A monitorização terapêutica permite a individualização do regime de dosagem, assegurando a eficácia clínica e minimizando os efeitos adversos dos fármacos prescritos. Atualmente, as estatinas têm sido monitoradas, pois, embora eficazes e muito utilizadas, apresentam alguns efeitos adversos não desejáveis. Neste trabalho, as técnicas SPME e cromatografia gasosa acoplada à espectrometria de massas (GC-MS) foram avaliadas para a análise de estatinas (fluvastatina, simvastatina e atorvastatina) em plasma humano para fins de monitorização terapêutica. As condições de extração e derivatização foram otimizadas empregando planejamento experimental e avaliando a influência dos principais parâmetros envolvidos. Para otimização das condições de extração avaliou-se parâmetros como tempo e temperatura de extração, pH, volume de solução tampão e força iônica; e para otimização das condições de derivatização avaliou-se parâmetros como volume de reagente derivatizante, volume de agente pareador iônico e pH. A extração foi realizada utilizando fibras de PDMS-DVB, e a dessorção feita termicamente no injetor do cromatógrafo a gás. O método desenvolvido foi validado segundo normas da ANVISA, apresentando linearidade na faixa de 20 a 500 ng mL-1, precisão com coeficientes de variação menor que 14% e recuperação relativa de 20 a 40%. Concluída a validação analítica, a metodologia proposta foi aplicada em amostras reais de plasma de pacientes em terapia com simvastatina concedidas pelo Laboratório Médico Dr. Maricondi e pela Casa de Saúde de São Carlos. / Therapeutic drug monitoring allows individualization of dosage regimen, ensuring the clinical efficacy and minimizing the adverse effects of prescribed drugs. Currently, statins have been monitored; despite they are effective, some statins have undesirable adverse effects. In this work, SPME technique and gas chromatography / mass spectrometry (GC-MS) were evaluated for analysis of statins (fluvastatin, simvastatin and atorvastatin) in human plasma for therapeutic drug monitoring. The extraction and derivatization conditions were optimized using experimental design and evaluating the influence of the main parameters involved in the SPME procedure. To optimize the extraction conditions were evaluated parameters such as time and extraction temperature, pH, volume of buffer and ionic strength, and to optimize the derivatization conditions were evaluated parameters as derivatization reagent volume, ionic agent pareador volume and pH. The extraction was performed using PDMS-DVB fibers, and thermal desorption performed in the injector of the gas chromatograph. The method was validated according to ANVISA, showing linearity in the range 20 to 500 ng mL-1, the precision with coefficients of variation less than 14% and relative recovery from 20 to 40%. The proposed methodology was applied to real samples of plasma from patients on therapy with simvastatin provided by the Laboratório Médico Dr. Maricondi and Casa de Saúde of São Carlos.

La Directive Cadre sur l'Eau (DCE) (2000/60) a mis en place une liste de 33 substances prioritaires, avec des normes qualité de l'environnement (NQE) pour chaque substance, et leur concentration dans les milieux aquatiques qui ne doivent pas dépasser c es NQE. De plus, elle exige des performances analytiques spécifiques pour ces méthodes: la limite de quantification doit être au moins aussi basse que 30% des NQE et l'incertitude de la méthode au niveau de la NQE doit être inférieure à 50%, pour k = 2. Par conséquent, le défi analytique actuel est de mesurer de faibles concentrations de ces polluants dans les matrices parfois difficiles. Ceci peut être réalisé en améliorant la technique d'extraction utilisée pour obtenir un extrait de l'échantillon plus concentré et plus propre. Dans ce contexte, les trois méthodes d'analyse ont été mises au point pour déterminer les composés musqués, alkylphénoliques et organométalliques dans les matrices environnementales. Ces techniques d'extraction et de pré-concentration innovantes ont ensuite été appliquées pour l’évaluation de la présence de ces composés dans les stations d'épuration locales et dans les cours d'eau récepteurs. Enfin, les niveaux de concentrations de fond au niveau national ont été mises à jour pour les composés organométalliques. / The ambitious Water Framework Directive (WFD) (2000/60) set up a list of 33 priority substances, with Environmental Quality Standards (EQS) for each substance, and their concentration in aquatic environments should not go beyond the EQS. Additionally, it requires specific analytical method performances: the limit of quantification must be at least as low as 30 % of the EQS and the uncertainty of the method at the EQS level must be inferior to 50 %, for k=2. Therefore, the current analytical challenge is to measure low concentrations of these pollutants in sometimes difficult matrices. This can be achieved by improving the extraction technique used to obtain a more concentrated and cleaner sample extract. In this context, 3 analytical methods were developed to determine musk, alkylphenols and organometallic compounds in environmental matrices. Recent extraction and pre-concentration techniques were applied and later the occurrence of these compounds in the local WWTPs and in the receiving water bodies where they are discharged was evaluated. Additionally, updated French background concentrations were established for organometallic compounds.

Esta tese tem como objetivo a derivatização da celulose sob condições homogêneas de reação, através de um método simples, reprodutível e eficiente. As três etapas de derivatização da celulose (ativação, dissolução, e reação) foram estudadas com ênfase na relação entre a estrutura do biopolímero, as condições da reação e as propriedades dos derivados obtidos. Foi realizado estudo do intumescimento de celuloses (microcristalina, algodão, eucalipto, algodão mercerizado e eucalipto mercerizado) em solventes próticos e apróticos. O intumescimento foi correlacionado com as propriedades dos solventes. Nos próticos, as celuloses nativas e mercerizadas foram sensíveis aos mesmos quatro descritores (acidez, basicidade, dipolaridade/polarizabilidade e volume molar), porém, a contribuição relativa dessas propriedades foi diferente, sendo que no caso da celulose MC e das nativas a dipolaridade/polarizabilidade foi mais significativo e para as celuloses mercerizadas o volume molar foi o descritor mais importante. Para o intumescimento em solventes apróticos, para as celuloses mercerizadas, boas correlações foram obtidas empregando apenas um descritor (dipolaridade/polarizabilidade). No intumescimento intracristalino, investigamos as mudanças nas propriedades físico-químicas após a mercerização. Este tratamento resultou em: ocorreu aumento no teor de α-celulose; diminuição da cristalinidade; redução da espessura da fibra; remoção de fragmentos da superfície; aumento na área superficial. Salientamos que não ocorre uma diminuição significativa no grau de polimerização das celuloses. Empregamos uma nova classe de solvente (líquidos iônicos) para a dissolução e subsequente funcionalização da celulose. Tanto na dissolução por aquecimento térmico ou por micro-ondas a integridade física da celulose foi mantida. Alem disto, observamos que a dissolução facilita a acessibilidade/reatividade da celulose, pois ocorre a diminuição do índice de cristalinidade e o aumento da área superficial. O uso de aquecimento por micro-ondas mostrou-se mais rápido e eficiente do que aquecimento térmico, sendo que tempo necessário para a dissolução e acilação da celulose foi de 25 a 30% menor daquele com aquecimento térmico. O líquido iônico (AlBuImCl) mostrouse um excelente solvente em termos de controle do GS e reprodutibilidade do mesmo. Realizou-se um estudo da dependência das propriedades dos acetatos de celulose e seus filmes com o grau de substituição do biopolímero. Foram empregadas sondas solvatocrômicas e medidas térmicas para investigar as propriedades de filmes de acetatos de celulose. Os resultados obtidos mostraram que a dependência de tais propriedades sobre o grau de substituição dos acetatos de celulose pode ser descrita por equações simples. Por fim, desenvolveu-se um método simples, rápido, e preciso para a determinação do GS de ésteres de celulose (acetato, butirato e hexanoato), através do uso de sondas solvatocrômicas / The objective of this thesis is to study some aspects of the derivatization of cellulose under homogeneous reaction conditions. The three steps of this reaction scheme (activation, dissolution and derivatization) were studied, with emphasis on the relationship between the biopolymer structure, the conditions of the reaction and the properties of the products. Swelling of different celluloses (microcrystalline (MC), cotton linter, eucalyptus, cotton linter mercerized, eucalyptus mercerized) by protic and aprotic solvents was determined. The results were correlated with a series of solvent descriptors. For protics solvents, although native and mercerized celluloses are sensitive to the same set of four solvent properties (acidity, basicity, dipolarity/polarizability, and molar volume), the relative contributions are different; π* is most important for MC and native celluloses, VS is most important for mercerized celluloses. Because of absence of hydrogen-bon donation by aprotics solvents, a smaller number of solvent descriptors is required in order to describe cellulose swelling. For example, the swelling of mercerized cellulose can be reasonably described by a single descriptor (dipolarity/polarizability). The effect of mercerization on cellulose properties was investigated; it leads to: increase of α-cellulose content; decrease of Ic; decrease of fiber cross section, smoothing of its surface, and increase of its surface area. The ionic liquid 1-allyl-3-(1-butyl)imidazolium chloride showed to be a convenient reaction medium for the dissolution and derivatization of cellulose, with reproducible easily controlled degree of substitution, DS. The physical integrity of the cellulose is maintained during dissolution by using either \"conventional\" or convection-, or microwave heating. Compared with the former, MW irradiation has resulted in considerable decrease in dissolution- and reaction times. The value DS was found to be DSethanoate > DSpropanoate > DSbutanoate. The values of DSpentanoate and DShexanoate were found to be slightly higher than DSethanoate. The dependence of the properties of cellulose acetates and their films on the degree of biopolymer substitution was investigated. Solvatochromic probes and thermal analysis have been employed. The results showed that the dependence of the properties (solvatochromic parameters and thermal properties) of CAs on their DS can be described by simple equations; a consequence of the substitution of the OH by the ester group. Finally, an expedient, accurate method for the determination of the degree of substitution of cellulose carboxylic esters (ethanoate, butanoate and hexanoate) was developed, using Uv-vis spectroscopy (dye perichromism)

Esta dissertação avaliou a reação de amidação de poli(metacrilato de metila) (PMMA) comercial de massa molecular de 90000 g/mol (determinado por viscosimetria) com alilamina. A reação foi estudada a temperatura ambiente e sob refluxo. A reação apresentou baixos índices de conversão, 0,5 %, tanto após 24 dias, a temperatura ambiente, quanto sob refluxo por 2 horas. Experimentos executados sob refluxo por períodos maiores apresentaram diminuição no índice de conversão. Todos os experimentos foram acompanhados pela análise elementar e FT-IR e RMN-1H. O material derivatizado foi epoxidado pelo tratamento com ácido m-cloro-perbenzóico (AMCPB) seguido de tratamento com ácido periódico gerado in situ (NaIO4/HCl). Todos os produtos preparados foram submetidos à análise térmica apresentando, em sua maioria, um aumento na Tg relativa ao PMMA / This dissertation valued the reaction of amidation of the commercial poly(methyl methacrylate)(PMMA) of molecular mass of 90000 g/mol (determinated by viscosimetric method) with allylamine. The reaction was studied the room temperature and reflux. The reaction there presented low rates of conversion, 0,5 %, so much after 24 days the room temperature all that under reflux for 2 hours. Experiments executed under reflux for bigger periods presented reduction in the conversion rate. All the experiments were accompanied by the elementary analysis and FT-IR and NMR-1H. The material derivatizated was epoxidated for the treatment with m-chloro-perbenzoic acid following of treatment with periodic acid produced in situ (NaIO4/HCl). All the prepared products were subjected the thermal analysis presenting, in his majority, an increase in the relative Tg to the PMMA

Understanding the composition of atmospheric organic particulate matter (OPM) is essential for predicting its effects on climate, air quality, and health. However, the polar oxygenated fraction (PO-OPM), which includes a significant mass contribution from carboxylic acids, is difficult to speciate and quantitatively determine by current analytical methods such as gas chromatography-mass spectrometry (GC-MS). The method of chemical derivatization and two-dimensional GC with time of flight MS (GC×GC/TOF-MS) was examined in this study for its efficacy in: 1) quantifying a high percentage of the total organic carbon (TOC) mass of a sample containing PO-OPM; 2) quantitatively determining PO-OPM components including carboxylic acids at atmospherically relevant concentrations; and 3) tentatively identifying PO-OPM components. Two derivatization reagent systems were used in this study: BF₃/butanol for the butylation of carboxylic acids, aldehydes, and acidic ketones, and BSTFA for the trimethylsilylation (TMS) of carboxylic acids and alcohols. Three α-pinene ozonolysis OPM filter samples and a set of background filter samples were collected by collaborators in a University of California, Riverside environmental chamber. Derivatization/GC×GC TOF-MS was used to tentatively identify some previously unidentified α-pinene ozonolysis products, and also to show the characteristics of all oxidation products determined. Derivatization efficiencies as measured were 40-70% for most butyl derivatives, and 50-58% for most trimethylsilyl derivatives. A thermal optical method was used to measure the TOC on each filter, and a value of the quantifiable TOC mass using a gas chromatograph was calculated for each sample using GC×GC separation and the mass-sensitive response of a flame ionization detector (FID). The TOC quantified using TMS and GC×GC-FID (TMS/TOCGC×GC FID) accounted for 15-23% of the TOC measured by the thermal-optical method. Using TMS and GC×GC/TOF-MS, 8.85% of the thermal optical TOC was measured and 48.2% of the TMS/TOCGC×GC-FID was semi-quantified using a surrogate standard. The carboxylic acids tentatively identified using TMS and GC×GC/TOF-MS accounted for 8.28% of the TOC measured by thermal optical means. GC×GC TOF-MS chromatograms of derivatized analytes showed reduced peak tailing due in part to the lesser interactions of the derivatized analytes with the stationary phase of the chromatography column as compared to the chromatograms of underivatized samples. The improved peak shape made possible the greater separation, quantification, and identification of high polarity analytes. Limits of detection using derivatization and GC×GC/TOF-MS were μL injected for a series of C2-C6 di-acids, cis-pinonic acid, and dodecanoic acid using both butylation and TMS. Derivatization with GC×GC/TOF-MS was therefore effective for determining polar oxygenated compounds at low concentrations, for determining specific oxidation products not previously identified in OPM, and also for characterizing the probable functional groups and structures of α-pinene ozonolysis products.

Aldehydes in lung cancer cell culture have been investigated using gas chromatography/mass spectrometry and solid-phase microextraction with on-fiber derivatization. In this study, the poly(dimethylsiloxane/divinylbenzene (PDMS/DVB) fiber was used and o-2,3,4,5,6-(pentafluorobenzyl) hydroxylamine hydrochloride (PFBHA) was first loaded on the fiber. Aldehydes in the headspace of lung cancer cell culture were extracted by solid-phase microextraction (SPME) fiber and subsequently derivatized by PFBHA on the fiber. Finally, the aldehyde oximes formed on the fiber were analyzed by gas chromatography/mass spectrometry (GC/MS). Using this method, acetaldehyde decrease was found in both non-small lung cancer cell cultures studied compared to the medium control study. The results of spiking the cell culture with acetaldehyde solution showed that 5 million SK-MES-1 cell lines could consume up to 4.5 uM acetaldehyde in 15-ml medium, and 5 million NCI-H522 cell lines could consume 5.9 uM acetaldehyde in 15-ml medium. The decrease of acetaldehyde may contribute to the metabolism of lung cancer cells. It was proved that GC/MS and SPME with on-fiber derivatization is a simple, rapid, sensitive and solvent-free method for the detection of aldehydes in lung cancer cell culture.

Aldehydes in lung cancer cell culture have been investigated using gas chromatography/mass spectrometry and solid-phase microextraction with on-fiber derivatization. In this study, the poly(dimethylsiloxane/divinylbenzene (PDMS/DVB) fiber was used and o-2,3,4,5,6-(pentafluorobenzyl) hydroxylamine hydrochloride (PFBHA) was first loaded on the fiber. Aldehydes in the headspace of lung cancer cell culture were extracted by solid-phase microextraction (SPME) fiber and subsequently derivatized by PFBHA on the fiber. Finally, the aldehyde oximes formed on the fiber were analyzed by gas chromatography/mass spectrometry (GC/MS). Using this method, acetaldehyde decrease was found in both non-small lung cancer cell cultures studied compared to the medium control study. The results of spiking the cell culture with acetaldehyde solution showed that 5 million SK-MES-1 cell lines could consume up to 4.5 uM acetaldehyde in 15-ml medium, and 5 million NCI-H522 cell lines could consume 5.9 uM acetaldehyde in 15-ml medium. The decrease of acetaldehyde may contribute to the metabolism of lung cancer cells. It was proved that GC/MS and SPME with on-fiber derivatization is a simple, rapid, sensitive and solvent-free method for the detection of aldehydes in lung cancer cell culture.

Neste trabalho estudou-se o desenvolvimento de metodologia analitica para a determinação e quantificação de sete anti-inflamatórios não esteroides, amplamente consumidos para tratamento humano, além da cafeína, determinada como marcador antropogênico, em amostras aquosas ambientais. Os analitos estudados foram acetaminofeno (AC), ácido salicílico (AS), cafeína (CA), cetoprofeno (CE), diclofenaco (DC), dipirona (DP), ibuprofeno (IB) e naproxeno (NA) . Como padrão internos, foi utilizado o lindano (LI). A determinação destes analitos foi realizada utilizando-se cromatografia a gás acoplada à espectrometria de massas (GC-MS) utilizando MSTFA/Imidazol como derivatizante. As condições para a reação de derivatização foram otimizadas utilizando o planejamento Doehlert. O procedimento de pré-concentração utilizado foi a extração em fase sólida (SPE), tendo como sorvente um sistema de fase polimérica reversa. O procedimento de SPE foi baseado em trabalhos publicados na literatura, com metanol e água (ajustada a pH 3,0) para o condicionamento e eluição com acetonitrila. Os parâmetros de desempenho do método, como recuperação, linearidade, limite de detecção, limite de quantificação, repetitividade e reprodutibilidade foram avaliados de acordo com as normas estabelecidas pela ANVISA e INMETRO. Os limites de detecção ficaram entre 1,09 e 1079,14 ng L-1 e os de quantificaçõ entre 3,63 e 3597,12 ng L-1. Após as definições em relação ao método, amostras de água do Arroio Dilúvio (em Porto Alegre – RS) e de uma Estação Piloto de tratamento de efluente pertencente ao Instituto de Pesquisas Hidráulicas (IPH/UFRGS) , foram analisadas para avaliar a presença destes analitos. As amostras da ETE-piloto do IPH, foram coletadas nos meses de janeiro e fevereiro e as amostras do Arroio Dilúvio também foram coletadas no mesmo período. Considerando as amostras reais analisadas em algumas foram detectados e em outras quantificados os antiinflamatórios estudados. Nas amostras que estes compostos foram quantificados, a faixa de concentração variou entre 0,09 e 23,16 μg L-1. / In this work the development of an analytic methodology was studied to determine and quantify seven non-steroidal anti-inflammatory drugs, widely used in human treatment, and caffeine considered an anthropogenic marker. The compounds studied were acetaminophen (AC), salicylic acid (AS), caffeine (CA), ketoprofen (CE), diclofenac (DC), dipyrone (DP), ibuprofen (IB), naproxen (NA) and lindane (LI) as internal standard. The determination of these compounds was performed using gas chromatography coupled to mass spectrometry (GC-MS) with derivatization of the target analytes using MSTFA/Imidazole. The derivatization conditions were optimized with Doehlert design. Solid phase extraction (SPE) with a polymeric reversed solid phase was used as a pre-concentration system. The SPE procedure conditions were based previously established data in the literature, using methanol and water (adjusted to pH 3.0) for the conditioning step and acetonitrile for the elution step The performance parameters, such recovery, linearity, detection limit, quantification limit, repeatability and reproducibility were evaluated according to ANVISA and INMETRO determinations. The detection limits was in the range of 1,09 and 1079,14 ng L -1 and the quantification limits 3,63 and 3597,12 gn L-1. After method establishment, samples from a piloto sewage treatment plant and river water, both in Porto Alegre-RS, were analysed. The samples were collected in January and February 2012, both in the pilot plant and in the river water. In some real samples the antiinflammatories were detected and in others was possible quantify. In the samples were the analytes were quantified, the concentration range was 0,09 to 23,16 μg L-1.

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No. of bitstreams: 1 DISS_2015_Marília Souza do Nascimento.pdf: 1042834 bytes, checksum: db99d2cde69a10a3a45dc5aece84fc7f (MD5) Previous issue date: 2015-02-28 / Dentro da classe de contaminantes emergentes estão os estrógenos (hormônios sexuais femininos), que são compostos orgânicos hidrofóbicos e de baixa volatilidade, encontrados no meio aquático nas formas naturais (17β-estradiol (E2), estriol (E3), estrona (E1)) e/ou sintéticas (17α-etinilestradiol (EE2)) utilizados na composição de medicamentos contraceptivos. Por ser um campo recente de pesquisa, há poucos trabalhos nacionais publicados abordando o monitoramento desses contaminantes em águas naturais, não havendo ainda uma legislação específica que regulamente a emissão de hormônios no ambiente ou que estabeleça limite máximo para tais compostos. As fontes de contaminação incluem a urina excretada por seres humanos e mamíferos em águas residuais, podendo ser encontrados em água superficial, esgoto doméstico, efluentes, carne, leite e seus derivados. Devido à complexidade das matrizes ambientais (fisiologicamente ativas) e pelas concentrações muito baixas de estrógenos encontradas, para o monitoramento ambiental, é necessário utilizar metodologias analíticas sensíveis e seletivas e que, em geral, compreendem procedimentos longos e trabalhosos. Os métodos reportados na literatura consistem na extração dos analitos da matriz, seguida ou não de derivatização, com identificação e quantificação por cromatografia. Quanto aos métodos de extração, a extração em fase sólida com diferentes adsorventes é a mais utilizada devido ao elevado fator de concentração que esta técnica permite. Entretanto, outros procedimentos de extração têm sido reportados. As técnicas como micro-extração em fase sólida ou líquida e extração em barra de agitação ou ainda uso de nanopartículas como fase sólida foram relatadas apresentando como vantagem a facilidade de uso e baixa manipulação da amostra bem como a menor produção de resíduos. A derivatização dos analitos é necessária quando a cromatografia a gás é utilizada devido à baixa volatilidade e aos grupos hidroxila que causam encaudamento dos picos. A sililação com diferentes agentes derivatizantes é a reação mais utilizada, mas diversos autores reportam problemas tais como reação incompleta e formação de sub-produtos durante o processo de sililação que devem ser cuidadosamente controlados. Com relação às técnicas cromatográficas tanto a cromatografia a gás como a líquido acoplada a espectrometria de massas são as mais utilizadas. A cromatografia a gás, apesar de requerer a derivatização, tem a vantagem de ter maior capacidade de resolução e elevada sensibilidade. Por outro lado, o surgimento de equipamentos modernos de cromatografia líquida de ultra-performance acoplada a espectrometria em tandem permitiu atingir baixos limites de detecção também com essa técnica. Entretanto o elevado custo destes equipamentos ainda é um fator limitante para sua utilização. Destaca-se assim a necessidade de desenvolvimento de técnicas sensíveis e de baixo custo para permitir o monitoramento contínuo destes hormônios. / Estrogens (female sex hormones) belong to the emerging contaminants group that comprises hydrophobic organic compounds with low volatility which have been found in water in the natural (17β-estradiol (E2), estriol (E3), estrone (E1)) and/or synthetic form (17α-ethynilestradiol (EE2)) used in the formulation of contraceptive medicines. As a recent research field, there are few published national studies concerning the analysis of these contaminants in natural waters and so far, there is no specific legislation governing the issue of hormones in the environment or establishing maximum limits for such compounds. Contamination sources include urine excreted by humans and mammals in wastewater and can be found in surface water, sewage, wastewater, meat, milk and dairy products. Thus, it is important to monitor these agents. Due to the complexity of environmental matrices (physiologically active) and the very low concentrations which occur in the environment, for environmental monitoring, it is necessary to use sensitive and selective analytical methods which, in general, envolve tedious and laborious procedures. Methods reported in the literature consist on the extraction of the analytes from the matrix, followed or not by derivatization, with identification and quantification by chromatography. Regarding extraction procedures, solid phase extraction (SPE) with different adsorbents is the most frequently used method due to the high concentration factor that can be achieved with this procedure. However, other extraction procedures have been reported recently. Techniques such as solid- or liquid-phase micro-extraction, stirring bar sorptive extraction (SBSE) or the use of nanoparticles as solid phase have been reported presenting the advantage of being easy, requiring little sample manipulation as well as producing less waste residues. Analytes derivatization is necessary when gas chromatography is used due to their low volatility and the presence of hydroxyl groups that cause peak tailing. Silylation with different derivatizing agents is the mostly used reaction but several authors reported problems such as incomplete reaction and formation of by-products that need to be carefully controlled. In relation to the chromatographic techniques, gas or liquid chromatography coupled to mass spectrometry is the mostly used one. Gas chromatography, despite needing derivatization of the estrogens, has the advantage of having more resolution and high sensitivity. On the other hand, the modern equipment of ultra-performance liquid chromatography tandem mass spectrometry have allowed the achievement of very low detection limits also with this technique. However, the high cost of this equipment is still a limiting factor for its most widely use. Therefore, it is still necessary to develop low cost sensitive techniques to allow the continuous monitoring of these hormones.

Esta dissertação avaliou a reação de amidação de poli(metacrilato de metila) (PMMA) comercial de massa molecular de 90000 g/mol (determinado por viscosimetria) com alilamina. A reação foi estudada a temperatura ambiente e sob refluxo. A reação apresentou baixos índices de conversão, 0,5 %, tanto após 24 dias, a temperatura ambiente, quanto sob refluxo por 2 horas. Experimentos executados sob refluxo por períodos maiores apresentaram diminuição no índice de conversão. Todos os experimentos foram acompanhados pela análise elementar e FT-IR e RMN-1H. O material derivatizado foi epoxidado pelo tratamento com ácido m-cloro-perbenzóico (AMCPB) seguido de tratamento com ácido periódico gerado in situ (NaIO4/HCl). Todos os produtos preparados foram submetidos à análise térmica apresentando, em sua maioria, um aumento na Tg relativa ao PMMA / This dissertation valued the reaction of amidation of the commercial poly(methyl methacrylate)(PMMA) of molecular mass of 90000 g/mol (determinated by viscosimetric method) with allylamine. The reaction was studied the room temperature and reflux. The reaction there presented low rates of conversion, 0,5 %, so much after 24 days the room temperature all that under reflux for 2 hours. Experiments executed under reflux for bigger periods presented reduction in the conversion rate. All the experiments were accompanied by the elementary analysis and FT-IR and NMR-1H. The material derivatizated was epoxidated for the treatment with m-chloro-perbenzoic acid following of treatment with periodic acid produced in situ (NaIO4/HCl). All the prepared products were subjected the thermal analysis presenting, in his majority, an increase in the relative Tg to the PMMA