Submitted by Biblioteca da Faculdade de Farmácia (bff@ndc.uff.br) on 2018-01-16T13:45:19Z No. of bitstreams: 1 GLAUCE CHRISTIAN ALVES DUARTE.PDF: 7412666 bytes, checksum: f0301da81bceac842c42e74f9d99cf80 (MD5) / Made available in DSpace on 2018-01-16T13:45:19Z (GMT). No. of bitstreams: 1 GLAUCE CHRISTIAN ALVES DUARTE.PDF: 7412666 bytes, checksum: f0301da81bceac842c42e74f9d99cf80 (MD5) / Santander Universidades / A Ipecacuanha é uma planta medicinal de grande interesse da indústria farmacêutica e representatividade econômica devido à atividade dos seus principais metabólitos emetina e cefalina. Considerando que esses metabólitos são encontrados nas raízes, sua colheita foi extrativista, colocando a espécie na lista de espécies ameaçadas de erosão genética e de extinção. Desse modo, o objetivo do presente estudo foi avaliar, por meio de técnicas de RMN, o efeito da sazonalidade associado a fatores agronômicos e climáticos sobre os teores de emetina e cefalina em indivíduos da espécie cultivados na região de Niterói. Os indivíduos foram cultivados sob 4 diferentes tipos de substrato e 3 diferentes graus de sombreamento. Foram realizadas 4 colheitas referentes às 4 estações do ano, no período de 1 ano. Os extratos brutos obtidos a partir das raízes foram submetidos à doseamento por CLAE-DAD e analisados por duas técnicas de RMN, a saber, RMN em solução e HRMAS. Nessa última técnica, foram realizadas análises dos extratos e das raízes pulverizadas. Os resultados de doseamento por CLAE-DAD mostraram que, no outono, os indivíduos cultivados em terra preta + areia + bokashi e 70% de sombreamento apresentaram os maiores teores de emetina e cefalina (0,63 e 1,84, respectivamente). Apesar de não ser possível quantificar os alcaloides por meio das técnicas de RMN, as análises quimiométricas vieram a corroborar com os resultados e mostraram uma tendência a agrupamento das amostras coletadas no inverno, o que sugere diferenças metabólicas nesta estação. Dessa forma, conclui-se que, tanto na técnica cromatográfica quanto na espectroscópica, a sazonalidade foi o principal fator determinante para a escolha do período ótimo de colheita na região onde o estudo foi conduzido / The Ipecac is a medicinal plant of great interest to the pharmaceutical and economic representativeness industry due to the activity of its main metabolites emetine and cephaeline. Considering that these metabolites are found in the roots, his crop was harvested by hand, placing the species on the list of species threatened by genetic erosion and extinction. Thus, the aim of this study was to evaluate the effect of seasonality associated with agronomic and climatic factors on the content of emetine and cephaeline in individuals grown in the Niteroi region by NMR techniques. Individuals were cultured in 4 different types of substrate and 3 degrees of shading. 4 samples were collected regarding the four seasons, in the period of 1 year. The crude extract obtained from roots were assayed by HPLC-DAD and analyzed by two NMR techniques, namely solution NMR and HRMAS. In the latter technique, analyzes were performed of extracts and powdered roots. The results of determination by HPLC-DAD showed that in the fall, the grown individuals in black soil + sand + Bokashi and 70% shading showed higher levels of emetine and cephalin (0.63 and 1.95, respectively). Although it is not possible to quantify the alkaloids by NMR techniques, chemometric analysis came to corroborate the results and showed a tendency to cluster the samples collected in winter, suggesting metabolic differences in this season. Thus, we concluded that both the chromatographic technique as in spectroscopy, seasonality was the main determining factor for choosing the optimal harvest period in the region where the study was conducted

Copaifera langsdorffii (Fabaceae, Caesalpinioideae), conhecida popularmente como \"copaíba\", \"copaibeira\" ou \"pau d\'óleo\", é uma árvore de grande porte que se encontra amplamente distribuída pelo Brasil, desde a floresta amazônica até a vegetação do cerrado. A oleorresina, constituída principalmente por sesquiterpenos e diterpenos, é utilizada na medicina popular no tratamento de desordens infecciosas e inflamatórias. Por outro lado, estudos sobre suas folhas, as quais são constituídas majoritariamente por flavonoides e derivados galoilquínicos, são escassos. Assim, foi proposto o isolamento de marcadores químicos, desenvolvimento e validação de método analítico por CLAE-UV-DAD, bem como o estudo sazonal. O extrato bruto obtido das folhas foi particionado com solventes de polaridade crescente: diclorometano, acetato de etila e n-butanol. As frações em n-butanol e aquosa apresentaram, majoritariamente, compostos polares, dentre os quais se destacaram os derivados galoilquínicos. Para isolamento desses compostos utilizaram-se a cromatografia de permeação em gel de Sephadex LH-20 e a cromatografia líquida de alta eficiência preparativa. Nas análises por CLAE-UV-DAD empregou-se coluna analítica Synergi Polar-RP (100 mm x 3,0 mm, 2,5 ?m) e fase móvel composta por ácido fórmico-água (0,1:99,9, solvente A) e isopropanol- metanol-acetonitrila (0,5:4:6, solvente B). O gradiente de eluição foi A:B (90:10 para 85:15) em 8,33 minutos, seguido por A:B (85:15 para 64:36) até 29,17 minutos, utilizando vazão de 0,68 mL/min. Os estudos de sazonalidade foram realizados com 10 acessos de C. langsdorffii cultivados no Sítio Beija-Flor (Cajuru/SP). A partir da fração aquosa foram isolados e identificados 16 derivados galoilquínicos: ácido 5\'-O-metil-3-Ogaloilquínico (AGQ-1), ácido 5\'\'-O-metil-3,4-di-O-galoilquínico (AGQ-2), ácido 5\',5\'\'-di-Ometil- 3,4-di-O-galoilquínico (AGQ-3), ácido 3,4-di-O-galoilquínico (AGQ-4), ácido 5\'\'-Ometil- 3,5-di-O-galoilquínico (AGQ-5), ácido 5\'-O-metil-3,5-di-O-galoilquínico (AGQ-6), ácido 5\'-O-metil-3,4-di-O-galoilquínico (AGQ-7), ácido 5\',5\'\'-di-O-metil-3,5-di-Ogaloilquínico (AGQ-8), ácido 5\',5\'\'-di-O-metil-4,5-di-O-galoilquínico (AGQ-9), ácido 3,5-di- O-galoilquínico (AGQ-10), ácido 4,5-di-O-galoilquínico (AGQ-11), ácido 5\'-O-metil-4,5-di- O-galoilquínico (AGQ-12), ácido 5\'\'-O-metil-4,5-di-O-galoilquínico (AGQ-13), ácido 3,4,5- tri-O-galoilquínico (AGQ-14), ácido 5\'\'-O-metil-3,4,5-tri-O-galoilquínico (AGQ-15), ácido 5\',5\'\',5\'\'\'-tri-O-metil-3,4,5-tri-O-galoilquínico (AGQ-16). Além disso, por meio das análises realizadas por CLAE-EM foi possível constatar a presença de outros 10 derivados galoilquínicos: ácido 3-O-galoilquínico, ácido 4-O-galoilquínico, ácido 5-O-galoilquínico, ácido 5\'-O-metil-4-O-galoilquínico, ácido 5\'-O-metil-5-O-galoilquínico, ácido 5\'-O-metil- 3,4,5-tri-O-galoilquínico, ácido 5\'\'\'-O-metil-3,4,5-tri-O-galoilquínico, ácido 5\',5\'\'-di-Ometil- 3,4,5-tri-O-galoilquínico, ácido 5\',5\'\'\'-di-O-metil-3,4,5-tri-O-galoilquínico, ácido 5\'\',5\'\'\'-di-O-metil-3,4,5-tri-O-galoilquínico. O método analítico mostrou-se adequado para quantificação de nove derivados galoilquínicos (AGQ-1, AGQ-5, AGQ-6, AGQ-7, AGQ-8, AGQ-9, AGQ-10, AGQ-15, AGQ-16) e dois flavonoides, quercitrina e afzelina, frente aos parâmetros seletividade, linearidade, sensibilidade, precisão e exatidão. Por meio de análise estatística multivariada dos estudos sazonais concluiu-se que os acessos apresentaram perfis químicos qualitativos e quantitativos semelhantes nas coletas isoladas e perfis quantitativos diferentes ao longo dos meses. / Copaifera langsdorffii (Fabaceae, Caesalpinioideae), popularly known as \"copaíba\", \"copaibeira\" or \"pau d\'oleo\", is a large tree widely distributed in Brazil, from Amazon rainforest to savannah vegetation. Its oleoresin, composed mainly of sesquiterpenes and diterpenes, is widely used in folk medicine to treat inflammatory and infectious disorders. On the other hand, studies about its leaves, composed mainly of flavonoids and galloylquinic acid derivatives, are scarce. Therefore, it was proposed to isolate leaves major compounds, to develop and validate an analytical method by HPLC-UV-DAD, as well as to udertake seasonal studies. The crude extract of the leaves was partitioned with solvents of increasing polarity: dichloromethane, ethyl acetate and n-buthanol, in sequence. Chemical profiles of n-buthanol and aqueous fractions showed to be composed of polar compounds, especially galloylquinic acid derivatives. These compounds were isolated by gel permeation chromatography using Sephadex LH-20 and preparative high-performance liquid chromatography. The HPLC-UV-DAD analyses were carried out on a Synergi Polar-RP (100 x 3.0 mm, 2.5 ?m) column. The mobile phase was made up of formic acid-water (0.1:99.9, solvent A), and isopropanol-methanol-acetonitrile (0.5:4:6, solvent B). The elution gradient was A:B (90:10 to 85:15) in 8.33 minutes, followed by A:B (85:15 to 64:36) up to 29.17 minutes using a flow rate of 0.68 mL/ min. The seasonal studies were performed from 10 C. langsdorffii accesses grown on Beija-Flor farm (Cajuru/SP). From the aqueous fraction it was isolated and identified 16 galloylquinic acid derivatives: 5\'-O-methyl-3-Ogalloylquinic acid (GQA-1), 5\'\'-O-methyl-3,4-di-O-galloylquinic acid (GQA-2), 5\',5\'\'-di-Omethyl- 3,4-di-O-galloylquinic acid (GQA-3), 3,4-di-O-galloylquinic acid (GQA-4), 5\'\'-Omethyl- 3,5-di-O-galloylquinic acid (AGQ-5), 5\'-O-methyl-3,5-di-O-galloylquinic acid (GQA-6), 5\'-O-methyl-3,4-di-O-galloylquinic acid (AGQ-7), 5\',5\'\'-di-O-methyl-3,5-di-Ogalloylquinic acid (GQA-8), 5\',5\'\'-di-O-methyl-4,5-di-O-galloylquinic acid (GQA-9), 3,5-di- O-galloylquinic acid (GQA-10), 4,5-di-O-galloylquinic acid (GQA-11), 5\'-O-methyl-4,5-di- O-galloylquinic acid (GQA-12), 5\'\'-O-methyl-4,5-di-O-galloylquinic acid (GQA-13), 3,4,5- tri-O-galloylquinic acid (GQA-14), 5\'\'-O-methyl-3,4,5-tri-O-galloylquinic acid (GQA-15), 5\',5\'\',5\'\'\'-tri-O-methyl-3,4,5-tri-O-galloylquinic acid (GQA-16). Furthermore, through HPLC-MS analysis it was identified additional 10 galloylquinic acid derivatives: 3-Ogalloylquinic acid, 4-O-galloylquinic acid, 5-O-galloylquinic acid, 5\'-O-methyl-4-Ogalloylquinic acid, 5\'-O-methyl-5-O-galloylquinic acid, 5\'-O-methyl-3,4,5-tri-Ogalloylquinic acid, 5\'\'\'-O-methyl-3,4,5-tri-O-galloylquinic acid, 5\',5\'\'-di-O-methyl-3,4,5-tri- O-galloylquinic acid, 5\',5\'\'\'-di-O-methyl-3,4,5-tri-O-galloylquinic acid, 5\'\',5\'\'\'-di-O-methyl- 3,4,5-tri-O- galloylquinic acid. The HPLC developed method was suitable to quantify nine galloylquinic derivatives (GQA-1, GQA-5, GQA-6, GQA-7, GQA-8, GQA-9, GQA-10, GQA-15, GQA-16) and two flavonoids, quercitrin and afzelin, related to the selectivity, linearity, sensitivity, precision and accuracy parameters. Through multivariate statistical analysis, it was possible to conclude that all ten diferrent populations of C. langsdorffii cultivated displayed similar qualitative and quantitative chemical profiles among isolated months and different quantitative profiles among different months.

Cerca de 10% da flora mundial é representada pela família Asteraceae, uma das maiores famílias de Angiospermae, caracterizada não só pela diversidade morfológica e taxonômica, como também pela riqueza de metabólitos secundários apresentada pelas espécies estudadas dessa família. Lychnophora salicifolia Mart. é a espécie de maior distribuição geográfica do gênero (ocorrendo na Serra do Espinhaço na Bahia, em Minas Gerais e no sudeste de Goiás) e a mais polimórfica também. Entre seus usos etnobotânicos, destaca-se a ação anti-inflamatória e analgésica. Neste trabalho, realizamos o estudo da variação dos metabólitos polares dessa espécie, sendo que para isso foi utilizada a desreplicação do extrato bruto (metanol/água obtido a partir da folhas) através da análise por CLAE-DAD-EM, a qual permitiu a caracterização dos constituintes dessa mistura através da análise dos espectros de UV e dados de EM. Assim foi possível identificar 20 substâncias: ácido protecatecuico; ácido 3-O-E-cafeoilquínico; ácido 3-O-p-cumaroilquínico; ácido 4-O-E-cafeoilquínico; ácido 5-O-E-cafeoilquínico; ácido 4-O-p-cumaroilquínico; ácido 5-O-p-cumaroilquinico; ácido 5-O-feruloilquínico; vicenina-2 (6,8-di-C--glcosilapigenina); ácido 3,4-di-O-E-cafeoilquínico; ácido 3,5-di-O-E-cafeoilquínico; ácido 3-O-cumaroil 5-O-p-cafeoilquínico; ácido 3-O-cafeoil, 5-O-p-cumaroilquínico; ácido 4,5-di-O-E-cafeoilquínico; ácido 4-feruloil-5-O-E-cafeoilquínico; ácido 3,4 di-O-p-cumaroilquínico; ácido 3,5 di-O-p-cumaroilquínico; ácido 4,5 di-O-p-cumaroilquínico; ácido lychnofólico e o ácido 2-O-acetil lychnofólico. Para a validação da metodologia analítica foi utilizada uma substância pertencente a cada classe de compostos: ácido 5-O-E-cafeoilquínico, vicenina-2 e o ácido 2-O-acetil lychnofólico. Quanto à validação da metodologia analítica, esta garantiu a confiabilidade dos resultados e a credibilidade do método para os propósitos deste estudo, abrangendo a faixa de concentração necessária para as análises de variação populacional, além apresentar valores de limites de detecção e limites de quantificação, precisão e recuperação adequados. Na análise intrapopulacional, verificou-se uma variabilidade quantitativa entre indivíduos da mesma população, porém, em média os indivíduos pertencentes à mesma população são parecidos quimicamente. Já em relação ao estudo da variação populacional, pudemos verificar diferenças tanto quanti como qualitativas entre populações coletadas em regiões distintas do Brasil, sendo que a partir da análise estatística, verificamos que há uma correlação entre isolamento geográfico e diminuição da semelhança do perfil de metabólitos polares entre as plantas de populações diferentes indicando que o padrão encontrado para concentração dos metabólitos é influenciado pela distribuição geográfica das amostras. Todavia, não é possível determinar a localização das amostras unicamente pelas variáveis metabólicas estudadas. Assim, a concentração e presença dos metabólitos são influenciadas pela distribuição geográfica das amostras. / About 10% of the world flora is represented by the Asteraceae family, which has been extensively studied since it is one of the largest families of Angiospermae, characterized not only by morphological and taxonomic diversity but also the wealth of secondary metabolites produced by the species studied of this family. Lychnophora salicifolia Mart. is the most widely distributed species of the genus (occurring in the Serra do Espinhaço in Bahia, Minas Gerais and in the southeast of Goiás) and also is the most polymorphic. Its popular use is due to the anti-inflammatory and analgesic activity. In this work, we studied the variation of polar metabolites of this species using the dereplication of the crude extract (methanol/water obtained from the leaves) by the HPLC-DAD-MS analysis, which led us to identify the constituents of this mixture by analyzing the UV spectra and MS data. Thus it was possible to identify 20 substances: protocatechuic acid; 3-O-E-caffeoylquinic acid; 3-O-p-coumaroylquinic acid; 4-O-E-caffeoylquinic acid; 5-O-E-caffeoylquinic acid; 4-O-p-coumaroylquinic acid; 5-O-p-coumaroylquinic acid; 5-O-feruloylquinic acid; vicenin-2 (6,8-di-C--glucosylapigenin); 3,4-di-O-E-caffeoylquinic acid, 3,5-di-O-E-caffeoylquinic acid; 3-O-coumaroyl-5-O-p-caffeoylquinic acid; 3-O-caffeoyl acid, 5-O-p-coumaroylquinic acid; 4,5-di-O-E-caffeoylquinic acid, 4-feruloyl-5-O-E-caffeoylquinic acid; 3,4-di-O-p-coumaroylquinic acid; 3,5-di-O-p-coumaroylquinic acid; 4,5-di-O-p-coumaroylquinic acid; lychnofolic acid and 2-O-acetyl lychnofolic acid. To the validation of analytical methodology were used one substance belonging to each class of compounds: 5-O-E-caffeoylquinic acid, vicenin-2 and 2-O-acetyl lychnofolic acid. So, the validation of analytical method ensured the reliability and credibility of the results of the method for purposes of this study, covering the concentration range required for analysis of population variation and presents appropriates values of detection and quantification limits, precision and recovery. For intrapopulation analysis, there was a quantitative variability between individuals of the same population, but on average the individuals of the same population are similar chemically. In relation to the study of interpopulation variation, we could see quantitative and qualitative differences between populations collected from different regions of Brazil, and from the statistical analysis, we found that there is a correlation between geographic isolation and decrease of the similarity of the polar metabolites profile between plants of different populations. This indicated that the pattern found for the concentration of metabolites is influenced by the geographical distribution of samples. However, it is not possible to determine the location of the samples only by the metabolic variables studied. Thus, the presence and concentration of metabolites are influenced by the geographical distribution of samples.

No description available.

This research explored how and in what ways early childhood and fatherhood are constructed in Taiwanese father-run baby blogs. Nowadays, many parents use the internet to record and share their experiences of being (and becoming) parents. There is a growing body of literature on mothers on the internet, but the subjects of fathers on the internet and the child as recorded by the parents are both under-explored. This research selected three public Taiwanese baby blogs to study. All of the blogs were being run by new fathers and all were named (entitled) using the child's name or nickname. The entries and interactions within these blogs up until the blogged children turned three years old were observed. The blog entries and the interactions within them were treated as public texts, and a qualitative method suitable for analysing different forms of blog contents was developed. In relation to the new doing of fathering - blogging - the interactive nature of the internet and its function of creating and strengthening the identity were not obvious in this research. Although these blogs seemed to be isolated from other online communities, one of the studied cases provides us with an example of how the blog and the participants' off-line activities enrich each other. The findings of this research also suggest that these public presentations of family life have the purpose of displaying family, in order to confirm the family relationship with their readers and especially with the recorded child in the future. This displaying provided us with the three fathers' versions of fatherhood. It was found that the fatherhood being constructed in these blogs is closer to the old version of a good father. The father's role still appeared as that of supporter of the mother, who was still seen as shouldering the main responsibility for child raising. However, from an analysis of the process and the descriptions of the decision making displayed in these blogs, this research suggests that the supporter (father) - leader (mother) relationship (Sanchez & Thomson, 1997; S. Williams, 2008) should be understood as a relationship between the project director (father), who oversees the project of child raising, and the project manager (mother), who has to get the project done. Although their child-raising record showed the characteristics of intensive parenting, because of this director-manager relationship, the intensive parenting shown by the father should in fact be seen as a type of intensive mothering. With regard to the displayed child, it was found that the Taiwanese child is surveyed and defined (normal or abnormal) by the state, the medical system, and parents' daily practices. The child is also nurtured with traditional gender stereotypes and traditional aspirations (to be filially obedient) in mind. In the nurturing process, the importance of education is highlighted and the child is taken to participate in competitive activities from under one year old. It was concluded that, overall, the fatherhoods and childhoods found in this research join forces in constructing and confirming (old) Taiwanese norms relating to fathers and to the 'normal' and competitive child. Since the children in this research were represented by the father and lacked agency, it is suggested that there is a pressing need for further research into the subsequent experience of these once-displayed-in-public children, that will give us a better understanding of the practice of sharing one's child(ren)'s information online.

Yellow pigment (YP) concentration is an important quality trait in durum wheat (<i>Triticum turgidum</i> L. var <i>durum</i>) and is comprised primarily of carotenoids. The main objective of our study was to measure the accumulation of carotenoids during the grain fill period to improve our understanding of the physiological basis for differences among durum wheat cultivars. Thirteen cultivars and breeding genotypes with large variation in total YP concentration (<6 µg g-1 to >15 µg g-1) were studied. Spikes were sampled from replicated field plots in 2007 and 2008 near Saskatoon and Swift Current, Saskatchewan, Canada, at 14, 21, 28 and 35 days after heading (DAH). The remainder of each plot was combined at grain maturity for YP and carotenoid analysis. Carotenoids were extracted with 1:1 methanol:dichloromethane (0.1% BHT) and quantified with HPLC. <i>Trans</i> (E)-lutein was the predominant carotenoid at maturity and was detected at 14 DAH in all genotypes. The rate and duration of E-lutein accumulation was variable among genotypes expressing high, intermediate and low YP. The accumulation of all carotenoids was lowest in genotypes expressing low YP, and suggests rate limitations early in the carotenoid biosynthetic pathway. E-zeaxanthin concentrations were highest in mature grain, but no significant differences were detected among genotypes. However, the ratio of E-zeaxanthin to E-lutein was inversely correlated with total YP, suggesting that the â,å branch of lycopene cyclization is favoured over the â,â branch in high-YP genotypes. These results provide insights to the regulation of the carotenoid biosynthetic pathway during grain fill stage in durum wheat and will facilitate breeding for higher carotenoid concentration.

Yellow pigment (YP) concentration is an important quality trait in durum wheat (<i>Triticum turgidum</i> L. var <i>durum</i>) and is comprised primarily of carotenoids. The main objective of our study was to measure the accumulation of carotenoids during the grain fill period to improve our understanding of the physiological basis for differences among durum wheat cultivars. Thirteen cultivars and breeding genotypes with large variation in total YP concentration (<6 µg g-1 to >15 µg g-1) were studied. Spikes were sampled from replicated field plots in 2007 and 2008 near Saskatoon and Swift Current, Saskatchewan, Canada, at 14, 21, 28 and 35 days after heading (DAH). The remainder of each plot was combined at grain maturity for YP and carotenoid analysis. Carotenoids were extracted with 1:1 methanol:dichloromethane (0.1% BHT) and quantified with HPLC. <i>Trans</i> (E)-lutein was the predominant carotenoid at maturity and was detected at 14 DAH in all genotypes. The rate and duration of E-lutein accumulation was variable among genotypes expressing high, intermediate and low YP. The accumulation of all carotenoids was lowest in genotypes expressing low YP, and suggests rate limitations early in the carotenoid biosynthetic pathway. E-zeaxanthin concentrations were highest in mature grain, but no significant differences were detected among genotypes. However, the ratio of E-zeaxanthin to E-lutein was inversely correlated with total YP, suggesting that the â,å branch of lycopene cyclization is favoured over the â,â branch in high-YP genotypes. These results provide insights to the regulation of the carotenoid biosynthetic pathway during grain fill stage in durum wheat and will facilitate breeding for higher carotenoid concentration.

Phytoestrogens are naturally occurring chemicals of plant origin that have the ability to cause estrogenic and/or anti-estrogenic effects due to their structural similarities to the human hormone oestradiol. It has been proposed that phytoestrogens protect against a wide range of ailments, including breast and prostate cancers, cardiovascular disease, osteoporosis, and menopausal symptoms. Daidzein, biochanin A and especially genistein which has been reported to be the most biologically active dietary phytoestrogen attract great deal of interest in today&rsquo / s researches. In this study, twenty different food items, including legumes, fruits, nuts and herbs, (haricot beans, chickpeas, green lentils, red lentils, soybeans, licorice root, yarrow, dried chestnuts, prunes, raisins, currants, black cumin, dried apricots, dried parsley, dried dates, dried figs, sage (from Aegean region), sage (from Mediterranean region), grapevine leaves, gilaburu) were selected. Following an extraction procedure employing acid hydrolysis and heating / they were analysed for their daidzein, genistein and biochanin A contents using a reversed-phase C18 column with linear gradient elution on a high-performance liquid chromatography (HPLC) coupled with diode-array detector (DAD). Soybeans were found to contain high amounts of daidzein (91.36 mg/100 g) and genistein (85.57 mg/100 g). Chickpeas were found to contain much less amount of genistein (0.89 mg/100 g) compared with that of soybeans and also biochanin A (0.95 mg/100 g) which was not detected in soybeans. None of daidzein, genistein and biochanin A was detected in the remaining eighteen food items.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Poluentes orgÃnicos emergentes (POEs) ou simplesmente contaminantes emergentes referem-se a qualquer composto quÃmico presente numa variedade de produtos comerciais como medicamentos, produtos de uso veterinÃrio, embalagens de alimentos, produtos de higiene, agrotÃxicos, ou alguns microrganismo. Os POEs podem ser encontrados em matrizes ambientais e biolÃgicas, nÃo sÃo usualmente monitorados ou ainda nÃo possuem legislaÃÃo regulatÃria correspondente, e apresentam risco potencial à saÃde humana e ao meio ambiente. Neste trabalho, foi desenvolvido e validado um mÃtodo para a determinaÃÃo de cafeÃna, ciprofloxacina, 17&#946;-estradiol, 17&#945;-etinilestradiol e dietilestilbestrol, considerados interferentes endÃcrinos. O mÃtodo desenvolvido utilizou extraÃÃo em fase sÃlida (SPE) e cromatografia lÃquida de alta eficiÃncia acoplada a um detector de arranjo de diodos. Foram estabelecidas condiÃÃes cromatogrÃficas com eluiÃÃo por gradiente utilizando acetonitrila e Ãgua ultrapura pH 2,0. O planejamento fatorial realizado por SPE indicou que melhores respostas sÃo alcanÃadas quando utiliza-se o cartucho C18, 500 mL de volume de amostra, pH 3,0 e volume de eluiÃÃo igual a 2,0 mL de metanol 100%. As figuras de mÃrito de validaÃÃo do mÃtodo indicaram seletividade, sensibilidade, linearidade, precisÃo, exatidÃo e robustez satisfatÃrias para a maioria dos compostos estudados. Os limites de detecÃÃo (LD) variaram entre 0,283 e 1,543 &#956;g/L (ppb) e os limites de quantificaÃÃo (LQ) variaram entre 0,944 e 5,142 &#956;g/L (ppb). Foi proposta uma nova estratÃgia de controle de qualidade utilizando padrÃo surrogate, e estabelecido um fator de relaÃÃo (FR) a fim de corrigir as concentraÃÃes dos compostos de interesse em amostras reais. O mÃtodo validado foi aplicado nas anÃlises de Ãgua superficial dos aÃudes que fazem parte do abastecimento de Ãgua da RegiÃo Metropolitana de Fortaleza/CE. Os compostos 17&#946;-estradiol, 17&#945;-etinilestradiol foram detectados numa concentraÃÃo mÃxima de 989 e 980 ng/L, respectivamente. / Emerging organic pollutants (EOP), or Emerging Contaminants, is a term that is used to refer any chemical compound insert in variety of comercial products such as medicines, veterinary products, food packaging, pesticides, or any microorganism. The EOP can be found in environmental and ecological arrays not usually monitore or government unregulated, and poses risks to human health na environment. The methodological approach of this thesis included a developed and validated method to determine caffeine, ciprofloxacin, 17&#946;-estradiol, 17&#945;-ethinylestradiol and diethylstilbestrol, considered endocrine disruptors. The method uses a Solid-Phase Extraction (SPE) and high performance liquid cromatography coupled to a diode array detector. Chromatografic conditions were established by gradiente elution using acetonitrile and ultrapure water (pH = 2). The experimental design performed by SPE showed that better responses are achieved when it is used the cartridge C18, 500 mL sample volume, pH 3,0 and 2,0 mL 100% methanol elution volume. The method validation parameters indicated satisfatory selectivity, sensitivity, linearity, precision, accuracy and robustness. Detection limits (DL) ranged from 0,283 to 1,543 &#956;g/L (ppb) and quantification limits (QL) ranged from 0,944 e 5,142 &#956;g/L (ppb). A new quality control strategy using surrogate standard was proposed, and a relation factors (RF) was established to correct of concentrations of compounds of interest in real samples. The validated method was applied to the analysis of surface waters reservoirs from water supply system in metropolitan region of Fortaleza. The compounds 17&#946;-estradiol, 17&#945;-ethynyl estradiol was detected in a maximum concentration of 989 to 980 ng / L, respectively.

Lors de leur conservation, les principes actifs (médicaments, nutriments) peuvent être sujets à une dégradation susceptible de modifier leurs propriétés initiales et les rendre non disponibles. Aussi, les industriels et les pharmaciens hospitaliers réalisant des préparations pharmaceutiques et/ou des compléments alimentaires ont-ils la nécessité de réaliser des études de stabilité. Ces études sont longues et coûteuses car elles doivent tenir compte de tous les paramètres environnementaux susceptibles d’influencer la stabilité du principe actif, de la matrice et du conditionnement. L’objectif de cette thèse consiste à développer un outil qui permet d’estimer les taux de dégradation des vitamines et de se projeter sur la durée de vie de principes actifs nutritionnels en se basant sur l’utilisation des modèles de calcul intégrant à la fois les caractéristiques des produits, matrice et des conditions de conservation. Le projet s’est déroulé en plusieurs phases en ciblant les vitamines hydrosolubles. Tout d’abord, un développement et validation d’une méthode de dosage chromatographique qui permet de quantifier toutes les vitamines en une seule analyse sans interférence avec les éventuels produits de dégradation. Une étude de l’influence des paramètres les plus importants a été réalisée via un plan d’expériences. Les cinétiques de dégradation ont été étudiées et modélisées en plusieurs approches. A partir du modèle le plus adapté, un premier niveau de simulation a été conçu permettant de déterminer les facteurs d’influence pertinents dans la dégradation des vitamines au regard des données exploitables. Le livrable, le calculateur, devrait ainsi permettre de guider les utilisateurs industriels et hospitaliers dans le choix des conditions d’étude de vieillissement accéléré. / When stored, the active ingredients (drugs, nutrients) may be subject to degradation that may change their original properties and make them unavailable. In addition, manufacturers and hospital pharmacists carrying out pharmaceutical preparations and / or dietary supplements have the need to carry out stability studies. These studies are long and costly because they must consider all the environmental parameters likely to influence the stability of the active principle, the matrix and the packaging. The aim of this thesis is to develop a tool that allows to estimate the degradation rates of vitamins and to project on the life span of nutritional active principles based on the use of computational models integrating at the same time product characteristics, matrix and storage conditions. The project took place in several phases targeting the water-soluble vitamins. First, a development and validation of a chromatographic assay method that quantifies all vitamins in a single analysis without interference with any degradation products. A study of the influence of the most important parameters was carried out with a design of experiments. The kinetics of degradation have been studied and modeled in several approaches. From the most appropriate model, a first simulation level was designed to determine the relevant influencing factors in the degradation of vitamins in terms of exploitable data. The deliverable, the calculator, should thus help guide industrial and hospital users in the choice of accelerated aging study conditions.