Dispositivos moleculares fluorescentes contendo receptores poliamínicos

O objectivo desta tese é a caracterização global de algumas famílias de compostos poliamínicos com grupos aromáticos fluorescentes. Estes têm potencial deaplicação como dispositivos moleculares, incluindo quimiossensores, interruptores moleculares,máquinas moleculares ou sistemas de processamento de informação moleculares. Estes compostos possuem poliaminas que podem actuar como unidades receptoras de várias espécies químicas, como protões, iões metálicos ou aniões, e os tornam solúveis em água. Contêm também grupos aromáticos fluorescentes (naftaleno, antraceno, pireno), que actuam como unidades sinalizadoras do estado do receptor. No Capítulo 1 são apresentados métodos de síntese e purificação de compostos poliamínicos, juntamente com descrições pormenorizadas das sínteses. Nos Capítulos 2 a 8 são caracterizados diversos compostos, quando livres em solução aquosa, e na presença de iões de metais de transição e de ATP. São usadas técnicas de espectrofotometria no UV-visível, espectrofluorimetria no estado estacionário e de contagem de fotão único correlacionada no tempo, complementadas com dados potenciométricos e de RMN fornecidos pelo grupo do Prof. Enrique García-España da Universidade de Valência, Espanha. No Capítulo 2 estudam-se compostos com grupos antraceno. Verifica-se supressão de emissão a pH básico, comum a todos os compostos poliamínicos, e caracterizam-se factores que influenciam nesse fenómeno. No Capítulo 3 analisam-se compostos de naftaleno. Verificam-se excímeros intramoleculares em compostos com dois grupos naftaleno. Para os formar ocorre um movimento fotoinduzido de flexão, pelo que esses compostos podem ser considerados máquinas moleculares. No Capítulo 4 estudam-se compostos com grupos pireno. Observam-se excímeros intramoleculares nos compostos com dois fluoróforos. No Capítulo 5 caracterizam-se compostos com dois grupos aromáticos diferentes(vários compostos com naftaleno e antraceno, um com pireno e antraceno e um com pireno e naftaleno). Verifica-se transferência de energia do grupo naftaleno para o antraceno (que parece evoluir de acordo com a teoria de Förster), de pireno para antraceno e de naftaleno para pireno. No Capítulo 6 examinam-se dois compostos de antraceno na presença de iões metálicos. Verifica-se aumento de emissão presença de Zn(II) e Cd(II), e supressão de emissão na presença de Cu(II) e Ni(II). Caracteriza-se o comportamento de um deles do ponto de vista de operações lógicas ao nível molecular. No Capítulo 7 caracteriza-se um composto de naftaleno na presença de vários iões metálicos. Verifica-se supressão de emissão com iões de metais de transição do 3ºperíodo com níveis na presença de Zn(II), Cd(II) e Al(III). Não se verifica efeito na presença de iões alcalinos, alcalino-terrosos, lantanídeos, Sn(II) e Pb(II). No Capítulo 8 estuda-se a interacção de compostos poliamínicos com ATP. Verifica-se em qualquer pH a ocorrência de empilhamento aromáticos do ATP e composto poliamínico, e ancoragem do grupo polifosfato do ATP com a poliamina. Verifica-se supressão de emissão do composto poliamínico a pH ácido, principalmente por transferência electrónica fotoinduzida do seu grupo aromático para o grupo adenina protonado do ATP. Num composto com antraceno e naftaleno, continua-se a verificar transferência de energia d incompletamente preenchidos, e com Hg(II), e aumento de emissãoπ-π entre os grupos

Contextual and individual indicators associated with the presence of teeth in adults

OBJECTIVE The objective of this study was to analyze whether socioeconomic conditions and the period of availability of fluoridated water are associated with the number of teeth present.METHODSThis cross-sectional study analyzed data from 1,720 adults between 20 and 59 years of age who resided in Florianópolis, SC, Southern Brazil, in 2009. The outcome investigated was the self-reported number of teeth present. The individual independent variables included gender, age range, skin color, number of years of schooling, and per capita household income. The duration of residence was used as a control variable. The contextual exposures included the period of availability of fluoridated water to the households and the socioeconomic variable for the census tracts, which was created from factor analysis of the tract’s mean income, education level, and percentage of households with treated water. Multilevel logistic regression was performed and inter-level interactions were tested.RESULTS Residents in intermediate and poorer areas and those with fluoridated water available for less time exhibited the presence of fewer teeth compared with those in better socioeconomic conditions and who had fluoridated water available for a longer period (OR = 1.02; 95%CI 1.01;1.02). There was an association between the period of availability of fluoridated water, per capita household income and number of years of education. The proportion of individuals in the poorer and less-educated stratum, which had fewer teeth present, was higher in regions where fluoridated water had been available for less time.CONCLUSIONS Poor socioeconomic conditions and a shorter period of availability of fluoridated water were associated with the probability of having fewer teeth in adulthood. Public policies aimed at reducing socioeconomic inequalities and increasing access to health services such as fluoridation of the water supply may help to reduce tooth loss in the future.

Contributo para a valorização da concha de ostra como suplemento alimentar: caracterização química da concha

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do Grau de Mestre em Tecnologia Alimentar/ Qualidade

Estudo comparativo de três câmaras de ionização para medição directa do equivalente de dose individual, a 10 mm de profundidade, Hp(10)

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Biomédica

Redox-active cytotoxic diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes: Reduction behaviour and theoretical interpretation

Two series of new diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl), formulated as the mononuclear [R2Sn(HL)(2)] (1:2) (a, R=Bu-n and Ph) and the polymeric [R2SnL](n) (1:1) (b, R=Bu-n) compounds, were prepared and fully characterized. Single crystal X-ray diffraction for [(Bu2Sn)-Bu-n{C5H9C(O)NHO}(2)] (3a) discloses the cis geometry and strong intermolecular NH center dot center dot center dot O interactions. The in vitro cytotoxic activities of the complexes were evaluated against HL-60, Bel-7402, BGC-823 and KB human tumour cell lines, the greater activity concerning [(Bu2Sn)-Bu-n(HL)(2)] [HL=C3H5C(O)NHO (1a), C6H11C(O)NHO (4a)] towards BGC-823. The complexes undergo, by cyclic voltammetry and controlled-potential electrolysis, one irreversible overall two-electron cathodic process at a reduction potential that does not appear to correlate with the antitumour activity. The electrochemical behaviour of [R2Sn(C5H9C(O)NHO)(2)] [R=Bu-n (3a), Ph (7a)] was also investigated using density functional theory (DFT) methods, showing that the ultimate complex structure and the mechanism of its formation are R dependent: for the aromatic (R = Ph) complex, the initial reduction step is centred on the phenyl ligands and at the metal, being followed by a second reduction with Sn-O and Sn-C ruptures, whereas for the alkyl (R=Bu-n) complex the first reduction step is centred on one of the hydroxamate ligands and is followed by a second reduction with Sn-O bond cleavages and preservation of the alkyl ligands. In both cases, the final complexes are highly coordinative unsaturated Sn-II species with the cis geometry, features that can be of biological significance.

The effect of Schistosoma mansoni infection on child morbidity in the State in Bahia, Brazil: II — Analysis at the individual level

The present investigation was carried out on a sample of 840 children (5 to 16 years old) from ten small towns of the State of Bahia in northeastern Brazil. The objetive was to study, by using a cross sectional methodology, the evolution of schistosomiasis morbidity (hepatic and splenic enlargement) in children, and the role of the intensity of S. mansoni infection in this process. The children were analised in three age groups (5 to 8, to 12 and 13 to 16 years old) and classified as uninfected, mildly infected, moderately infected and heavily infected according to the number of eggs in the stool. In children aged 5 to 8 years, increasing egg counts were not associated with increasing frequencies of hepatic or splenic enlargement. In the 9 to 12 years old group and association was observed with the prevalence of hepatic enlargement, but not with the prevalence of spleen enlargement. In the oldest group, 13 to 16 years old, an association was observed with the prevalence of enlargement of both organs. It was evident that in this population schistosomiasis morbidity develops in the early period of life as a gradual process starting with liver enlargement and followed by spleen enlargement some years later. It was found that the intensity of infection has a fundamental role in this process, although there is a latent period of some years before clinical splenomegaly appears in moderate-heavily infected children. The Authors suggest that the prevalence of splenomegaly in the 13 to 16 years old group is a good measure of the community level of schistosomiasis morbidity and could be used to measure the impact of control programs.

O trabalho individual e o trabalho de grupo no processo de ensino-aprendizagem do estudo do meio no 1º Ciclo

Relatório Final apresentado à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ensino do 1º e 2º ciclo do Ensino Básico

Análise de pavimentos de parques infantis feitos com granulados de pneus usados: avaliação do potencial risco para a saúde das crianças

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia do Ambiente, Perfil Engenharia Sanitária

Malária humana: padronização e optimização de testes sorológicos para diagnóstico individual e inquéritos soroepidemiológicos

O teste de imunofluorescência indireta (IFI) é considerado teste de referência na soroiogia da malária. Neste trabalho procuramos optimizar o teste empregando P. falciparum obtido de sangue humano e de cultura e P. vivax obtido de sangue de paciente como antígenos, para pesquisa de anticorpos IgG e IgM. Das variáveis técnicas estudadas melhores resultados foram obtidos quando os soros foram diluidos ern PBS contendo 1% de Tween 80 e as lâminas contendo a suspensão antigênica foram estabilizadas em dessecadores ou fixadas com acetona. Foi também padronizado o teste imunoenzimático ELISA com antigenos de P. falciparum obtidos em cultura. O estudo comparativo com o teste de imunofluorescência indireta para pesquisa de anticorpos IgG mostrou: a) nos pacientes primo infectados por P. falciparum a sensibilidade para ambos os testes foi de 71%; b) nos pacientes primo infectados pelo P. vivax a sensibilidade foi de 40% para ambos os testes; c) nos pacientes não primo infectados e com malária atual pelo P. falciparum a sensibilidade para ambos os testes foi de 100%; d) nos pacientes não primo infectados e com malária atual pelo P. vivax a sensibilidade foi de 85% para o teste ELISA e de 92% para a IFI; e) nos pacientes com malária mista a sensibilidade para ambos os testes foi de 100%. A especificidade da IFI foi de 100% e do teste ELISA 95% nos casos de indivíduos não maláricos. Os resultados obtidos sugerem ser o teste ELISA, uma boa alternativa para o teste de IFI, para a pesquisa de anticorpos IgG anti P. falciparum, na soroiogia da malária.

Reduced schedule of human anti rabies immunization with Fuenzalida & Palacios vaccine

The present study evaluates the humoral and cellular immune responses in 35 volunteers submited to short antirabies vaccination schedules with the Fuenzalida & Palacios vaccine based on the administration of doses on non consecutive days. The volunteers were divided into two groups. The first group received a total number of five doses given on days 0, 4, 7, 20 and 35. The other group received four doses, the first one being a double dose given on day 0 and than three other single doses on days 7, 20 and 35. The evaluation of humoral immune response was carried out by serum neutralization (SN) and indirect immunofluorescense (IIF) tests, while the cellular immune response was evaluated by lymphoblastic transformation assay (LTA) and skin test (ST). According to our results these reduced schedules elicited early and effective humoral and cellulafimmune responses to rabies antigen suggesting that new reduced schedules should be extensively studied in order to give the proper bases to the proposition of changes in the current long-term schedule.

Simplification of Immune Adherence Hemagglutination test for detection of rabies antibodies in human serum

In the present work the immune adherence hemagglutination test (IAHA) was standardized in a simplified procedure. This test showed good reproducibility, better than the classical mice serum neutralization test (SN). The tests showed high correlation degree: high titers in one test corresponded to high titers in the other one, and the same occured with low titers. The IAHA test is extremely simple, fast to perform, and of low cost when compared to tests such as SN or indirect immunofluorescense (IIF). It also proved to be useful in less sophisticated laboratories or even as a screening test for the titration of rabies antibodies.

Eosinophil levels in the acute phase of experimental chagas' disease

Eosinophil dynamics, in bone marrow, blood and peritoneal exudate, of resistant C57B1/6 (C57) and susceptible A/Snell (A/Sn) mice was comparatively studied during the acute phase of infection by Trypanosoma cruzi Y strain. A decline was observed in bone marrow eosinophil levels in A/Sn, but not in C57 mice, soon after infection, those of the former remaining significantly below those of the latter up to the 4th day of infection. Bone marrow eosinophil levels of C57 mice declined subsequently to levels comparable to those of A/Sn mice, the number of these cells in this compartment remaining 50% those of non infected controls, in both strains, up to the end of the experiment on the 14th day of infection. The fluctuations in eosinophil levels in blood and peritoneal space were similar in both mice strains studied. Concomitantly with depletion of eosinophils in the marrow, depletion in blood and a marked rise of these cells in the peritoneal space, initial site of infection, occurred in both strains. The difference in eosinophil bone marrow levels, between C57 and A/Sn mice, observed in the first four days of infection, suggests a higher eosinopoiesis capacity of the former in this period, which might contribute to their higher resistance to T. cruzi infection.

Exposição de profissionais de saúde a radiações ionizantes : confiança dos profissionais nas leituras de dosimetria individual

Resumo - O avanço tecnológico e científico no campo da Medicina tem favorecido a aplicação das radiações ionizantes nas áreas da Medicina Nuclear, Radiologia, Radioterapia e noutras especialidades relacionadas com a medicina de intervenção, como a Cardiologia. As Organizações de Saúde, com profissionais com risco de exposição a radiações ionizantes, são responsáveis, legislativamente, por assegurar a sua vigilância. Certificando a observação controlada das doses de exposição, os profissionais são monitorizados com dosímetros individuais e submetidos a vigilância médica. As leituras de dosímetria individual destes profissionais, originam por vezes, nos próprios, desconfianças e incertezas quanto aos valores medidos. Objectivo: avaliar o grau de confiança dos profissionais de saúde, expostos a radiações ionizantes, no sistema de monitorização individual. Metodologia: estudo observacional do tipo analítico- transversal, por questionário. Amostra de 190 Técnicos de Diagnóstico e Terapêutica de Cardiopneumologia, Medicina Nuclear, Radiologia, Radioterapia, expostos a radiações ionizantes, que exercem a sua actividade profissional em hospitais do concelho de Lisboa. Resultados: 51,1% dos Técnicos de Diagnóstico e Terapêutica não confiam nas leituras dos dosímetros, não se determinou uma relação estatisticamente significativa entre essa confiança, o tipo de dosímetro e a empresa que realiza as leituras. A confiança é maior nos que exercem em Organizações de Saúde públicas. 40,2% das Organizações de Saúde apresentam plano de vigilância médica, constatando-se uma falta de conformidade entre os Técnicos de Diagnóstico e Terapêutica, nalguns hospitais, relativamente à existência desse plano no respectivo hospital. A margem de erro associado ao estudo é de 5,09%, com um nível de confiança de 95%. -----------Abstract - The technological and scientific advances in the field of medicine has encouraged the application of ionizing radiation with a considerable positive contribution in the areas of Nuclear Medicine, Radiology, Radiotherapy and other specialties related to medical intervention like Cardiology. The Health Organizations that arise the risk of occupational exposure to ionizing radiation and is their responsibility to ensure monitoring, according the law. To ensure the monitoring of controlled doses of exposure, the exposed works use an individual dosimeter and undergo medical supervision. The individual dosimetry readings of health-care professionals, is sometimes questionable for themselves, arising distrust and uncertainty about the values measured. Objective: evaluate the degree of confidence of health professionals, exposed to radiation, on the system of individual monitoring. Methods: Observational study of cross-type analysis by questionnaire. Sample of 190 of technologists of Cardiopneumology, Nuclear Medicine, Radiology, Radiotherapy, exposed to ionizing radiation, which work in hospitals on the region of Lisbon. Results: 51.1% of technologists does not rely on the readings of their dosimeters, and wasn’t determined a statistically significant relationship between this trust, the type of dosimeter and the company that makes the readings(s) of their(s) dosimeter(s). The confidence in the readings is higher in public Health Organizations. 40.2% of the Health Organizations have medical monitoring plan and there is a disagreement between technologists, in some hospitals, relatively to the existence of this plan in their hospital. It was estimated that the u

Biochemical analysis of the methylic antigen of Paracoccidioides brasiliensis

Yeast forms of five strains of Paracoccidioides brasiliensis (SN, 2, 18, 192 and JT- 1) were cultured in a synthetic medium for obtaining methylic antigens. These antigens were lyophilized and studied for each strain, to determine their partial biochemical composition, through measurements of total lipid, protein and carbohydrate contents. Lipids of methylic antigens were purified and analysed for sterols, phospholipids, glycolipids, li-poproteins, and partial characterization of sterols. Significant differences were found among antigenic preparations derived from distinct P. brasiliensis strains, in relation to the quantitative determinations. On the other hand, sterol analysis revealed the presence of ergosterol, lanosterol and squalene in all samples. The diversity verified in the biochemical characteristics of antigens derived from different P. brasiliensis strains, confirm the need of using a pool of fungal samples in order to produce antigen preparations for serological procedures without hampering their sensitivity.