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Memoria para optar al título de Químico Farmacéutico / En esta Memoria se desarrolló una metodología por HPLC, para ser empleada en el estudio de estabilidad hidrolítica del fármaco hipocolesterolémico pravastatina. Las condiciones óptimas fueron alcanzadas luego de llevar a cabo el ensayo de aptitud del sistema (system suitability test, USP XXVII), y consistieron en una fase móvil isocrática: acetonitrilo/tampón fosfato 30 mM, pH 2.0 (28/72), flujo 1 mL/min a 40 ºC. Las condiciones óptimas se seleccionaron en base a la combinación adecuada entre los valores de resolución (R), factor de capacidad (k’), selectividad (α),tiempos de retención de cada señal y el tiempo de corrida del cromatograma. En estas condiciones pravastatina exhibió un tiempo de retención (tr) promedio de 8.95 min (n=10), R= 2.1, k’= 5.5 y =1.16. La metodología exhibió características analíticas de repetibilidad (CV=0.11 %) y reproducibilidad (CV=0.49 %) adecuadas para ser empleada en estudios de estabilidad. Para la cuantificación se empleó el método de la curva de calibración, que estuvo descrita por la ecuación: ABC = 2.74×1010 [c] + 72267 (r= 0.99992; n= 7). Los límites de detección y cuantificación calculados fueron 3.4×10-7 M y 3.7×10-6 M, respectivamente. El estudio de estabilidad se realizó a cuatro concentraciones iniciales, tres temperaturas y cinco pH en tampón fosfato 30 mM, con el fin de lograr interpretar la influencia de estas variables sobre la velocidad de degradación de pravastatina. En todas las condiciones de pH y temperatura ensayadas se obtuvo una cinética mixta, en las cuales se ajustó a una cinética de seudo primer orden hasta aproximadamente el 50 % de degradación del fármaco. Para evaluar la influencia del pH en la degradación, se ensayaron los pH 3, 5, 7, 9 y 12. A pH < 7 los cromatogramas presentan cinco nuevas señales correspondientes a los productos de degradación, a tr de 10.21 min; 11.83 min; 15.91 min; 17.60 min y 19.47 min. A pH > 7 sólo se observa la aparición de una nueva señal, a tr de 1.90 min. En todos los casos estudiados, las nuevas señales presentan un espectro UV análogo al de pravastatina, lo cual indica que la hidrólisis no afecta la estructura cromófora del fármaco. Con el objeto de evaluar la influencia de la temperatura sobre la degradación de pravastatina, se llevaron a cabo experimentos a 40, 60 y 80 ºC, obteniéndose que la constante de velocidad de degradación (k) aumenta en forma concomitante con el incremento de la temperatura. Además se reportan los valores de energías de activación, vidas medias y t90 calculadas para la degradación de pravastatina. Adicionalmente se estudió la reactividad de pravastatina frente a radicales libres y peroxinitrito, como modelos predictivos de su estabilidad oxidativa tanto en preformulaciones como in vivo. Se empleó como técnica analítica la espectrofotometría UV-Visible y como generadores de radicales alquilo ABAP+ N2, radicales alquilperoxilo ABAP + O2, y ABTS (radicales ABTS+). Para evaluar la reactividad frente a peroxinitrito se empleó SIN-1. La reactividad frente a ABAP y SIN-1 se llevó a cabo siguiendo la señal del fármaco a 240 nm, empleando el método de la curva de calibración (A = 2.04×10-8 [c] + 4.55×10-9). Para ABTS+ se siguió el decaimiento de su señal a 734 nm. Pravastatina (40 M a 100 M) fue reactiva frente a todos los compuestos ensayados, encontrándose que el orden de reactividad fue: peroxilo (k=1.13×10-2 min-1)  alquilo (k=7.07×10-3 min-1) > peroxinitrito (k=2.68×10-3 min-1)  ABTS.+ (k=1.20×10-3 min-1). Además, se informa la reactividad de estos compuestos frente otros análogos estructurales de la pravastatina: los profármacos lovastatina y simvastatina, y sus análogos de cadena abierta obtenidos experimentalmente por hidrólisis alcalina exhaustiva. / In this Thesis a methodology by high HPLC was developed, with aim to be used in the stability study in front of hydrolysis of the hypocholesterolemic drug pravastatin. The optimal conditions were reached after carried out the system suitability test according to USP XXVII, which consisted of an isocratic mobile phase of 30 mM acetonitrile/phosphate buffer, pH 2.0 (28/72), flow rate of 1 mL/min at 40 ºC. The optimal conditions were selected on the basis of the combination between the values of resolution (R), capacity factor (k'), selectivity (α), the retention times of each signal and the run time of the chromatogram. In these conditions pravastatin exhibited a retention time (Rt) average of 8.955 min (n =10), R = 2.1, k' = 5.5 and α = 1.16. The methodology exhibited analytical characteristics of repeatability (CV=0.11 %) and reproducibility (CV=0.49%) adequate to be used in stability studies. For the quantification the calibration curve method was used, and was described by the equation: ABC=2.74×1010 [c] + 72267 (r =0.99992; n=7). The detection and quantification limits were 3.4×10-7 M and 3.7×10-6 M, respectively. The stability study were carried out at four initial concentrations, three temperatures and five pH in 30 mM phosphate buffer, with the aim of evaluate the influence of these variables on the pravastatin degradation. In all the tested conditions of pH and temperature a mixed kinetic was obtained, in which it adjusted to a pseudo-first order kinetic until approximately 50% of degradation of the drug. In order to evaluate the effect of pH on the degradation, pH 3, 5, 7, 9 and 12 were assayed. At pH<7, five new signals corresponding to degradation products appears in the chromatograms, with Rt of 10.21 min; 11.83 min; 15.91 min; 17.60 min and 19.47 min. At pH>7 only a new signal in the chromatograms was observed, at the same Rt of 1.90 min. In all the studied cases, the new signals display an UV spectrum similar to that of pravastatin, which indicates that the hydrolysis process does not affect the chromophore structure of the drug. With the aim to evaluate the influence of temperature on the hydrolytic degradation; experiments at 40, 60 and 80 ºC were carried out. From these experiments was obtained that the degradation rate constant (k) increases concomitantly as the temperature increase. Also, activation energies values, half lives and t90 values for the degradation of pravastatin are reported. Additionally, the reactivity of pravastatin in front of free radicals and peroxinitrite, as predictive models of its oxidative stability in both preformulations and in vivo, were studied. For this study UV/Vis spectrophotometry was used as analytical technique and ABAP + N2 as alkyl radical’s generator, ABAP + O2 as alkylperoxyl radical’s generator, and ABTS (ABTS+). The reactivity with peroxynitrite was evaluated by using SIN-1. The reactivity of pravastatin in front of ABAP and SIN-1 was assess following the spectrophotometric signal of the drug at 240nm, using the calibration curve method (A = 2.04×10-8[c] + 4.55×10-9). For ABTS+ the decay of its signal at 734 nm was used. Concentrations of pravastatin in the range of 40 μM to 100 μM were studied. The drug was reactive in front to all the compounds assayed, and the reactivity ranking was: ABAP+O2 (k=1.13×10-2 min-1) ≥ ABAP+ N2 (k=7.07×10-3 min-1) > SIN-1 (k=2.68×10-3 min-1) ≥ ABTS (k=1.2×10-3 min-1), that means: alkylperoxyl ≥ alky > peroxynitrite ≥ ABTS•+. In addition, the reactivity of these compounds in front other structural analogous of pravastatin: the prodrugs lovastatin and simvastatin, and their analogous of open chain experimentally obtained by exhaustive alkaline hydrolysis are reported.

Orientador: Adriana Zerlotti Mercadante / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-07-31T19:36:36Z (GMT). No. of bitstreams: 1 Silva_SandraReginada_D.pdf: 29343911 bytes, checksum: 865db1d94cca7ffdd5f0bf50c9178d50 (MD5) Previous issue date: 2002 / Resumo: Neste trabalho determinou-se a composição de carotenóides e o valor de vitamina A de maracujá-amarelo in natura, de diferentes produtos comerciais de maracujá (polpa congelada, sucos pasteurizado e concentrado congelado açucarado, bebidas à base de suco e soja e à base de suco e iogurte) e de polpa congelada de açaí. Os carotenóides pró-vitamínicos A de produtos comerciais de manga (polpa congelada, sucos pronto para beber, pasteurizado e concentrado congelado) foram investigados. Todas as 99 amostras foram adquiridas em Campinas, São Paulo. Em todas as amostras os carotenóides foram extraídos com acetona e após transferência para éter de petróleo/éter etílico, o extrato foi saponificado. Os carotenóides foram separados em cromatógrafo líquido de alta eficiência equipado com detector de arranjo de diodos e coluna C18 e como fases móveis acetonitri/almetanol/acetato de etila nas proporções de 75:15:1O para maracujá e açaí e de metanollacetato de etila, 90:10 para os produtos de manga. Em todas as amostras de maracujá e em seus produtos foram encontrados os seguintes carotenóides: beta-criptoxantina, prolicopeno, 'dzeta'-caroteno, cis-'dzeta'-caroteno, all-trans-'dzeta'-caroteno, e 13-cis-beta-caroteno, além de outros carotenóides minoritários. ... Observação: O resumo, na íntegra, poderá ser visualizado no texto completo da tese digital. / Abstract: In this work the carotenoid composition and vitamin A value of fresh yellow passion fruit, different commercial products of passion fruit (frozen pulp, pasteurized, ready-to-drink and sweetened concentrated frozen juices, and soft drinks made with soy and yogurt), and of frozen pulp of açaí were determined. The provitamin A carotenoids from many mango commercial products (frozen pulp, ready-to-drink, pasteurized and sweetened concentrated frozen juices) were investigated. All 99 samples were acquired in Campinas, São Paulo. The carotenoids trom ali samples were extracted with acetone, transterred to petroleum ether/diethyl ether and saponified. The carotenoids were separated by high performance liquid chromatography equipped with diode array detector and 'C IND. 18' column with the following mobile phases acetonitrile/methanollethyl acetate (75: 15:10) for passion fruit and açaí, and methanollethyl acetate (90:10) for mango products. In all samples of fresh passion fruit and its different products the following carotenoids were found: beta-cryptoxathin, prolycopene, cis 'dzeta'-carotene, 'dzeta'-carotene, all-trans-beta-carotene, 13-cis-beta-carotene, and other minor carotenoids. ... Note: The complete abstract is available with the full electronic digital thesis or dissertations. / Doutorado / Doutor em Ciência de Alimentos

Memoria para optar al título profesional de Ingeniero Agrónomo y tesis para optar al grado de Magíster en Enología y Vitivinicultura / En este estudio, se evaluó la evolución de los compuestos fenólicos de vinos de los cultivares Cabernet Sauvignon y Carménère durante la crianza en barricas de roble de origen francés y americano de primer uso y tostado medio. Los análisis químicos generales (acidez total, pH, grado alcohólico, azúcares reductores, anhídrido sulfuroso y acidez volátil), espectrofotométricos (fenoles, taninos y antocianos totales, índice de gelatina, intensidad colorante, matiz y fraccionamiento de taninos) y de cromatografía líquida de alta resolución (perfil antociánico, compuestos fenólicos de bajo peso molecular y floroglucinólisis) fueron aplicados periódicamente durante 7 meses. Los resultados demostraron que el contenido total de compuestos fenólicos disminuyó hacia el final del período de crianza en ambos ensayos estudiados. Asimismo, en todos los vinos analizados se pudo observar un aumento del tirosol y una disminución de ácido trans-cafeico durante la crianza. Sin embargo, el comportamiento del resto de los compuestos no flavonoides varió en función del tipo de barrica y/o vino utilizado. Por el contrario, variaciones en el contenido de antocianinas glucosiladas, acetiladas y cumariladas resultaron en una disminución del contenido de antocianos totales en todos los vinos criados tanto en barricas de origen francés como americano. Finalmente, el contenido de flavanoles no mostró variaciones de concentración durante el estudio, salvo algunos muestreos puntuales. En relación a estos últimos compuestos, se observaron en el vino del cultivar Cabernet Sauvignon los máximos valores de grado medio de polimerización, peso molecular promedio y oligómeros entre el segundo y cuarto muestreo. Al comparar los resultados obtenidos entre vinos criados en barricas de origen americano y francés, fue posible observar en el cultivar Cabernet Sauvignon que los primeros presentaron una mayor concentración de flavonoles totales al final del estudio, mientras que los criados en barricas de origen francés mayores concentraciones de antocianinas totales y glucosiladas en la mayoría de los muestreos. Así también, se advirtió en ambos cultivares mayores concentraciones de ácido elágico durante la crianza en barrica de origen francés. / In this study, the evolution of phenolic compounds in wines from Cabernet Sauvignon and Carménère cultivars during aging in French and American oak barrels first used and medium toasted was evaluated. General chemical analyses (total acidity, pH, alcohol content, reducing sugars, sulfur dioxide and volatile acidity), spectrophotometric analyses (total phenols, tannins and anthocyanins, gelatin index, color intensity, hue and fractionation of tannins) and high performance liquid chromatography analyses (anthocyanin profile, low molecular weight phenolic compounds and mean degree of polymerization using phloroglucinol) were applied regularly for 7 months. The results showed that total phenolic content decreased towards the end of the aging period in both studied trials. Also, during aging in every analyzed wines, a tyrosol increase and a trans-caffeic acid decrease was observed. However, the behavior of the other non-flavonoid compounds varied depending on the type of barrel and/or wine used. On the other hand, glycosylated, acetylated and cumarilated anthocyanin variations resulted in a decrease of the total anthocyanin content in all wines aged in barrels of both French and American oak. Finally, the flavanol contents didn’t show concentration changes during the study, except in some specific samples. Regarding the latest compounds, in Cabernet Sauvignon cultivar wines the highest values of average degree of polymerization, mean molecular weight and oligomers were observed between the second and fourth sampling times. By comparing the results between aged wines in barrels of American and French oak in Cabernet Sauvignon cultivar, it was observed that the first had higher concentration of total flavonols at the end of the study, while those wines aged in French oak barrels presented higher concentrations of total and glycosylated anthocyanins in most samplings. Also, in both cultivars increasing concentrations of ellagic acid during aging in French oak barrels were observed.

Orientador: Eva Gonçalves Magalhães / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-07-23T22:13:34Z (GMT). No. of bitstreams: 1 Nogueira_MarisaAlves_D.pdf: 6389081 bytes, checksum: d3bb25f95973a5732c9744c32926d0ad (MD5) Previous issue date: 1998 / Doutorado

Orientador: Isabel Cristina Sales Fontes Jardim / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-07-24T01:41:50Z (GMT). No. of bitstreams: 1 Melo_LucioFlavioCosta_M.pdf: 2630353 bytes, checksum: 4c2f798e472fbf4b2cd2f1232b1b89b0 (MD5) Previous issue date: 1998 / Mestrado

Orientador: Eva Gonçalves Magalhães / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-07-24T06:11:23Z (GMT). No. of bitstreams: 1 Ruiz_AnaLuciaTascaGois_M.pdf: 3596278 bytes, checksum: 7ed9784fcb93623487d38260733b3022 (MD5) Previous issue date: 1998 / Mestrado

Orientador: Isabel Cristina Sales Fontes Jardim / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-07-24T07:24:30Z (GMT). No. of bitstreams: 1 Silva_CesarRicardoda_M.pdf: 2555049 bytes, checksum: d86781396350cecdb1267f041e6427ea (MD5) Previous issue date: 1998 / Mestrado

Orientador : Isabel Cristina Sales Fontes Jardim / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-07-18T06:22:37Z (GMT). No. of bitstreams: 1 Hespanhol_MariadoCarmo_M.pdf: 4715127 bytes, checksum: 4806b1942e755bb4fd3ecb621d5fe342 (MD5) Previous issue date: 1993 / Mestrado

Orientador: Maria Cecilia Figueiredo Toledo / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-07-18T23:17:42Z (GMT). No. of bitstreams: 1 Pupin_AntonioMarcos_M.pdf: 3268218 bytes, checksum: 26b631d2f6cf0b857e22a39427bd579d (MD5) Previous issue date: 1994 / Resumo: Amostras de óleos comerciais de alho, arroz, canola, girassol, railho, palma (azeite de dendê) e soja e de azeites deoliva foram analisadas quanto ao teor de benzo(a)pireno (B(a)P).Foram também avaliadas possíveis fontes de contaminação de óleos de milho e soja, incluindo a secagem do grão, diferentes etapas do processo de refino e o solvente de extração. A metodologia analítica envolveu extração liquido liquido, limpeza em coluna de sílica gel e determinação por cromatografia líquida de alta eficiência. 0 limite de detecção do B(a)P foi de 0,5 jig/Kg e sua recuperação média, 97,2%. Os teores médios de B(a)P encontrados em óleos de arroz, girassol, milho, palma, soja e em azeite de oliva foram respectivamente: 1,8 ; 0,2 ; 10,8 ; 2,1; 2,2 e 10,9 ug/Kg. Nos óleos de alho e canola não foi detectada a presença de B(a)P. As amostras de azeites de oliva apresentaram níveis variados de contaminação.Os menores níveis de B(a)P (n.d. a 1,2 ug/Kg) foram determinados em azeites de oliva importados da Europa. Azeites importados da Europa, porém embalados no Brasil, e azeites de oliva mistos com óleos de soja e milho mostraram teores relativamente maiores de B (a)P, variando entre n.d. a 9,7 e 2,2 a 9,2 jig/Kg, respectivamente. Azeites de oliva provenientes da Argentina apresentaram os maiores níveis de contaminação, com até 164, 4 j-íg/Kg de B (a) P. Não foi detectada a presença de B{a)P em grãos de milho e de soja antes e após o processo de secagem. A hexana, solvente de extração do óleo, mostrou-se contaminada com níveis médios de B{a)P de 4,1 ug/Kg, sugerindo sua participação na contaminação de óleos. A partir dos níveis de B(a)P encontrados nos óleos analisados e com base em dados de consumo destes produtos pela população, estimou-se que os óleos de soja e de milho contribuem com 0,09 e 0,4 [iq de B(a)P na dieta total diária do consumidor brasileiro, respectivamente / Abstract: Samples of vegetable oils on the brazilian market including canola, corn, soybean, sunflower, rice, palm, garlic and olive oils were analysed for benzo(a)pyrene (B(a)P). Possible sources of contamination of soybean and corn oils, such as the grain drying, different steps of the refining process and the extraction solvent were also evaluated. The analytical method involved liquid-liquid extraction, clean-up on silica gel column and determination by high performance liquid chromatography with fluorescence detector. The limit of detection was 0.5 ug/Kg, and the mean recovery was 92,7%. The mean level of B(a)P in rice, sunflower, soybean, corn, palm and olive oils were: 1.8 ; 0.2 ; 2.1 ; 10.8 ; 2.2 and 10.9 ug/Kg, respectively. No B(a)P was detected in garlic and rapeseed oils. Samples of olive oils showed variable levels of contamination. The lowest B(a)P levels (n.d. to 1.2 ug/Kg) were determined in olive oil imported from Europe. European olive oils packed in Brazil and olive oils blended with soybean and corn oils showed relatively higher levels of B(a)P, in the range of n.d. to 9.7 and 2.2 to 9.2 ug/Kg, respectively. Olive oils imported from Argentine showed the highest levels of contamination, up to 164.4 ug/Kg. No B(a)P was found in soybean and corn grains either before or after the drying process. Hexan, the oil extraction solvent, showed a mean level of 4.1 ug/Kg B(a)P, suggesting its participation in the oil contamination. Based on the average consumption of vegetable oils in Brazil and on their content of B(a)P, individual daily intakes of 0.09 and 0.4 ug B(a)P through the consumption of soybean and corn oils were estimated, respectively / Mestrado / Mestre em Ciência de Alimentos