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Orientador: Fabio Augusto / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-10T22:09:41Z (GMT). No. of bitstreams: 1 Biajoli_AndreFranciscoPivato_M.pdf: 976777 bytes, checksum: 46d1432f77507bee6dedced57031e3c3 (MD5) Previous issue date: 2008 / Resumo: Este trabalho descreve a obtenção de fibras para microextração em fase sólida a partir do processo sol-gel utilizando-se 3-aminopropiltrimetoxissilano (APTMS) como precursor/modificador orgânico e polidimetilsiloxano hidroxiterminado (PDMS-OH) como modificador orgânico. O material preparado foi caracterizado física e quimicamente através de espectroscopia de absorção no infravermelho e análise termogravimétrica. As fibras recobertas com este material foram avaliadas morfologicamente através de microscopia eletrônica de varredura e caracterizadas analiticamente através do estudo de seus perfis de extração e de dessorção, além de terem sido comparadas com fibras comerciais. Como resultados, verificou-se que os recobrimentos produzidos podem ser utilizados em temperaturas de até 300 °C e que estes apresentam uma morfologia irregular, aspecto favorável para dispositivos de SPME. O perfil de extração mostrou que a fibra possui tempos de equilíbrio rápidos para hidrocarbonetos aromáticos (da ordem de 5 min); o perfil de dessorção mostrou que, após 5 s de injeção, os mesmos analitos são completamente removidos do recobrimento. Comparada com fibras comerciais de poliacrilato (PA - polar) e PDMS (apolar), a fibra sol-gel apresentou melhores propriedades sortivas tanto no tocante a compostos polares (ácidos carboxílicos e álcoois) quanto a compostos de media polaridade (ésteres). A fibra sol-gel foi aplicada com sucesso em determinações quantitativas de clorofenóis em madeiras e águas / Abstract: This work describes the preparation of Solid Phase Microextraction Fibers through the sol-gel process using 3-aminopropyltrimethoxysilane as precursor/organic modifier and polydimethylsiloxane (PDMS) as organic modifier. The chemical and physical properties of the material obtained were studied through infrared absorption spectroscopy and thermogravimetric analysis. The morphology of the fibers obtained were evaluated by scanning electron microscopy; their analytical properties were studied through extraction and desorption profiles and also through comparison with commercial SPME fibers. As results, it was observed that the coatings prepared presented an irregular, rugged surface, desirable characteristics for SPME devices, and may be used up to 300 °C with no thermal decomposition. The extraction profile showed that the fiber allows fast equilibration times (in the order of 5 min) and fast desorption kinetics, with 5 s being needed for complete removal of extracted compounds from the fiber coating. Compared to commercial polyacrylate (PA, polar) and PDMS (apolar) fibers, the sol-gel fiber presented enhanced sorptive properties for polar compounds (carboxylic acids and alcohols) as well as for intermediate polarity ones (esters). The sol-gel fiber was successfully applied to quantitative determination of chlorophenols in wood and water / Mestrado / Quimica Analitica / Mestre em Química

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O uso de plantas ou extratos de plantas para propósitos medicinais tem sido realizado a milhares de anos. O estudo químico e biológico de plantas constitui numa estratégia alternativa na procura de novos agentes terapêuticos para a identificação de compostos bioativos. A espécie Davilla kunthii A. St. Hil, pertencente à família Dilleniaceae, é conhecida popularmente como cipódefogo e podem ser encontradas em regiões de savana. Este trabalho teve como objetivo realizar o estudo fitoquímico e ensaios biológicos da espécie Davilla kunthii A. St. Hil, tendo em vista que até o presente não foram encontrados registros químicos e biológicos a respeito desta espécie. A espécie foi coletada no Campus Cauamé do Centro de Ciências Agrárias da Universidade Federal de Roraima (CCA/UFRR). Para a preparação dos extratos hexanico e etanólico das folhas de D. kunthii A. St. Hil os materiais vegetais foram acondicionados em mariotes de vidro para extração a frio em n-hexano e, depois, etanol. O extrato etanólico das folhas, que após particionados, renderam as frações em hexano, clorofórmio, acetato de etila e metanol. As frações do extrato clorofórmico foram purificadas e analisadas através de métodos cromatográficos. Os compostos foram identificados através de técnicas espectroscópicas e comparados com dados da literatura. O estudo fitoquímico das folhas levou ao isolamento e identificação de uma mistura de ácidos graxos na forma de seus ésteres metílicos (determinados por CG), uma mistura de β-Sitosterol e Estigmasterol e do álcool Triacontan-1-ol (Álcool Melíssilico). Nos ensaios biológicos o extrato das folhas apresentaram uma variação MIC (Mínima Concentração Inibitória) de 6,2 a 53,7% para as bactérias S. aureus e S. sanguinis. Já para as bactérias E. coli e S. tiphymurium o MIC variou de 9,23 a 38,2% e para a levedura C. albicans o MIC foi de 92,5 a 95,3%. Conclui-se que o extrato etanólico das folhas de D. kunthii A. St. Hil apresentou uma baixa toxicidade frente à Artemia salina, uma excelente atividade contra a levedura C. albicans além de revelar uma grande capacidade antioxidante da espécie pelo método de redução do radical DPPH. No entanto, como ainda não foram encontrado relato sobre a referida espécie espera-se que estes resultados possam contribuir para o estudo fitoquímico desta planta. / The use of plants or plant extracts for medicinal purposes has been done for thousands of years. The chemical and biological study of plants is an alternative strategy in the search for new therapeutic agents for the identification of bioactive compounds. The Davilla kunthii A. St.-Hil species belonging to Dilleniaceae family, is popularly known as vine-of-fire and can be found in savanna regions. This work aimed to make the phytochemical study and biological assays of the species Davilla kunthii A. St.-Hil, considering that to date regarding chemical and biological records of this species were not found. The species was collected in the Campus Center Cauamé Agricultural Sciences, Federal University of Roraima (CCA / UFRR). For the preparation of hexane and ethanol extracts of the leaves of D. kunthii A. St.-Hil plant materials were placed in glass mariotes for cold extraction in n-hexane and then ethanol. The ethanol extract of the leaves, which after partitioned, yielded fractions in hexane, chloroform, ethyl acetate and methanol. The fractions of the chloroform extract were purified and analyzed by chromatographic methods. The compounds were identified by spectroscopic techniques and compared with literature data. The phytochemical study of leaves led to the isolation and identification of a mixture of fatty acids as their methyl esters (determined by GC), a mixture of β-sitosterol and stigmasterol and alcohol Triacontan-1-ol (Alcohol Melíssilico). In biological assays leaves extract showed a MIC (Minimum Inhibitory Concentration) variation from 6.2 to 53.7% for S. aureus and S. sanguinis bacteria. As for the E. coli bacteria and S. tiphymurium the MIC ranged from 9.23 to 38.2% and the yeast C. albicans MIC was 92.5 to 95.3%. It is concluded that the ethanol extract of the leaves of D. kunthii A. St.-Hil showed low toxicity on Artemia salina, an excellent activity against the yeast C. albicans as well as revealing a great antioxidant capacity of the species by the method of reduction the DPPH radical. However, they were not reported on the species is expected that these results will contribute to the phytochemical study of this plant family.

Orientador: Cesar Costapinto Santana / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-19T02:22:30Z (GMT). No. of bitstreams: 1 Vieira_JoaoPauloFernandes_M.pdf: 2071458 bytes, checksum: 4e3166090a9b86f0b92b425b128fb73f (MD5) Previous issue date: 2011 / Resumo: A enantiosseparação de alguns compostos é um brilhante e interessante tópico de muitas áreas da química analítica, principalmente na farmacêutica e biomédica. Sabe-se que apesar dos enantiômeros apresentarem fórmulas e massa molecular iguais, quando expostos em um ambiente biológico podem mostrar grandes diferenças nas suas atividades biológicas. O Fmoc-POAC (9-fluorenilmetiloxicarbonil -2,2,5,5-tetrametilpirrolidina-N-oxil-3-amino-4- ácido carboxílico) é um marcador paramagnético quiral com grande potencialidade de uso como derivado marcador de estruturas peptídicas com funções no organismo animal. De acordo com a literatura consultada, não há relatos de escalas semipreparativas na separação enantiomérica desse composto, extremamente necessária para testes de clínicos-analíticos. Este estudo teve como objetivo o desenvolvimento de métodos inovadores na separação enantiomérica do Fmoc-POAC e obtenção dos parâmetros necessários para um aumento de escala. O presente trabalho realizou uma avaliação experimental através de Cromatografia Líquida de Alta Eficiência (CLAE) para enantiosseparação desse composto, com eluição isocrática e nas colunas quirais de fase estacionária normal e reversa: i) analítica da OD-RH Chiralcel® (150x4,6 mm); ii) Analítica Lux Cellulose-2 da Phenomenex® (250x4,6 mm); iii) Semipreparativa OD da Chiralcel® (150x10 mm); iv) Semipreparativa OD-RH da Chiralcel® (250x21 mm). A partir desses ensaios experimentais, foram estimados os parâmetros cromatográficos da enantiosseparação do marcador molecular Fmoc-POAC nas colunas estudadas, além de parâmetros de transferência de massa e termodinâmicos. Os resultados desse trabalho foram que todas as colunas estudadas apresentaram a possibilidade de separação enantiomérica do Fmoc-POAC através desses métodos relativamente simples comparados aos apresentados na literatura, com destaque para a coluna de fase estacionária normal Lux Cellulose-2 (250x4,6 mm), com resolução de até 18,4. De acordo com resultados obtidos, temos a possibilidade de realizar a separação e recuperação desse composto, lançando-se mão de técnicas cromatográficas de maior rendimento, como sistemas contínuos de separação cromatográfica / Abstract: The enantioseparation of some compounds has interesting application in several areas of analytical chemistry, especially in pharmaceutical and biomedical. It is well known that some compounds with same chemical formulas and molecular mass, when exposed to a biological environment, may show different biological activities. The 9- fluorenilmetiloxicarbonil-2,2,5,5-tetrametilpirrolidina-N-oxil-3-amino-4-carboxylic acid (Fmoc-POAC) is a chiral paramagnetic marker with great potential as a marker for peptide structures with functions in the animal organism. According to the literature, there are no reports of enantiomeric separation of this compound unless in laboratory scale and large scale would be necessary for clinical and analytical testing. This study aimed at the development of innovative methods for the enantiomeric separation of Fmoc-POAC as well as obtaining the necessary parameters for scale up of their purification. The present work carried out an experimental evaluation using High Performance Liquid Chromatography (HPLC) for this compound enantioseparation with isocratic elution and columns with normal and reverse chiral stationary phase: i) Analytical Chiralcel® OD-RH (150x4, 6 mm ), ii) Analytical Lux Cellulose-2 from Phenomenex® (250x4, 6 mm), iii) Semi-preparative Chiralcel OD® (150x10 mm), iv) Semi-preparative Chiralcel OD-RH® (250x21 mm). From these assays, chromatographic parameters were estimated for the enantioseparation of Fmoc-POAC molecular marker beside parameters related to the thermodynamics and mass transfer. The conclusions in this research were that all columns present the possibility of enantiomeric separation of Fmoc-POAC by methods relatively simple compared to those presented in the literature, specially the column with normal stationary phase Lux Cellulose-2 (250x4, 6 mm) with resolution of up to 18.4. The results indicate the possibility of enantioseparation and recovery of these compounds by high yield continuous chromatography techniques / Mestrado / Desenvolvimento de Processos Biotecnologicos / Mestre em Engenharia Química

The isolation and purification of calpastatin from ostrich liver is presented, along with its physicochemical and kinetic properties. By using extraction from liver, ion-exchange chromatography on DEAE-Toyopearl, heating to 90 °C for 10 min and rechromatography on Toyopearl Super-Q 650 S, ostrich calpastatin was isolated and purified from ostrich liver. The purified intact calpastatin showed homogeneity on SDS-PAGE (Mr of 105.6 K). Amino acid analysis showed that ostrich calpastatin resembled that of rabbit liver and human erythrocyte calpastatin. An N-terminal sequence could not be obtained because the N-terminus was found to be blocked by an as yet unknown amino acid residue. The Mr values of degradative forms of ostrich liver calpastatin were determined to be 56 K and 90 K. By using PAG-IEF the pI of the intact form was determined to be 5.1. Ostrich liver calpastatin behaved characteristically like other calpastatins during kinetic analysis. Calpastatin inhibited calpain from pH 6 to 9 and was found to be unaffected by temperatures as high as 100 °C. Calpastatin also inhibited calpain activity at Ca2+ concentrations ranging from 1 to 10 mM. The inhibitor was shown to be phosphorylated because after incubation with alkaline phosphatase there was a decrease in inhibitory activity. No inhibitory effects were detected against other proteases such as chymotrypsin and trypsin, with both proteases inactivating calpastatin completely. Ostrich liver calpain was shown to have a pH optimum of 7.5 and a temperature optimum of 30 °C. In terms of its thermodynamic properties it resembled that of other ostrich proteases; DH, DS and DG being 47.07 kJ/mol, -91.1 J/mol/K and 74.237 kJ/mol, respectively. Ostrich liver calpain showed a Km of 0.14 % (w/v). The enzyme was active at both milli- and micro-molar concentrations of Ca2+. Ostrich liver calpastatin showed many physical, chemical and kinetic properties similar to those of other known calpastatins.

Phenylpropanolamine (PPA), a synthetic sympathomimetic amine structurally related to ephedrine has been widely used over t he past 40 years as a nasal decongestant and appetite suppressant. It has been the focus of much controversy concerning the efficacy of the drug in its use as an anorectic agent, and due to the side effects caused by the higher doses of PPA required for appetite suppression. Although extensively used, there is little information concerning the determination of PPA in biological fluids and on the pharmacokinetics of this drug. An adaptation of a published high-performance liquid chromatographic (HPLC) assay for PPA in serum and urine using U.V. detection at 210 nm is presented. PPA was separated in the reversed phase mode. The method has a limit of sensitivity of 5.0 ng/mL and 10.0 ng/mL in serum and urine respectively. Serum concentration data following a single 25 mg dose of phenylpropanolamine in human volunteers demonstrate the application of the analytical method for bioavailability and pharmacokinetic studies. After the administration of 25 mg, 50 mg or 100 mg PPA.HCl solutions to 5 human volunteers, a dose proportionality study demonstrated that PPA appears to exhibit linear kinetics. Linear one body compartment kinetics were assumed and the wagner-Nelson method used to transform in vivo serum data to absorption plots. The serum data were fitted to a model using nonlinear regression techniques to characterize the pharmacokinetic processes of PPA. The absorption of phenylpropanolamine appears to be discontinuous and the drug seems to favour a two body compartment model. The pharmacokinetic parameters obtained from a steady state study using multiple dosing of PPA.HCl solutions compared with those found from previous studies after the administration of sustained-release formulations. A plasma protein binding study using equilibrium dialysis demonstrated that PPA is not highly protein bound in the blood.