with TLC-MALDI. A fast and accurate separation was achieved and analysis could be done directly from the plate. The optimized methods were evaluated according to linearity and precision, LOD, mass accuracy and matrix stability. The linearity and precision was good in a higher concentration range (50 μg/mL and higher), but the test for limit-of-detection (LOD) indicated that concentrations from 20-30 μg/mL could be analyzed with no interference from the background. The mass accuracy was within the acceptable limits according to Bruker Daltonics when a mass calibration was done for each analyzed sample. The stability of the matrix in solution was difficult to study because of the day-to-day variation in intensities given by the MALDI-TOF-MS technique.

Master of Science / Department of Chemistry / Christopher T. Culbertson / Chemists have been trying to relate the structure and composition of different cereal proteins to their physical properties to better inform their product use for more than 250 years now. Among these cereals, wheat is considered the most important due to its unique ability to form viscoelastic dough and retain gas during fermentation, the latter being important for bread making. This property is due to the endosperm part of wheat that contains proteins mostly gliadins and glutens. It is known that the composition and relative ratio of these proteins is determined by both the growing environment and genetics. Manipulation of the genetics allows one for control of only about 50% of the end use quality of the wheat and the rest is controlled by environment. Currently, the bread making quality of wheat is determined by baking test loaves of bread. This process is time consuming and wasteful. The main goal of this project was to create fingerprints of gliadin proteins for different wheat cultivars as a function of environmental conditions. This would then allow wheat kernels to be analyzed and assessed right after harvest to determine their appropriateness for making the various wheat products. Researchers have tried to create a catalogue of information for individual wheat cultivars by ‘fingerprinting’ the gliadins proteins in wheat using various analytical techniques including capillary electrophoresis (CE). CE offers advantages like high separation efficiency, and faster analysis. Further miniaturization of CE on microfluidic devices has enhanced the speed and efficiency of separation. Furthermore, it is possible to integrate multiple chemical analysis processes like sample preparation, separation and detection in a single microfluidics device. Microfluidic uses micron sized separation channels defined in a glass, quartz or polymer. This dissertation is focused on fabricating multilayer microfluidic devices from Poly(dimethylsiloxane) (PDMS) and using these devices to electrophoretically separate wheat gliadin proteins followed by detection using UV absorption in less than 5 min. PDMS is cheap, easy to fabricate and is optically transparent above ~230nm. Initial results of the UV absorbance detector developed for this device are presented.

Pollution poses serious threats to both the environmental and the organisms that depend on their environment for survival. Due to the toxicity of most contaminants, there is a dire need for remediation of polluted sites. Remediation studies were conducted on two high priority pollutants: 2,4,6-trinitrotoluene (TNT) and crude oil. TNT was the most common explosive used in the 20th century. Continuous contamination has resulted in an urgent need for remediation. Fenton reagent provides an advanced oxidation process that is capable of remediating recalcitrant explosives, such as TNT. One drawback of Fenton chemistry is that the reaction requires acidic pH to prevent precipitation of iron. Our studies have investigated Fenton degradation of TNT at near neutral pH with several modifiers present: β-cyclodextrin, carboxymethyl-β-cyclodextrin, alcohols, and polyethylene glycol (PEG, MW 200, 400, or 600 g/mol). Fenton degradation was also carried out on other nitroaromatics to better understand the reaction mechanism with PEG 400. Further mechanistic studies investigated the production of nitrate and ammonium with and without PEG 400. The Deepwater Horizon oil spill devastated the Gulf of Mexico and the surrounding wetlands. There are several mechanisms for degradation of oil released into aquatic environments. Bioremediation is one of the most important remediation methods; however degradation becomes stagnant in low nutrient waters. Furthermore, larger molecular weight alkanes and polycyclic aromatic hydrocarbons (PAHs) are not readily available for biodegradation. Transformation of these molecules often requires initial photodegradation. We have investigated the photochemical transformation of oil films with and without photocatalysts present. To better understand the photochemical transformations that occur to the Deepwater Horizon oil, we have conducted additional studies with dispersants present.

Estudou-se o comportamento de íons de cobre (II) em soluções de tiocianato de sódio por via espectrofotométrica e polarográfica. O estudo espectrofotométrico em força iônica 2,0M, a 25°C, levou a determinação da constante de formação da primeira espécie, Cu SCN+, com máximo de absorção a 342 nm, sendo β1 = 56 M-1 e ε1,max = 495?.mol-1 cm-1. Tentativas de estudar a formação sucessiva dos outros três complexos não levaram a resultado satisfatório devido à instabilidade de cor do sistema cobre(II/SCN-. Extenso estudo levou ao esclarecimento do comportamento polarográfico do cobre (II) em tiocianato, onde havia sérias discordâncias na literatura. Comprovou-se que parte do cobre (II) oxida o ligante, passando a cobre (I), havendo formação de SO=4 e HCN. Há três ondas polarográficas: a primeira, catódica, mas sem descontinuidade com o componente anódico de dissolução de mercúrio pelo eletrólito suporte, devido ao cobre (II) remanescente; a segunda trata da redução do cobre (I) ao amálgama de cobre; a terceira é a onda de redução dos íons de hidrogenia liberados pela oxidação do ligante. Fizeram-se estudos de medidas de potencial no sistema (SCN)2/SCN- com tiocianogênio gerado coulometricamente, ou por agentes químicos oxidantes. Novas perspectivas de trabalho são discutidas. Polarogramas no sistema cobre(I)/SCN-, em força iônica 4,0M, a 25°C, levaram ao primeiro estudo completo de equilíbrio do sistema, caracterizado pelas seguintes constantes de equilíbrio: (Ver no arquivo em PDF) Para o cobre (II) foi estimado o seguinte valor de constante: (Ver no arquivo em PDF) / The behavior of copper (II) in sodium thiocyanate solutions was examined by polarography and spectrophotometry. The spectrophotometric study performed in an ionic strength 2.0M at 25°C, lead to the determination of the formation constant β1 = 56 M-1, referred to Cu SCN+ specie. Its absorption maximum is 342 nm and ε1,max = 495?.mol-1 cm-1. Attempts to study the formation of the others successive complexes were unsuccess full due to color instability in the copper(II)/SCN system. Extensive study lead to the elucidation of the polarographic behavior of copper (II) in thiocyanate supporting electrolite. Severe disagreement was found in the literature about this subject. It has been found that copper (II) oxidises partially the ligand to SO=4 and HCN, with partial formation of copper (I). Three waves were well characterized: the first one is cathodic, but with no discontinuity with the anodic wave of mercury dissolution by thiocyanate, resulting from the presente of the remaining copper (II); the second one is referred to the reduction of copper (I) to copper a malgam; the third wave in the reduction of hydrogen ion released during the oxidation of the ligande. Potential measurement were carried out in the (SCN)2/SCN- system, with thiocyanogen generated by coulometry, or by the action of chemical oxidising agents. New prospects and ideas to be worked were discussed. Polarograms from the copper(I)/SCN- system, were obtained in 4,0M ionic strength and 25°C. They lead to the first complete equilibrium study of this system, with the determination of the following equilibrium constants: (See in PDF file) With regard to copper (II) the foliowing formation constant was estimated: (See in PDF file)

Orientador: Maria Valnice Boldrin Zanoni / Banca: Maria del Pilar Taboada Sotomayor / Banca: Christiane de Arruda Rodrigues / Banca: Marcos Roberto de Vasconcelos Lanza / Banca: Luiz Henrique Dall'Antonia / Resumo: O presente trabalho ilustra diversas aplicações da técnica de fotoeletrocatálise, tais como: degradação de corantes têxteis, corantes de curtumes, surfatantes, redução de Cr(VI) a Cr(III) e redução de bromato a brometo, usando eletrodos de filmes finos de Ti/TiO2 e luz ultravioleta. A oxidação fotoeletrocatalítica de soluções simuladas de efluentes de curtumes contendo dicromato de potássio, o corante ácido vermelho e o surfatante Tamol® foi investigada em Na2SO4 0,1 mol L-1 usando anodos de filme fino de TiO2 sob potencial de + 1,0 V e irradiação UV-Vis. Foi obtido 100% de remoção do corante ácido vermelho 151 e 98,5% de redução de Cr(VI) a Cr(III) e 94,6% de remoção de carbono orgânico total (COT), após 60 min de fotoeletrocatálise em pH = 2,0. A técnica de fotoeletrocatálise foi ainda aplicada na degradação de dois efluente industriais contendo corantes dispersos em Na2SO4 0,1 mol L-1. Os resultados obtidos mostraram descoloração de 95%, 97%, e 100% de remoção dos corantes dispersos: laranja, rubi e vermelho dispersil, sendo que a porcentagem de mineralização foi de 62,7%; 43,3% e 61,3%, respectivamente. Remoção de 80-89% da coloração dos efluentes foram conseguidas após 360 min de fotoeletrocatálise, concomitante à redução de 49,8% e 46,8% de COT e 50% de redução da demanda química de oxigênio (DQO). O método mostrou-se ainda adequado para a redução de 0,25 mg L-1 de bromato a brometo com máxima performance sob potencial de -0,2 V e luz UV, usando o Ti/TiO2 como fotocátodo. O método promoveu 65% de redução de bromato após 75 min de tratamento. / Abstract: In the present work has been studied the application of photoelectrocatalytic process to degradation of acid dyes, disperse dyes, surfactant, Cr (VI)/Cr (III) reduction and BrO3 -/Brreduction, using Ti/TiO2 electrodes and UV- Vis irradiation. The photoeletrocatalytic oxidation of simulated leather industry wastewater containing Cr(VI), acid red 151 dye, Tamol® surfactant was investigated in Na2SO4 0,1 mol L-1 solution using Ti/TiO2, potencial of + 1.0V and UV irradiation. 100% of color removal, 98.5% of Cr(VI)/Cr (III) reduction and 94.6% of TOC removal were obtained after 60 min of treatment at pH = 2.0. The photoelectrocatalytic process was successfully applied in the wastewater degradation of textile industry too. The results have shown 95%, 97% and 100% of color removal for orange, ruby e red disperse dyes concomitant to reduction of 62,7%; 43,3% e 61,3% TOC values, respectively. Two wastewater was analyzed and the results present 80-89% of color removal, 49,8% and 46,8% of TOC removal and 50% of COD after 360 min of photoeletrocatalytic treatment. The reduction of bromate to bromide was also followed by photoeletrocatalytic treatment testing 0.25 mg L-1 of bromate in NaCl using Ti/TiO2 electrode, UV irradiation and potential of - 0.2V. The method has shown 65% of bromate concentration reduction after 75 min of treatment. / Doutor

Orientador: Maria Valnice Boldrin / Banca: Valdir Souza Fereira / Banca: Mauro Bertotti / Resumo: O presente trabalho propõe um método eletroanalítico para determinação dos disruptores endócrinos bisfenol A e nonilfenol em meio micelar utilizando-se eletrodos de carbono vítreo (ECV) e eletrodos de carbono impresso (ECI). Estes disruptores endócrinos têm levantado grande preocupação pois podem promover alterações no sistema endócrino e nível hormonal de humanos, além de sérios efeitos adversos nos organismos aquáticos, mesmo em baixas concentrações. A oxidação do grupo fenólico nos compostos BPA e NP ocorre em potencial 0,42 e 0,56 V, respectivamente em eletrodo de carbono vítreo e em 0,29 e 0,25V para eletrodo de carbono impresso. Curvas voltamétricas obtidas na presença de surfactante brometo de cetiltrimetilamônio (CTAB) têm mostrado maior intensidade de corrente, curvas melhores definidas e minimização dos efeitos de envenenamento da superfície do eletrodo provocado pela adsorção do produto oxidado. Usando-se as melhores condições otimizadas para a determinação de BPA: eletrólito suporte tampão BR pH 8, relação [CTAB]/[BPA] = 2:1 (mol L-1), com os parâmetro de VOQ: f= 60 Hz, Es= 6 mV e Esw= 50 mV e para NP : eletrólito suporte tampão BR pH 11, relação [CTAB]/[NP] = 1:2 (mol L-1), com os parâmetro de VOQ: f= 80 Hz, Es= 6 mV e Esw= 50 mV, construiu-se as curvas analíticas para BPA no intervalo de 1x10-6 a 1x10-5 mol L-1, obtendo-se os limites de detecção e quantificação 7,1x10-7 e 2,4x10-7 mol L-1, respectivamente, em ECV e no intervalo de 3x10-7 a 5x10-6 mol L-1, com LD= 1,1x10-7 mol L-1 e LQ= 3,7x10-7 mol L-1 em ECI. Para NP a curva construida utilizando-se ECV apresentou uma relação linear entre 1x10-9 e 1x10-7 mol L-1, LD= 9,0x10-10 mol L-1 e LQ=2,9x10-9 mol L-1 e em ECI uma relação linear entre 1x10-9 e 4x10-7 mol L-1, LD= 1,0x10-9 mol L-1 e LQ= 3,3x10-9 mol L-1. O método proposto foi aplicado na determinação desses em águas... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This paper proposed an electrochemical method for determination of endocrine disruptors bisphenol A and nonylphenol in micellar media using glassy carbon (GCE) and screen printed electrodes (SPE). This endocrine disruptors can promote changes in the endocrine system and hormone levels in humans, and serious adverse effects on aquatic organisms, even at low concentrations. The oxidation of phenolic group of this compounds BPA and NP occurs in potential at 0.42 and 0.56 V, respectively in ECV and at 0.29 and 0.25 V in SP. The hydrophobic film of CTAB positively charged on the electrode surface promotes both preconcentration of NP and acts as antifouling agent facilitating the removal of its oxidized product that usually passivates the electrode surface. Using the best experimental conditions for BPA: B-R buffer pH8, ratio of [CTAB]/[BPA] = 2:1 (mol L-1), parameters SWV: f= 60 Hz, Es= 6 mV and Esw= 50 mV an for NP: B-R buffer pH 11, ratio of [CTAB]/[NP] = 1:2 (mol L-1), parameters SWV: f= 80 Hz, Es= 6 mV e Esw= 50 mV, the linear calibration graphs were constructed for BPA from 1.0x10-6 to 1.0x10-5 mol L-1 with detection limit of 7.1x10-7 mol L-1 and quantification of 2,4 x10-7 mol L-1 in GCE and from 3.0x10-7 to 5.0x10-6 mol L-1, with LOD= 1.1x10-7 mol L-1 and LOQ= 3.7 x10-7 mol L-1 in SPE. For NP the linear calibration graphs were constructed from 1.0x10-9 to 1.0x10-7 mol L-1, LOD= 9.0x10-10 mol L-1 and LOQ=2.9x10-9 mol L-1 in GCE and from 1.0x10-9 to 4.0x10-7 mol L-1, LOD= 1.0x10-9 mol L-1 and LOQ= 3.3x10-9 mol L-1 in SPE. The electroanalytical method developed was applied for analysis of these compounds in river water and sewage without prior treatment and the results were very satisfactory.A chromatographic method HPLC/DAD was also developed for the determination of BPA and NP. The best conditions were established as mobile-phase acetonitrile/water and flow rate 0.8 mL min-1... (Complete abstract click electronic access below) / Mestre

Resumo: Os estudos realizados do comportamento do eletrodo de vidro combinado em etanol anidro e misturas etanol-água mostraram que o tempo para realizar as medidas dos valores de pH foi 60 segundos, uma vez que a partir desse tempo nota-se uma tendência à estabilidade dos valores das medidas do pH. Foi também verificado que as medidas de pH em meio básico se diferenciam do meio ácido, sendo que a composição etanol-água tem influência significativa sobre os valores medidos e que a adição de eletrólito contribui para medidas de pH com desvios padrões menores. Os estudos da determinação dos fatores de correção para eletrodo de vidro mostram que os resultados obtidos estão próximos aos previstos. Por outro lado, na determinação desses fatores na região de pH compreendida entre 6 e 9, os resultados obtidos mostram que não é possivel a sua aplicação em amostras reais de etanol combustível. Para aplicação em amostras reais de etanol combustível, propõe-se um método alternativo utilizando curvas de correção que apresentaram relações lineares com coeficientes de correlação de 0,99 para misturas contendo 0,3, 5 e 10% m/m de água em etanol, proporções as quais se aproximam do etanol combustível anidro e hidratado. / Abstract: Studies of the behavior of a combined glass electrode in anhydrous ethanol and ethanol-water mixtures showed that 60 s was a enough time to perform the pH measurements, since for times equal and greater than 60 s the pH values tend to be stable. For all ethanol-water mixtures the behavior of pH measurements in alkaline medium was very different from that observed in the acidic one, and the ethanol-water composition had a significant influence on the pH values. The addition of electrolyte to the water-ethanol mixture contributed to decrease standard deviations of the pH values. Studies for determining the correction factors for the glass electrode showed values near the expected ones. Furthermore, the determination of these factors in the pH 6 to 9 region showed that they are not applied for real samples of ethanol fuel. For application in real samples of ethanol fuel an alternative method of correction was proposed using linear curves which showed correlation coefficients around 0.99 for mixtures containing 0.3, 5 and 10% m/m of water in ethanol. These mixtures are close to the anhydrous and hydrated ethanol fuel composition. / Orientador: Nelson Ramos Stradiotto / Coorientador: Paulo Paschoal Borges / Banca: Assis Vicente Benedetti / Banca: Marcelo Firmino de Oliveira / Mestre

Resumo: Neste trabalho foram desenvolvidos métodos analíticos com detecção espectrofotométrica na região visível para determinação de tetraciclina, doxiciclina, azitromicina, norfloxacina e ciprofloxacina em formulações farmacêuticas. As condições experimentais envolvidas em cada método foram cuidadosamente estudadas e otimizadas utilizando métodos multivariados (planejamentos fatoriais e metodologia de superfície de resposta), assim como método univariado. Para a determinação de tetraciclina e doxiciclina foi proposto método baseado na reação entre cloramina-T e os fármacos em meio alcalino de Na2CO3, produzindo compostos com coloração vermelha e absorbâncias em 535 e 525 nm para os produtos das reações da tetraciclina e doxiciclina, respectivamente. Posteriormente, este método foi automatizado utilizando sistema de análise por injeção em fluxo. Para a determinação de azitromicina foi proposto um método automatizado utilizando análise por injeção em fluxo com zonas coalescentes. O método é baseado na reação entre o fármaco e p-cloranil em meio metanólico na presença de H2O2 com formação de um complexo de transferência de carga de coloração roxa, o qual apresenta absorção em 540 nm. Para a determinação de norfloxacina e ciprofloxacina foi empregado um método utilizando análise por injeção sequencial. O referido método baseia-se na reação entre os fármacos e p-dimetilaminocinamaldeído em meio ácido (HCl) e micelar (sulfato de dodecil sódio). O produto formado apresentou coloração alaranjada com absorbância máxima em 495 nm. As substâncias comumente utilizadas como excipientes nas respectivas formulações farmacêuticas não interferiram nos métodos propostos. Todos os métodos propostos neste trabalho foram aplicados com sucesso na determinação destes fármacos em formulações farmacêuticas. Os resultados obtidos por estes... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this work were developed analytical methods with spectrophotometric detection in the visible region for tetracycline, doxycycline, azithromycin, norfloxacin and ciprofloxacin determination in pharmaceutical formulations. The experimental conditions involved in each method were carefully studied and optimized utilizing multivariate methods (design factorials and response surface methodology), as well as univariated method. For the tetracycline and doxycycline determination was proposed method based in the reaction between chloramine-T and the drugs in alkaline medium of Na2CO3 producing red color compounds with absorbance in 535 and 525 nm for the products of the reactions of tetracycline and doxycycline, respectively. Subsequently, this method was automated utilizing system of flow injection analysis. For the determination of azithromycin was proposed a method utilizing flow injection analysis with coalescent zones. The method is based in the reaction between the drug and p-chloranil in methanol medium in the presence of H2O2 with formation of a purple color charge-transfer complex, which presents absorption in 540 nm. For norfloxacin and ciprofloxacin determination was employed a method utilizing sequential injection analysis. The referred method based itself in the reaction between the drugs and p-dimethylaminocinnamaldehyde in acid (HCl) and micelar (sulphate of dodecil sodium) medium. The formed product presented orange color with maximum absorbance in 495 nm. The common excipients used as additives in the respective pharmaceutical formulations do not interfere in the proposed methods. All the proposed methods in this work were applied successfully to the determination of these drugs in pharmaceutical formulations. The analytical results obtained by applying the proposed methods compared very favorably with those obtained by the official or comparative methods, at 95% confidence level. / Orientador: Leonardo Pezza / Coorientador: Helena Redigolo Pezza / Banca: Clóvis Augusto Ribeiro / Banca: Matthieu Tubino / Banca: Ivo Milton Raimundo Junior / Banca: Carlos Roberto Bellato / Doutor

Orientador: André Henrique Rosa / Banca: Leonardo Fernades Fraceto / Banca: Edenir Rodrigues Pereira Filho / Banca: Marco Aurélio Zezzi Arruda / Banca: Cléssia Cristina Nascentes / Resumo: O biodiesel, também conhecido como diesel vegetal, é um combustível obtido de fonte renovável, considerado ambientalmente atraente e uma ótima alternativa em substituição ao diesel. Porém, contaminantes inorgânicos podem estar presentes em amostras de biodiesel devido à absorção de metais pela própria planta (matériaprima) do solo, e/ou podem ser incorporados durante o processo de produção/ transporte/estocagem. Desta forma, por meio de um controle analítico dos teores de contaminantes inorgânicos é possível gerenciar a qualidade dos combustíveis e avaliar o impacto ambiental destes. Este trabalho propõe o desenvolvimento de métodos analíticos para a determinação de Cu, Cd, Ni e Pb em amostras de biodiesel por espectrometria de absorção atômica em forno de grafite (GFAAS). Os procedimentos univariados e multivariados foram aplicados na avaliação das temperaturas ótimas de pirólise e atomização. O planejamento experimental foi usado também como ferramenta para a investigação de dois modificadores químicos (Pd + Mg e W) e dois diferentes procedimentos de preparo das amostras (amostras na forma de microemulsão e amostras digeridas por via úmida em sistema de microondas com radiação focalizada). Considerando que ao usar planejamento fatorial há um melhor entendimento das variáveis e das relações entre elas, os resultados usando o planejamento fatorial foram escolhidos para a determinação dos analitos nas amostras reais de biodiesel. Optou-se por trabalhar com W, pois os as determinações são mais rápidas, há poucos problemas relacionados ao background, durante a deposição do modificador na superfície do atomizador, as impurezas voláteis do modificador podem ser eliminadas, melhorando os limites de detecção, além do W ser um modificador permanente, o que pode aumentar o tempo de vida útil do atomizador. Os procedimentos... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Biodiesel, also known as vegetable diesel, is a fuel obtained from a renewable source and an excellent alternative to diesel. However, biodiesel samples may contain inorganic contaminants due to the plant's (raw material) absorption of metals in the soil, and/or be incorporated during production, transportation or storage. Therefore, based on the analytical control of the inorganic contaminant content, it is possible to manage the quality of fuels and evaluate their environmental impact. This work proposes the development of analytical methods for the determination of Cu, Cd, Ni and Pb in biodiesel samples using graphite furnace atomic absorption spectrometry (GFAAS). Univariate and multivariate procedures were applied in the evaluation of the optimal temperatures of pyrolysis and atomization. Experimental design was also used as a tool in the investigation of two chemical modifiers (Pd + Mg and W) and two different sample preparation procedures (microemulsions and wet digestion in a focused microwave system). Using a factorial design there is better understanding of variables and relations between them and the results using the factorial design were chosen for the determination of analytes in real samples of biodiesel. Therefore, it was decided to work with W, since the heating programs are faster, there are few background problems, the volatile impurities of the modifier can be eliminated during its deposition on the surface of the atomizer, improving the detection limits, and W is a permanent modifier, which may help prolong the service life of the atomizer. The developed analyticals procedures may also be considered satisfactory as were good values of recovery and low standard deviations for all analytes measured in samples of biodiesel. This work contributes to establish or to propose a suitable normalization, since there is not yet in the literature and / or legislation... (Complete abstract click electronic access below) / Doutor

Orientador: Marisa Spirandeli Crespi / Banca: Mercedes de Moraes / Banca: Pedro Paulo Corbi / Resumo: A produção e o processamento da cana-de-açúcar são partes integrantes da economia mundial, atendendo as necessidades e metas ligadas diretamente à produção do açúcar, e a produção do álcool combustível. A busca por melhorias tecnológicas para o processamento da cana objetivando a obtenção de um açúcar com alto padrão e um combustível eficiente, fez com que o nível de descartes (subprodutos ou resíduos) dessa agroindústria aumentasse significativamente nos últimos anos. Por estes resíduos apresentarem grande importância na indústria do setor e, principalmente, por suas diversas aplicabilidades, é necessário antes conhecer a composição real destes cinco subprodutos (bagaço, bagaço hidrolisado, torta de filtro, vinhoto e cinzas do bagaço). Dessa forma, o presente estudo apresenta a caracterização e estudo térmico destes resíduos os quais foram coletados na Usina Santa Luiza, localizado na cidade de motuca, SP. Os resultados obtidos através da caracterização espectroscópica mostrou que boa parte da composição destes resíduos é de matéria orgânica (exceto as cinzas). Também foi cosntatado a presença de metais como cálcio, potássio, ferro e silicio na composição destes resíduos, todos em concentrações que não excedem os valores de outros ambientes coletados. Os resultados obtidos das análises termoanalíticas (TG, DTA e DSC) evidenciaram que as amostras de torta de filtro, vinhaça e cinzas do bagaço apresentaram-se menos estáveis termicamente quando comparadas ao bagaço comum (que não passou por tratamento algum. O método isoconversional de Flynn-Wall permitiu a determinação dos parâmetros cinéticos (E e A) para reações de desidratação e de decomposição da matéria orgânica em intervalos fixos de temperatura. A relação linear entre lnA versus E foi verificada para as duas decomposições constatando o chamado efeito de compensação cinética (KCE) / Abstract: The production and processing of the sugar cane are an integral part of the world economy, attending the needs and goals connected directly to the production of sugar, and of the flammable alcohol. The search for technological improvements in the processing of the sugar cane with the purpose of obtaining a high standard sugar and an efficient fuel caused the level of discarded byproducts or residues of that agro-industry to increase significantly in the last years. Since these residues are of big importance in the industry of the sector and, mainly, by its diverse usages, it is necessary to know beforehand the real composition of these five byproducts (pulp, hydrolyzed pulp, filter cake, vinasse and the ash of the pulp). Therefore, the actual study presents the characterization and thermal study of these residues which were collected at Usina Santa Luiza, located in the city of Motuca, SP. The results obtained by spectroscopic characterization showed that much of the composition of this waste is organic matter (except for the ash). It was also noted the presence of metals such as calcium, potassium, iron and silicon in the composition of this waste, all of which at concentrations that do not exceed those collected from other environments. The results of the thermal analysis (TG, DTA and DSC) showed that samples of the filter cake, vinasse and pulp ash were less thermally stable compared to the common residue (which has not undergone any treatment. The isoconversional Flynn-Wall method enabled the determination of kinetic parameters (E and A) for reactions of dehydration and decomposition of organic matter at fixed temperatures. The linear relationship between lnA versus E was observed for the two decompositions noting the so-called kinetic compensation effect (KCE) / Mestre