Rigid poly[hydroxyethyl acrylate-co-poly(ethylene glycol) diacrylate] (Poly(HEA-co-PEGDA) monoliths were synthesized inside 75-µm i.d. capillaries by one-step UV-initiated copolymerization using methanol and ethyl ether as porogens. The optimized monolithic column was evaluated for hydrophobic interaction chromatography (HIC) of standard proteins. Six proteins were separated within 20 min with high resolution using a 20 min elution gradient, resulting in a peak capacity of 54. The performance of this monolithic column for HIC was comparable or superior to the performance of columns packed with small particles. Monoliths synthesized solely from PEGDA were also found to show excellent performance in HIC of proteins. Continuing efforts showed that rigid monoliths could be synthesized from PEGDA or poly(ethylene glycol) dimethacrylates (PEGDMA) containing different ethylene glycol chain lengths for HIC of proteins. Effects of PEG chain length, bi-porogen ratio and reaction temperature on monolith morphology and back pressure were investigated. Monoliths prepared from PEGDA 258 were found to provide the best chromatographic performance with respect to peak capacity and resolution. An optimized PEGDA 258 monolithic column was able to separate proteins using a 20-min elution gradient with a peak capacity of 62. The preparation of these in situ polymerized single-monomer monolithic columns was highly reproducible. The single-monomer synthesis approach clearly improves column-to-column reproducibility.The highly crosslinked monolith networks resulting from single crosslinking monomers were found to enhance the surface area of the monolith and concentrations of mesopores. Thus, monolithic columns were developed from four additional crosslinking monomers, i.e., bisphenol A dimethacrylate (BADMA), bisphenol A ethoxylate diacrylate (BAEDA, EO/phenol = 2 or 4) and pentaerythritol diacrylate monostearate (PDAM) for RPLC of small molecules. Gradient elution of alkyl benzenes and alkyl parabens was achieved with high resolution using all monolithic columns. Porogen selection for the BADMA and PDAM was investigated in detail with the intention of obtaining data that could possiblly lead to a rational method for porogen selection.

Background. Endocrine disruptors (EDC) are exogenous compounds that mimic the action of natural hormones and alter the normal endocrine system. Life-long chronic exposure to Bisphenol A (BPA), a putative EDC, has been linked with risk of metabolic disorders in epidemiological studies. Objectives. The aim was to study the human health effects of exposure to BPA, using an integrated approach combining environmental epidemiology and toxicology. Methods. Urinary levels of BPA exposure were measured in participants of the InChianti longitudinal study, a representative population-based study of Italian adults, at the Baseline (1998-00) and nine years later (3rd Wave, 2007-09). Hormones levels and the gene expression of specific target genes were the end points considered. Results were validated in laboratory studies on a human leukemic T-cell line (Jurkat cells). Results. In general, urinary BPA (uBPA) concentrations were higher among men and younger respondents, and within subjects uBPA concentrations were correlated (r=0.58; p=0.013, model adjusted for age, sex, urinary creatinine). At baseline, uBPA concentration were associated with higher total testosterone concentrations in men (β = 0.05; 95% CI, 0.02–0.08). In the 3rd wave, gene expression analysis revealed positive associations between uBPA concentrations and ESR2 (estrogen receptor beta) expression (β=0.18; 95% CI: 0.04, 0.32) and ESRRA (estrogen related receptor alpha) expression (β= 0.17; 95% CI: 0.02, 0.32). In a following in vitro study, BPA exposure (0.001-1 micro molar) led to enhanced expression of ESRRA and ESR2 in Jurkat cells over a period of 72 hours. Conclusions. Results indicate that BPA is bioactive in the human body and is able to alter circulating hormone concentrations and estrogen receptor/estrogen-related receptr gene expression. In particular, given the role of ERRα as a major control point for oxidative metabolism and heart development, this research provides indications on the possible molecular mechanisms of action of BPA in metabolic diseases.

O objetivo deste trabalho foi avaliar a influência de diferentes aminas terciárias no grau de conversão, na contração de polimerização, na taxa de contração, na microdureza Knoop, na estabilidade de cor e na transmitância de luz de resinas experimentais, contendo, em peso, BisGMA e TEGDMA (3:1), 0,25% de canforquinona (CQ) e 1% de amina (DMAEMA, CEMA, DMPT, DEPT ou DABE). A influência de diferentes protocolos de fotoativação também foi investigada. O grau de conversão foi avaliado através de FTIR-ATR e a contração pelo método do disco aderido. A partir da diferenciação numérica dos dados de contração em relação ao tempo, obteve-se a taxa de contração de polimerização. A estabilidade de cor e a transmitância foram avaliadas em diferentes períodos de envelhecimento artificial. Os resultados foram avaliados pelos testes de ANOVA, Tukey e T3 de Dunnett (&#945; = 0,05). As propriedades estudadas variaram em função da amina. O grau de conversão e a contração de polimerização variaram na sequência: CQ < DEPT < DMPT &#8804; CEMA &#8776; DABE < DMAEMA. O grau de conversão e a contração também foram influenciados pelo protocolo de fotoativação, sendo observadas correlações positivas entre o grau de conversão e a contração e entre o grau de conversão e a taxa de contração. A cor variou na sequência: DMAEMA < DEPT < DMPT < CEMA < DABE. A transmitância variou na sequência: DEPT &#8776; DABE < DABE &#8776; DMPT &#8776; CEMA < DMPT &#8776; CEMA &#8776; DMAEMA, sendo mais evidente para o comprimento de onda de 400nm. Não foram observadas correlações entre o grau de conversão e as propriedades ópticas. A resina contendo DMAEMA apresentou maior grau de conversão, contração, taxa de contração e dureza, além de melhor estabilidade nas propriedades ópticas. / The aim of this work was to evaluate de influence of different tertiary amines on degree of conversion (DC), shrinkage-strain, shrinkage-strain-rate, Knoop microhardness, and colour and transmittance stabilities of experimental resins containing BisGMA / TEGDMA (3:1 wt), 0,25wt% camphorquinone, 1wt% amine (DMAEMA, CEMA, DMPT, or DABE). Different light-curing protocols were also evaluated. DC was evaluated with FTIR-ATR and shrinkage-strain with the bonded-disc method. Shrinkage-strain-rate data were obtained from numerical differentiation of shrinkage-strain data with respect to time. Colour stability and transmittance were evaluated during different periods of artificial aging, according to ISO 7491:2000. Results were evaluated with ANOVA, Tukey and Dunnetts T3 tests (&#945; = 0.05). The studied properties varied according to amines. DC and shrinkage-strain were maximum at the sequence: CQ < DEPT < DMPT &#8804; CEMA &#8776; DABE < DMAEMA. Both DC and shrinkage were also influenced by the curing protocol, with positive correlations between DC and shrinkage-strain and DC and shrinkage-strain-rate. Colour varied in the sequence: DMAEMA < DEPT < DMPT < CEMA < DABE. Transmittance varied in the sequence: DEPT &#8776; DABE < DABE &#8776; DMPT &#8776; CEMA < DMPT &#8776; CEMA &#8776; DMAEMA, being more evident at the wavelength of 400nm. No correlations between DC and optical properties were observed. The resin containing DMAEMA showed higher DC, shrinkage-strain, shrinkage-strain-rate and microhardness, in addition with better optical properties.

Recentemente, pesquisas vêm claramente demonstrando que xenobióticos podem apresentar efeitos deletérios sobre o sistema endócrino e passam a ser de grande importância toxicológica à medida que se tornam contaminantes ambientais. Tais substâncias passaram a ser denominadas de desreguladores endócrinos (DEs). Entre os diferentes DEs identificados, muitos são praguicidas, amplamente utilizados no meio agropecuário em todo o mundo. Atualmente, já são bem estabelecidas as metodologias para avaliação do potencial efeito DE de diferentes substâncias em roedores; porém uma busca na literatura deixa clara a falta de estudos e de protocolos para avaliação de DEs em animais de produção ruminantes, os quais certamente estão expostos a um grande número de agentes tóxicos com estas características. Assim, foi objetivo desta pesquisa dar início ao desenvolvimento de um protocolo para avaliação de efeitos DEs de xenobióticos em ruminantes. Para tal, estudou-se o bisfenol A (BPA), o qual é, classicamente, um DE para roedores. Além disto, avaliou-se o potencial efeito DE da I. carnea, uma planta tóxica de grande importância para ruminantes no Brasil e em outros países. O estudo foi realizado em duas etapas, na primeira avaliou-se os efeitos do BPA e da planta nos caprinos machos púberes; na segunda etapa propôs-se avaliar os efeitos tóxicos da exposição in utero de caprinos machos púberes a estas mesmas substâncias. Os resultados obtidos mostraram que os bodes púberes expostos ao BPA apresentaram redução significante dos níveis séricos de tiroxina, e da qualidade espermática. Também observou-se nestes mesmos animais degeneração vacuolar na rete testis. Já os caprinos machos púberes que receberam a I. carnea apresentaram aumento significante do numero de espermatozoides com alterações morfológicas e degeneração vacuolar testicular. Ainda, estes mesmos animais apresentaram diminuição estatisticamente significante dos níveis séricos dos hormônios tireoidianos (T3 e T4). O protocolo empregado para avaliação dos efeitos da exposição in utero a I. carnea ou ao BPA em machos púberes, não evidenciou nenhuma alteração hormonal e/ou reprodutiva. Conclui-se que o protocolo empregado para avaliação de possíveis efeitos DEs de xenobióticos, em ruminantes foi eficaz, no entanto, futuras metodologias deverão ser introduzidas neste protocolo, para detectar alterações mais sutis no sistema endócrino. / Recently, many studies clearly showed that xenobiotics may have deleterious effects on the endocrine system. These substances are termed endocrine disruptors (EDs), and have great toxicological significance when they become environmental contaminants. Many of EDs are identified as pesticides, which were widely used in agriculture and livestock worldwide. Currently, there are already well-established methodologies for assessing the potential effect of endocrine disruptor (ED) of different substances in rodents; however, a literature search shows clearly the lack of studies and protocols for assessing EDs in ruminant livestock, which are indubitably exposed to a large number of these substances. Thus, the objective of the present research was to start developing a protocol for evaluation of possible effects of EDs in ruminants. For this, it was studied bisphenol A (BPA), a classic ED and also I. carnea, an important toxic plant to ruminants in Brazil and other countries. The study was conducted in two stages, in the first, it was evaluated the effects of BPA and I. carnea in pubescent male goats, and in the second stage it was studied the effects in pubescent male goats from mothers exposed, during pregnancy, to BPA or the toxic plant. The pubescent male goats treated with BPA showed significant reduction in serum thyroxine levels and in the sperm quality. Those animals also presented vacuolar degeneration in the rete testis. Pubescent male goats exposed to I. carnea showed many alterations: significant increase in morphological changes in the sperm, decrease in serum levels of thyroid hormones (T3 and T4) and testicular vacuolar degeneration. The used protocol for evaluation of the effects of in utero exposure to BPA or I. carnea in pubescent male goats showed no hormonal or reproductive changes in male goats evaluated at the puberty. In conclusion, the protocol used in the present study showed to be worthy to evaluate EDs effects in ruminants; however future methodologies should be introduced to detect more subtle changes in the endocrine system.

Bisfenol A (BFA) é usado em uma variedade de produtos de consumo, incluindo alguns tipos de papéis, principalmente os papéis termossensíveis, no qual é utilizado como revelador. Mesmo assim, pouco é conhecido sobre a magnitude da contaminação ou exposição humana ao BFA, como resultado do contato com papéis. Neste estudo, foi desenvolvido e validado uma metodologia para determinação de BFA por espectroscopia de fluorescência sincronizada. O método desenvolvido e validado é rápido, simples e de baixo custo e apresenta boa sensibilidade, sendo apropriado para aplicação em amostras de papéis. O método apresentou linearidade no intervalo de concentração entre 25 e 450 ?g.L-1 (r = 0,9993). Os limites de detecção e quantificação foram de 1,20 e 3,99 ?g.L-1, respectivamente. Valores de precisão inter e intra ensaio foram de 3,21 a 8,54% e de 0,29 a 3,92%, respectivamente. A exatidão variou de 87,4 a 111% (para as concentrações de 25, 250 e 450 ?g.L-1). Os valores de recuperação estiveram entre 100 e 102% (amostra extraída). A metodologia validada foi aplicada na determinação de BFA em 13 tipos de produtos de papel (n=444), incluindo papel termossensível (n=341), bilhete de loteria (n=7), bilhete de ônibus (n=5), cartão de visita (n=12), envelope (n=11), flyer (n=10), guardanapo (n=8), papel de impressão sulfite A4 (n=3), embalagem de alimento (n=20), papel higiênico (n=8), papel toalha (n=4) e revista (n=9), jornal (n=6). BFA foi encontrado em 98% das amostras de papel termossensível (n =341) com concentrações variando desde menores que o LQ até 27,7 mg.g-1 e média geométrica e mediana de 14,6 mg.g-1 e 17,7 mg.g-1, respectivamente. Já a maioria (96%) dos outros tipos de papéis analisados (n = 103) apresentou concentrações de BFA variando desde menores que oLQ até 379 ?g.g-1 e média geométrica e mediana de 14,7 ?g.g-1 e 17,3 ?g.g-1,respectivamente. Os papéis termossensíveis apresentaram mais altas concentraçõesde BFA (ordem de mg.g-1) comparado aos outros tipos de papéis analisados,principalmente os produzidos a partir de papel reciclado com concentrações na ordemde ?g.g-1. A estimativa da exposição humana ao BFA através da manipulação de ii diferentes tipos de papéis foi estimada baseado na concentração de BFA e frequência de manipulação. A ingestão diária aceitável de BFA, ajustada pelo peso corporal (calculado para a mediana das concentrações), através da absorção dérmica, via manipulação de papéis pela população em geral e por indivíduos expostos ocupacionalmente foi de 14,5 e 1070 (ng/Kg peso corporal/dia), respectivamente / Bisphenol A (BPA) is used in a variety of consumer products, including some paper products, particularly thermal receipt papers, for which it is used as a color developer. Nevertheless, little is known about the magnitude of BPA contamination or human exposure to BPA as a result of contact with papers. In this study, was develop and validate an methodology for determination of BPA by synchronous fluorescence spectroscopy. The developed and validated method was fast, easy, low cost, with a good sensibility and appropriate for application in paper samples. The method was linear on the range of to 25 a 450 ?g.L-1(r = 0,9993). The detection and quantification limits were 1,20 and 3,99 ?g.L-1 respectively. Inter and intraday precision were between 3,21 to 8,54% and 0,29 to 3,92%, respectively. Accuracy was between 87,4 to 111%. The recovery was between 100 to 102 % (extracted samples). The validated methodology was applied in the BPA determination in 13 types pf paper products (n=444), including thermal receipt papers (n=341), lottery tickets (n=7), bus tickets (n=5), business cards (n=12), mailing envelopes (n=11), flyers (n=10), napkins (n=8), printing paper (n=3), food contact paper (n=20), kitchen rolls (n=4), toilet paper (n=8), newspaper (n=6), and magazines (n=9). BPA was found in 98% of thermal receipt papers (n = 341) at concentrations ranging from below the limit of quantitation (LOQ) to 27,7 mg.g-1 with a geometric mean of 14,6 mg.g-1 and a median of 17,7 mg.g-1. The majority (96%) of other paper products (n = 103) contained BPA at concentrations ranging from below the LOQ to 379 ?g.g-1 with a geometric mean of 14,7 ?g.g-1 and a median of 17,3 ?g.g-1. Whereas thermal receipt papers contained the highest concentrations of BPA (milligram-per-gram), the others types of papers, especially those produced from recycled paper contain lower concentrations of BPA (microgram-per-gram). Estimation of human exposure to BFA through manipulation of different paper types was calculated based on the measure of concentration and frequency of manipulation. The estimated daily intake for BFA adjusted body weight (calculated at median concentrations) through dermal absorption from handling of papers was 14.5 and 1070 ng/day for the general population and occupationally exposed individuals, respectively.

O objetivo do presente trabalho foi a otimização, via metodologia de superfície de resposta, da síntese de compósitos de nitreto de carbono grafítico e óxido de grafeno reduzido, por via úmida, para aplicação em fotodegradação de poluentes orgânicos, empregando-se como poluente-modelo o Bisfenol A (BPA) em meio aquoso e em concentrações ambientais (100 µg L-1). O nitreto de carbono foi obtido por pirólise da melamina, enquanto o óxido de grafeno reduzido foi obtido a partir do grafite por um método de Hummers modificado e posteriormente reduzido com hidrazina em refluxo após a impregnação em g-C3N4. A impregnação se baseou em auto-montagem por interação eletrostática via tratamento sonoquímico esfoliativo em pH 3,0, em que os materiais apresentam cargas opostas. Inicialmente, três fatores foram estudados para a formação dos compósitos: o teor mássico de óxido de grafite utilizado, o tempo de sonicação da mistura das suspensões dos materiais precursores esfoliados por ultrassom de ponteira e a quantidade de hidrazina utilizada para redução do óxido de grafeno. Para tanto realizou-se um planejamento inicial de dois níveis e três fatores com réplicas em todos os pontos. Após o ajuste de um modelo linear e de se determinar região ótima percorrendo-se o caminho de máxima inclinação, um Planejamento Composto Central foi utilizado para se otimizar a reação. A quantidade de hidrazina empregada não se mostrou estatisticamente significativa nos níveis estudados. As condições ótimas de síntese foram: 16% em massa de GrO, 8,5 min de sonicação da mistura. A hidrazina foi fixada em seu nível baixo (1:4 GrO em massa). A remoção do BPA chegou a aproximadamente 65% após 0,5 h de adsorção no escuro e 1 h de irradiação, utilizando-se 0,05 g L-1 do compósito. O material obtido com as condições ótimas foi aproximadamente 2,7 vezes mais ativo que o obtido com as condições encontradas na literatura. O sistema reacional apresentou baixas fotólise (3%) e adsorção no escuro (22%). Em termos texturais, o material obtido apresenta área superficial específica maior (86 m2 g-1) que a da matriz original de g-C3N4 (26 m2 g-1) sem o tratamento sonoquímico. Para o compósito otimizado, a estrutura lamelar do g-C3N4 foi preservada no compósito conforme os perfis dos difratogramas de pó. A superfície dos precursores e do compósito mostraram-se bastante puras. As análises de DRS mostraram que as propriedades de separação de carga do compósito não diferem muito do bandgap do g-C3N4 puro (2,7 eV). / The objective of this work was the optimization of the synthesis of grafitic carbon ni-tride and reduced graphene oxide composites by Response Surface Metodology for the photodegradation of organic pollutants, using bisphenol A as a model pollutant in aque-ous medium and environmental concentrations (100 µg L-1). Carbon nitride was ob-tained by pyrolysis of melamine, while the reduced graphene oxide was obtained from grafite by a modified Hummers method. The graphene oxide formed was later reduced by hydrazine in reflux after the impregnation in g-C3N4. The synthesis was based on a self-assembly via eletrostatic interaction and exfoliative sonochemical treatment at pH 3.0, condition in which the materials presented opposite charges. Initially three factors were studied for the composites fabrication: the graphite oxide mass content, the sonication period of the precursor mixture, which was exfoliated by a sonotrode and the amount of hydrazine used for reducing graphene oxide. An initial experimental design with two levels and three factors and replicas at all points was carried out. After determining a linear model and finding the optimum region along the path of steepest ascent, a Central Composite Design was performed to optmize the reaction. The amount of hydrazine employed was not statistically significant within the levels studied. The optimum conditions of syhthesis were 16% in mass of graphite oxide and 8.5 min of soni-cation of the mixture. Hydrazine was set at its low level (1:4 to GrO in mass). The BPA removal reached approximately 65% after adsorption (30 min in the dark) and 1 h of irradiation with 0.05 g L-1 composite. The obtained material according to the optimal conditions was approximately 2.7 times more active than the one obtained using the conditions found in the literature. The reaction system presented low photolysis (3%) and adsorption (22%). Texturally speaking, the obtained material had greater specific surface area (86 m2 g-1) than the original g-C3N4 matrix (26 m2 g-1). In textural terms, the g-C3N4 lamelar structure was preserved in the composite according to the powder dif-fractograms profiles. The surface of precursors and composite was quite pure. DRS analyses showed that the charge separation properties of the composite do not signifi-cantly differ from the pure g-C3N4 bandgap (2.7 eV).

Plusieurs travaux suggèrent l'implication des polluants de l'environnement dans l'épidémie d'obésité et l'incidence du diabète. Cependant, l'impact cumulé de cette myriade de polluants auxquels l'homme est exposé à faibles doses pendant toute sa vie n'a pas été totalement appréhendé.Au laboratoire, nous utilisons un modèle souris d'exposition chronique (toute la vie) à un mélange de polluants (TCDD, PCB153, DEHP et BPA) via leur ajout à une alimentation obésogène ou standard. Les doses des polluants sont ajustées de sorte à ce que l'exposition soit de l'ordre de la Dose Journalière Tolérable, supposée sans effet chez l'homme, pour chacun des 4 polluants.Nos résultats montrent que dans un contexte d'obésité induite par le régime et à l'âge adulte, l'exposition au mélange de polluants altère le métabolisme hépatique du cholestérol chez les mâles et aggrave l'intolérance au glucose chez les femelles. L'analyse du profil métabolique de femelles immatures nourries avec le régime obésogène indique que les effets des polluants sont liés au contexte hormonal et à l'activité oestrogéno-mimétique des polluants. Enfin, en condition de régime standard, nous observons une dyslipidémie chez les femelles adultes exposées au mélange, possiblement en lien avec la dérégulation génique dans le foie de plusieurs voies métaboliques dont le rythme circadien et le métabolisme du cholestérol. En revanche, les polluants n'ont pas d'effet obésogène.En conclusion, nos travaux démontrent que les polluants en mélange exercent un impact métabolique adverse chez la souris à des doses supposées sans effet individuellement, et ces effets sont dépendants du sexe de l'âge et du contexte alimentaire / Pollutants are suspected to contribute to the etiology of obesity and related metabolic disorders but the current risk assessment does not take into account the cocktail effect resulting from the large amount of chemicals to which humans are exposed.We fed mice with high fat or standard diet with or without a mixture of food pollutants, either persistent pollutants (TCDD, PCB153) or short-lived pollutants (DEHP, BPA). Doses are adjusted resulting in mice exposure at the Tolerable Daily Intake dose range for each pollutant. Mice are chronically exposed from preconception to adult life.We demonstrated that a mixture of 4 pollutants triggers in the adult male offspring (12 weeks) an alteration of hepatic cholesterol metabolism. In females, there was a marked deterioration of glucose tolerance, which may be related to decreased hepatic estrogen signaling. The analyze of 7 week-old female mice, when they exhibit early signs of obesity and immature estrogen levels, shown that pollutant exposure alleviated HFSD-induced glucose intolerance, suggesting apparent biphasic effects of pollutants along with hormonal context. Then we compared hepatic signature of gene expressions from exposed non-obese or non exposed obese females and we highlight 4 main pathways that were targeted by both treatments and appeared to be affected by different but overlapping mechanisms. Plus, we showed that pollutants can markedly alter the circadian clock in the liver.Altogether, we emphasize that, pollutants presented in a mixture, have adverse metabolic effects at doses where they are supposed to be without any individual effect, and these effects depend on the gender, age and dietary context

Recentemente, pesquisas vêm claramente demonstrando que xenobióticos podem apresentar efeitos deletérios sobre o sistema endócrino e passam a ser de grande importância toxicológica à medida que se tornam contaminantes ambientais. Tais substâncias passaram a ser denominadas de desreguladores endócrinos (DEs). Entre os diferentes DEs identificados, muitos são praguicidas, amplamente utilizados no meio agropecuário em todo o mundo. Atualmente, já são bem estabelecidas as metodologias para avaliação do potencial efeito DE de diferentes substâncias em roedores; porém uma busca na literatura deixa clara a falta de estudos e de protocolos para avaliação de DEs em animais de produção ruminantes, os quais certamente estão expostos a um grande número de agentes tóxicos com estas características. Assim, foi objetivo desta pesquisa dar início ao desenvolvimento de um protocolo para avaliação de efeitos DEs de xenobióticos em ruminantes. Para tal, estudou-se o bisfenol A (BPA), o qual é, classicamente, um DE para roedores. Além disto, avaliou-se o potencial efeito DE da I. carnea, uma planta tóxica de grande importância para ruminantes no Brasil e em outros países. O estudo foi realizado em duas etapas, na primeira avaliou-se os efeitos do BPA e da planta nos caprinos machos púberes; na segunda etapa propôs-se avaliar os efeitos tóxicos da exposição in utero de caprinos machos púberes a estas mesmas substâncias. Os resultados obtidos mostraram que os bodes púberes expostos ao BPA apresentaram redução significante dos níveis séricos de tiroxina, e da qualidade espermática. Também observou-se nestes mesmos animais degeneração vacuolar na rete testis. Já os caprinos machos púberes que receberam a I. carnea apresentaram aumento significante do numero de espermatozoides com alterações morfológicas e degeneração vacuolar testicular. Ainda, estes mesmos animais apresentaram diminuição estatisticamente significante dos níveis séricos dos hormônios tireoidianos (T3 e T4). O protocolo empregado para avaliação dos efeitos da exposição in utero a I. carnea ou ao BPA em machos púberes, não evidenciou nenhuma alteração hormonal e/ou reprodutiva. Conclui-se que o protocolo empregado para avaliação de possíveis efeitos DEs de xenobióticos, em ruminantes foi eficaz, no entanto, futuras metodologias deverão ser introduzidas neste protocolo, para detectar alterações mais sutis no sistema endócrino. / Recently, many studies clearly showed that xenobiotics may have deleterious effects on the endocrine system. These substances are termed endocrine disruptors (EDs), and have great toxicological significance when they become environmental contaminants. Many of EDs are identified as pesticides, which were widely used in agriculture and livestock worldwide. Currently, there are already well-established methodologies for assessing the potential effect of endocrine disruptor (ED) of different substances in rodents; however, a literature search shows clearly the lack of studies and protocols for assessing EDs in ruminant livestock, which are indubitably exposed to a large number of these substances. Thus, the objective of the present research was to start developing a protocol for evaluation of possible effects of EDs in ruminants. For this, it was studied bisphenol A (BPA), a classic ED and also I. carnea, an important toxic plant to ruminants in Brazil and other countries. The study was conducted in two stages, in the first, it was evaluated the effects of BPA and I. carnea in pubescent male goats, and in the second stage it was studied the effects in pubescent male goats from mothers exposed, during pregnancy, to BPA or the toxic plant. The pubescent male goats treated with BPA showed significant reduction in serum thyroxine levels and in the sperm quality. Those animals also presented vacuolar degeneration in the rete testis. Pubescent male goats exposed to I. carnea showed many alterations: significant increase in morphological changes in the sperm, decrease in serum levels of thyroid hormones (T3 and T4) and testicular vacuolar degeneration. The used protocol for evaluation of the effects of in utero exposure to BPA or I. carnea in pubescent male goats showed no hormonal or reproductive changes in male goats evaluated at the puberty. In conclusion, the protocol used in the present study showed to be worthy to evaluate EDs effects in ruminants; however future methodologies should be introduced to detect more subtle changes in the endocrine system.

Observando o atual interesse em polímeros organometálicos para diversas aplicações, foi feita a síntese de uma série de polímeros conjugados contendo ferroceno na cadeia principal visando à investigação de suas propriedades, em especial fenômenos magnetorresistivos, magneto-ópticos e de óxido-redução. Os polímeros preparados pelo método de McMurry foram os seguintes: PFV: poli(1,1\'-ferrocenilenovinileno) e PFV-DOPPV-M: poli[1,1\'-ferrocenilenovinileno-alt-(2,5-di-n-octilóxi)-1,4-fenilenovinileno]. Outros dois polímeros foram preparados utilizando o método de polimerização de Wittig, o PFV-DOPPV-W: poli[1,1\'-ferrocenilenovinileno-alt-(2,5-di-n-octilóxi)-1,4-fenilenovinileno] e o PFV-DMPPV: poli[1,1\'-ferrocenileno-vinileno-alt-(2,5-dimetóxi)-1,4-fenilenovinileno]. A síntese de polímeros contendo segmentos &#960;-conjugados equenos e bem definidos separados por segmentos não-conjugados é uma das melhores stratégias para a obtenção de polímeros emissores de luz azul. Com base nesse argumento foi feita a síntese de uma série de polímeros contendo um derivado metoxilado de bisfenol-A (BPA) na cadeia principal, alternando-se com unidades de PPV ou PFV que apresentam segmentos conjugados bem definidos. Os polímeros preparados foram os seguintes: BPA-DOPPV:poli[2,2-bis(4-metoxifenil)-propano-alt-2,5-(di-n-octilóxi)-1,4-divinilbenzeno]; BPA-PPV: poli[2,2-bis(4-metoxifenil)-propano-alt-1,4-ivinilbenzeno]; BPA-DMPPV: poli[2,2-bis(4-metoxifenil)-propano-alt-2,5-dimetóxi-1,4-ivinilbenzeno]; BPA-DBPPV: poli[2,2-bis(4-metoxifenil)-propano-alt-2,5-dibromo-1,4-divinilbenzeno] e BPA-PFV: poli[2,2-bis(4-metoxifenil)-propano-alt-1,1\'-divinil-ferroceno]. Todos os polímeros obtidos foram caracterizados por métodos espectroscópicos (UV-VIS, IR, RMN), análises térmicas, SEC, entre outras. Algumas aplicações foram estudadas para esses polímeros, tais como a construção de um eletrodo de ORP modificado, a produção de diodos orgânicos emissores de luz (OLEDs) e a determinação da resposta \"olfativa\" de sensores de gases. / Owing to the current interest in organometallic polymers and their applications, a group of conducting polymers containing ferrocene in the main chain was synthesized aiming the study of their magnetoresistive, magneto-optic and redox properties. The following polymers were prepared via McMurry method: poly(1,1\'-ferrocenylenevinylene) (PFV) and poly[1,1\'-ferrocenylenevinylene-alt-(2,5-di-n-octiloxy)-1,4-phenylenevinylene] (PFV-DOPPV-M). Two other polymers were synthesized via Wittig method: poly[1,1\'-ferrocenylenevinylene-alt-(2,5-di-n-octiloxy)-1,4-phenylenevinylene] (PFV-DOPPV-W) and poly[1,1\'-ferrocenylene-vinylene-alt-(2,5-dimethoxy)-1,4-phenylenevinylene] (PFV-DMPPV). The synthesis of polymers with well-defined small &#960;-conjugated segments separated by non-conjugated segments is one of the best strategies to obtain blue light emitting polymers. Based on this statement the synthesis of several polymers formed by methoxylated bisphenol-A (BPA) alternated with PPV or PFV units was performed. The prepared polymers were the following: poly[2,2-bis(4-methoxyphenyl)-propane-alt-2,5-(di-n-octiloxy)-1,4-divinylbenzene] (BPA-DOPPV), poly [2,2-bis(4-methoxyphenyl)-propane-alt-1,4-divinylbenzene] (BPA-PPV), poly[2,2-bis(4-methoxyphenyl)-propane-alt-2,5-dimethoxy-1,4-divinylbenzene] (BPA-DMPPV), poly[2,2-bis(4-methoxyphenyl)-propane-alt-2,5-dibromo-1,4-divinylbenzene] (BPA-DBPPV) and poly[2,2-bis(4-methoxyphenyl)-propane-alt-1,1\'-divinylferrocene] (BPA-PFV). All the synthesized polymers were characterized by spectroscopic methods (UV/VIS, IR, NMR), thermal analysis, SEC, among others. Some applications to these polymers were studied: a modified ORP electrode, organic light emitting devices (OLEDs) and gas sensors.

Charles University, Faculty of Pharmacy in Hradec Králové, Department of Biological and Medical Sciences The University of Alcalá, Faculty of Medicine, Department of biomedicine and biotechnology Student: Zuzana Chvojanová Supervisor: PharmDr. Miroslav Kovařík, Ph.D. Consultant: María Isabel Arenas Jimenéz Title of the diploma thesis: Study of the variations in the expression of different adhesion and cytoskeletal proteins of podocytes (E-Cadherin, Podocin, Vimentin) due to Bisphenol A Bisphenol A (BPA) is one of the most widespread compounds in the world, producing over 6 billion metric tons per year. It is widely used as part of polycarbonate plastics and epoxy resins, from which reusable plastic bottles, food boxes and some medical equipment are made. It is also used to coat the inner layer of the cans. Previous studies have shown that BPA contributes to many chronic diseases in the human body, such as kidney disease - diabetic nephropathy. Podocytes - terminally differentiated cells of the Bowman's capsule in glomerulus - are an integral part of the filtration barrier, where they play an important role in preventing the plasmatic proteins from penetrating to the urine. Therefore, in this study, we looked at the effect of BPA on these cells and their particular proteins, using both in vivo and...