Mono(Eta(5)-cyclopentadienyl)metal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies, and first hyperpolarizabilities

A series of mono(eta(5)-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta(5)-C5H5)(L)(C C{C4H2S}(n)NO2)] (M = Fe, L = kappa(2)-DPPE, n = 1,2; M = Ru, L = kappa(2)-DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV-Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push pull systems.

Adapting remote labs to learning scenarios: case studies using VISIR and RemotElectLab

Remote laboratories are an emergent technological and pedagogical tool at all education levels, and their widespread use is an important part of their own improvement and evolution. This paper describes several issues encountered on laboratorial classes, on higher education courses, when using remote laboratories based on PXI systems, either using the VISIR system or an alternate in-house solution. Three main issues are presented and explained, all reported by teachers, that gave support to students' use of remote laboratories. The first issue deals with the need to allow students to select the actual place where an ammeter is to be inserted on electric circuits, even incorrectly, therefore emulating real-world difficulties. The second one deals with problems with timing when several measurements are required at short intervals, as in the discharge cycle of a capacitor. In addition, the last issue deals with the use of a multimeter in dc mode when reading ac values, a use that collides with the lab settings. All scenarios are presented and discussed, including the solution found for each case. The conclusion derived from the described work is that the remote laboratories area is an expanding field, where practical use leads to improvement and evolution of the available solutions, requiring a strict cooperation and information-sharing between all actors, i.e., developers, teachers, and students.

A construção do estado liberal. Elite política e burocracia na "Regeneração" (1851-1890)

Quem governa ? Qual a configuração e dinâmica da burocracia ? Sinteticamente, estas duas questões enunciam os objectivos principais da presente investigação sobre o sistema politico administrativo no Portugal oitocentista. No essencial, o âmbito cronológico do nosso estudo coincide com os limites temporais da "Regeneração ", no sentido lato do termo, isto e, com o novo ciclo liberal que tem como acto fundador o pronunciamento militar üsaldanhista" de finais de Abril de 1851 e se prolonga até à crise de 1890. comummente identificada pela historiografia portuguesa como um momento crucial de viragem. Este período de cerca de quarenta anos singulariza- se pela combinação de três aspectos fundamentais. Por um lado, tratou-se de uma época de relativa acalmia politica e social - apenas seriamente ameaçada na conjuntura critica de 1868 a 1871 -, durante a qual as manifestações de conflito violento, que tinham marcado a fase inicial do liberalismo, cederam o lugar às formas de conflito regulado. Esta alteração do tipo dominante de conflito, associada à institucionalização dos mecanismos e processos do sistema de "governo representativo", resultou da afirmação de uma lógica de compromisso (a "politica dos acordos") entre as várias parcialidades ou coligações rivais da elite, que implicava a subordinação da luta politica às regras da competição pacifica e a garantia de expectativas credíveis de alternância no poder. Em larga medida, essa transformação não teria sido possível sem uma ampla renovação do pessoal politico dirigente. Por outro lado, correspondeu a uma etapa decisiva na consolidação do aparelho burocrático do Estado liberal, que se traduziu numa dinâmica de expansão e modernização das estruturas e meios de administração. Finalmente, foi um ciclo marcado por importantes "melhoramentos materiais· e um razoável crescimento económico. embora à custa de um elevado endividamento público. Ocupando as principais posições de comando na hierarquia formal de poder e. como tal, intervindo activamente na construção das instituições e regulam o curso da vida colectiva, na elaboração das normas que as elites politicas são um dos actores centrais em todos os processos de mudança social, independentemente da avaliação positiva ou negativa do seu protagonismo histórico . Por essa razão. o estudo da sua formação e composição ou da sua acção transformadora constituem importantes eixos temáticos da investigação em sociologia politica.

Localization studies of the FemXAB protein family in Staphylococcus aureus

Dissertação apresentada para a obtenção do Grau de Mestre em Genética Molecular e Biomedicina, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Structuring and moodleing a course: case studies at the polytechnic of Porto - School of engineering

This work presents a comparative study covering four different courses lectured at the Polytechnic of Porto - School of Engineering, in respect to the usage of a particular Learning Management System, i.e. Moodle, and its impact on students' results. Even though positive correlation factors exist, e.g. between the number of Moodle accesses versus the final exam grade obtained by each student, the explanation behind it may not be straightforward. Mapping this particular factor to course numbers reveals that the quality of the resources might be preponderant and not only their quantity. This paper also addresses teachers who used this platform as a complement to their courses (b-learning) and identifies some particular issues they should be aware in order to potentiate students' engagement and learning.

Engaging students by moodleing a course? Case studies at the Polytechnic of Porto–School of Engineering

This work presents a comparative study covering four different courses lectured at the Polytechnic of Porto - School of Engineering, regarding the usage of a particular Learning Management System, i.e. Moodle, and its impact on students' results. This study addresses teachers who used this platform as a complement to their courses (b-learning) and identifies some particular issues in order to potentiate students' engagement and learning. Even though positive correlation factors exist, e.g. between the number of Moodle accesses versus the final exam grade obtained by each student, the explanation behind it may not be straightforward. Mapping this particular factor to course numbers reveals that the quality of the resources might be preponderant and not only their quantity. These results point to the fact that some dynamic resources might enlarge students' engagement.

Evaluation of the potential of translocated common cockle for ecological risk assessment studies: bioaccumulation and biomarkers test

Thesis submitted to the Faculdade de Ciências e Tecnologia to obtain the Master’s degree in Environmental Engineering, profile in Ecological Engineering

The Cornerstones of Modern Government Maps, Weights and Measures and Census in Liberal Portugal (19th century)

Thesis submitted for assessment with a view to obtaining the degree of Doctor in History and Civilisation from the European University Institute

Wetland Habitat Studies using various Classification Techniques on Multi-Spectral Landsat Imagery: Case study: Tram chim National Park, Dong Thap Vietnam

Dissertation submitted in partial fulfilment of the requirements for the Degree of Master of Science in Geospatial Technologies

Evolution of schistosomiasis in an hyperendemic area of the Minas Gerais state: two cross-sectional studies

Two cross-sectional studies on schistosomiasis mansoni were done in Comercinho, Minas Gerais (Brazil), at an interval of 7 years. In 1974 and 1981 feces examinations (KATO-KATZ method) were done in 89 and 90% of the population (about 1,500 inhabitants) and clinical examinations were done in 78 and 92% of the patients who excreted Schistosoma mansoni eggs in the feces, respectively. The rate of infection by S. mansoni did not change (69.9% in 1974 and 70.4% in 1981), but the geometrical mean of eggs per gram of feces (431 ± 4 and 334 ± 4, respectively) and the rate of splenomegaly (11 and 7%, respectively) decreased significantly in 1981, when compared to 1974. This reduction was observed only in the central zones of the town (zones 1-2) where the rate of dwellings with piped water increased from 17 to 44%. In the surroundings (zones 3-4), where the proportion of houses with piped water did not change significantly between 1974 (10%) and 1981 (7%), the geometrical mean of S. mansoni eggs and the rate of splenomegaly did not change either.

Immunopathologic studies in myocardial biopsies of patients with Chagas' disease and idiopathic cardiomyopathy

Right ventricular endomyocardial biopsies were studied in 30 patients, 15 with myocardiopathy from chronic Chagas'disease and 15 with idiopathic congestive myocardiopathy; five other myocardial samples were taken at necropsies of patients with chronic Chagas' disease. The authors tried to establish by means of direct immunofluorescence techniques whether there were immunoglobulins G, A and M, fibrinogen and C3 complement deposition in the myocardium; only one of these 30 patients exhibited a positive reaction to IgG, it was a patient with idiopathic congestive myocardiopathy. All fragments from patients with Chagas' disease showed no response to any of the fluorescent conjugates. These findings do not support the idea that anti-myoeardial antibodies have pathogenic importance in the evolution of dilated or chagasic myocardiopathies.

Serologic studies on the behaviour of influenza virus type A in persons of greater São Paulo during 1976, 1978 and 1979

Sera of persons of different age groups collected in 1976, 1978 and 1979 were tested for the presence of HI antibodies against various strains of the H3N2 and H1N1 subtypes of influenza virus. The occurrence of infection by H3N2 subtype was recorded during the 1976-1978 period but in 1979, circulation of this subtype of virus was limited. The prevalence of antibody against A/São Paulo/1/78 (H1N1) was significantly higher than that of antibody to A/USSB/90/77 (HIND in 1978. However in 1979 the predominant strain was A/USSR/90/77 (HIND. Persons under 20 years of age were the most affected by H1N1 subtype. Antibodies to H1N1 subtype were detected in sera of individuals older than 20 years in 1976, before the re-emergence of this strain. Serological results indicate that infections by H3N2 subtype in 1978 occurred in 65.4% of young children (0-4 year group). About 47.0% of children from the 0-4 year group had antibodies to H1N1 subtype in 1979. Antibodies to swine influenza virus were detected in 60% of 60+ year old people.

Radiometric studies on the oxidation of (1-14c) fatty acids by drug-susceptible and drug-resistant mycobacteria

A radiometric assay system has been used to study oxidation patterns of (1-14C) fatty acids by drug-susceptible and drug-resistant organisms of the genus Mycobacterium. Two strains of M. tuberculosis susceptible to all drugs, H37Rv and Erdman, were used. Drug-resistant organisms included in this investigation were M. tuberculosis H37Rv resistant to 5 ug/ml isoniazid, M. bovis, M. avium, M. intracellular, M. kansasii and M. chelonei. The organisms were inoculated in sterile reaction vials containing liquid 7H9 medium, 10% ADC enrichment and 1.0 uCi of one of the (1-14C) fatty acids (butyric, hexánoic, octanoic, decanoic, lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic). Vials were incubated at 37°C and the 14CO2 envolved was measured daily for 3 days with a Bactec R-301 instrument. Although each individual organism displayed a different pattern of fatty oxidation, these patterns were not distinctive enough for identification of the organism. No combination of fatty acids nor preferential oxidation of long chain or of short chain fatty acids were able to separate susceptible from resistant organisms. Further investigation with a larger number of drug susceptible mycobacteria including assimilation studies and oxidation of other substrates may be required to achieve a distinction between drug-susceptible and drug-resistant mycobacteria.

Radiometric studies of mycobacterium tuberculosis

An in vitro assay system that included automated radiometric quantification of 14CO2 released as a result of oxidation of 14C- substrates was applied for studying the metabolic activity of M. tuberculosis under various experimental conditions. These experiments included the study of a) mtabolic pathways, b) detection times for various inoculum sizes, c) effect of filtration on reproducibility of results, d) influence of stress environment e) minimal inhibitory concentrations for isoniazid, streptomycin, ethambutol and rifampin, and f) generation times of M. tuberculosis and M. bovis. These organisms were found to metabolize 14C-for-mate, (U-14C) acetate, (U-14C) glycerol, (1-14C) palmitic acid, 1-14C) lauric acid, (U-14C) L-malic acid, (U-14C) D-glucose, and (U-14C) D-glucose, but not (1-14C) L-glucose, (U-14C) glycine, or (U-14C) pyruvate to 14CO2. By using either 14C-for-mate, (1-14C) palmitic acid, or (1-14C) lauric acid, 10(7) organisms/vial could be detected within 24 48 hours and as few as 10 organisms/vial within 16-20 days. Reproducible results could be obtained without filtering the bacterial suspension, provided that the organisms were grown in liquid 7H9 medium with 0.05% polysorbate 80 and homogenized prior to the study. Drugs that block protein synthesis were found to have lower minimal inhibitory concentrations with the radiometric method when compared to the conventional agar dilution method. The mean generation time obtained for M. bovis and different strains of M. tuberculosis with various substrates was 9 ± 1 hours.

Influence of reconstruction parameters for FBP in semiquantification of brain studies with 123I-FPCIT

Brain dopamine transporters imaging by Single Photon Emission Tomography (SPECT) with 123I-FP-CIT has become an important tool in the diagnosis and evaluation of parkinsonian syndromes, since this radiopharmaceutical exhibits high affinity for membrane transporters responsible for cellular reabsorption of dopamine on the striatum. However, Ordered Subset Expectation Maximization (OSEM) is the method recommended in the literature for imaging reconstruction. Filtered Back Projection (FBP) is still used due to its fast processing, even if it presents some disadvantages. The aim of this work is to investigate the influence of reconstruction parameters for FBP in semiquantification of Brain Studies with 123I-FPCIT compared with those obtained with OSEM recommended reconstruction.