Elaboração de pós de ferrita de cobalto, CoFe2O4, nanoestruturados e hierarquizados: influência da morfologia sobre a detecção e oxidação catalítica de gases poluentes

This thesis is part of research on new materials for catalysis and gas sensors more active, sensitive, selective. The aim of this thesis was to develop and characterize cobalt ferrite in different morphologies, in order to study their influence on the electrical response and the catalytic activity, and to hierarchize these grains for greater diffusivity of gas in the material. The powders were produced via hydrothermal and solvothermal, and were characterized by thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, transmission electron microscopy (electron diffraction, highresolution simulations), and energy dispersive spectroscopy. The catalytic and electrical properties were tested in the presence of CO and NO2 gases, the latter in different concentrations (1-100 ppm) and at different temperatures (room temperature to 350 ° C). Nanooctahedra with an average size of 20 nm were obtained by hydrothermal route. It has been determined that the shape of the grains is mainly linked to the nature of the precipitating agent and the presence of OH ions in the reaction medium. By solvothermal method CoFe2O4 spherical powders were prepared with grain size of 8 and 20 nm. CoFe2O4 powders exhibit a strong response to small amounts of NO2 (10 ppm to 200 ° C). The nanooctahedra have greater sensitivity than the spherical grains of the same size, and have smaller response time and shorter recovery times. These results were confirmed by modeling the kinetics of response and recovery of the sensor. Initial tests of catalytic activity in the oxidation of CO between temperatures of 100 °C and 350 °C show that the size effect is predominant in relation the effect of the form with respect to the conversion of the reaction. The morphology of the grains influence the rate of reaction. A higher reaction rate is obtained in the presence of nanooctahedra. In order to improve the detection and catalytic properties of the material, we have developed a methodology for hierarchizing grains which involves the use of carbonbased templates.

Determinação de CD, PB, e TL em água produzida por HR-CS GF AAS após extração em ponto nuvem

Produced water is a major problem associated with the crude oil extraction activity. The monitoring of the levels of metals in the waste is constant and requires the use of sensitive analytical techniques. However, the determination of trace elements can often require a pre-concentration step. The objective of this study was to develop a simple and rapid analytical method for the extraction and pre-concentration based on extraction phenomenon cloud point for the determination of Cd, Pb and Tl in produced water samples by spectrometry of high resolution Absorption source continues and atomization graphite furnace. The Box Behnken design was used to obtain the optimal condition of extraction of analytes. The factors were evaluated: concentration of complexing agent (o,o-dietilditilfosfato ammonium, DDTP), the concentration of hydrochloric acid and concentration of surfactant (Triton X -114). The optimal condition obtained through extraction was: 0,6% m v-1 DDTP, HCl 0,3 mol L-1 and 0,2% m v-1 of Triton X - 114 for Pb; 0,7% m v-1 DDTP, HCl 0,8 mol L-1 and 0,2% m v-1 Triton X-114 for Cd. For Tl was evidenced that best extraction condition occurs with no DDTP, the extraction conditions were HCl 1,0 mol L-1 e 1,0% m v-1 de Triton X - 114. The limits of detection for the proposed method were 0,005 µg L-1 , 0,03 µg L-1 and 0,09 µg L-1 to Cd, Pb and Tl, Respectively. Enrichment factors Were greater than 10 times. The method was applied to the water produced in the Potiguar basin, and addition and recovery tests were performed, and values were between 81% and 120%. The precision was expressed with relative standard deviation (RSD) is less than 5%

Desenvolvimento de metodologia de extração e pré-concentração utilizando sistema microemulsionado para determinação de Cd, Co, Cu, Ni, Pb e Tl em águas naturais e produzidas por HR-CS AAS

The determination and monitoring of metallic contaminants in water is a task that must be continuous, leading to the importance of the development, modification and optimization of analytical methodologies capab le of determining the various metal contaminants in natural environments, because, in many cases, the ava ilable instrumentation does not provide enough sensibility for the determination of trace values . In this study, a method of extraction and pre- concentration using a microemulsion system with in the Winsor II equilibrium was tested and optimized for the determination of Co, Cd, P b, Tl, Cu and Ni through the technique of high- resolution atomic absorption spectrometry using a continuum source (HR-CS AAS). The optimization of the temperature program for the graphite furnace (HR-CS AAS GF) was performed through the pyrolysis and atomization curves for the analytes Cd, Pb, Co and Tl with and without the use of different chemical modifiers. Cu and Ni we re analyzed by flame atomization (HR-CS F AAS) after pre-concentr ation, having the sample introduction system optimized for the realization of discrete sampling. Salinity and pH levels were also analyzed as influencing factors in the efficiency of the extraction. As final numbers, 6 g L -1 of Na (as NaCl) and 1% of HNO 3 (v/v) were defined. For the determination of the optimum extraction point, a centroid-simplex statistical plan was a pplied, having chosen as the optimum points of extraction for all of the analytes, the follo wing proportions: 70% aqueous phase, 10% oil phase and 20% co-surfactant/surfactant (C/S = 4). After extraction, the metals were determined and the merit figures obtained for the proposed method were: LOD 0,09, 0,01, 0,06, 0,05, 0,6 and 1,5 μg L -1 for Pb, Cd, Tl, Co, Cu and Ni, re spectively. Line ar ranges of ,1- 2,0 μg L -1 for Pb, 0,01-2,0 μg L -1 for Cd, 1,0 - 20 μg L -1 for Tl, 0,1-5,0 μg L -1 for Co, 2-200 μg L -1 and for Cu e Ni 5-200 μg L -1 were obtained. The enrichment factors obtained ranged between 6 and 19. Recovery testing with the certified sample show ed recovery values (n = 3, certified values) after extraction of 105 and 101, 100 and 104% for Pb, Cd, Cu and Ni respectively. Samples of sweet waters of lake Jiqui, saline water from Potengi river and water produced from the oil industry (PETROBRAS) were spiked and the recovery (n = 3) for the analytes were between 80 and 112% confirming th at the proposed method can be used in the extraction. The proposed method enabled the sepa ration of metals from complex matrices, and with good pre-concentration factor, consistent with the MPV (allowed limits) compared to CONAMA Resolution No. 357/2005 which regulat es the quality of fresh surface water, brackish and saline water in Brazil.

Contribuições para o estudo do código neural

Os recentes avanços técnicos das duas últimas décadas para o registro de sinais neuroeletrofisiológicos foram essenciais para que se testassem hipóteses há muito propostas acerca de como células nervosas processam e armazenam informação. No entanto, ao permitir maior detalhamento dos dados coletados, as novas tecnologias levam inevitavelmente ao aumento de sua complexidade estatística e, consequentemente, à necessidade de novas ferramentas matemático-computacionais para sua análise. Nesta tese, apresentamos novos métodos para a análise de dois componentes fundamentais nas atuais teorias da codificação neural: (1) assembleias celulares, definidas pela co-ativação de subgrupos neuronais; e (2) o padrão temporal de atividade de neurônios individuais. Em relação a (1), desenvolvemos um método baseado em análise de componentes independentes para identificar e rastrear padrões de co-ativação significativos com alta resolução temporal. Superamos limitações de métodos anteriores, ao efetivamente isolar assembleias e abrir a possibilidade de analisar simultaneamente grandes populações neuronais. Em relação a (2), apresentamos uma nova técnica para a extração de padrões de atividade em trens de disparo baseada na decomposição wavelet. Demonstramos, por meio de simulações e de aplicação a dados reais, que nossa ferramenta supera as mais utilizadas atualmente para decodificar respostas de neurônios e estimar a informação de Shannon entre trens de disparos e estímulos externos.

Análise wavelet e modelo de manchas em curvas de luz estelares dos telescópios espaciais Kepler e CoRoT

Analogous to sunspots and solar photospheric faculae, which visibility is modulated by stellar rotation, stellar active regions consist of cool spots and bright faculae caused by the magnetic field of the star. Such starspots are now well established as major tracers used to estimate the stellar rotation period, but their dynamic behavior may also be used to analyze other relevant phenomena such as the presence of magnetic activity and its cycles. To calculate the stellar rotation period, identify the presence of active regions and investigate if the star exhibits or not differential rotation, we apply two methods: a wavelet analysis and a spot model. The wavelet procedure is also applied here to study pulsation in order to identify specific signatures of this particular stellar variability for different types of pulsating variable stars. The wavelet transform has been used as a powerful tool for treating several problems in astrophysics. In this work, we show that the time-frequency analysis of stellar light curves using the wavelet transform is a practical tool for identifying rotation, magnetic activity, and pulsation signatures. We present the wavelet spectral composition and multiscale variations of the time series for four classes of stars: targets dominated by magnetic activity, stars with transiting planets, those with binary transits, and pulsating stars. We applied the Morlet wavelet (6th order), which offers high time and frequency resolution. By applying the wavelet transform to the signal, we obtain the wavelet local and global power spectra. The first is interpreted as energy distribution of the signal in time-frequency space, and the second is obtained by time integration of the local map. Since the wavelet transform is a useful mathematical tool for nonstationary signals, this technique applied to Kepler and CoRoT light curves allows us to clearly identify particular signatures for different phenomena. In particular, patterns were identified for the temporal evolution of the rotation period and other periodicity due to active regions affecting these light curves. In addition, a beat-pattern vii signature in the local wavelet map of pulsating stars over the entire time span was also detected. The second method is based on starspots detection during transits of an extrasolar planet orbiting its host star. As a planet eclipses its parent star, we can detect physical phenomena on the surface of the star. If a dark spot on the disk of the star is partially or totally eclipsed, the integrated stellar luminosity will increase slightly. By analyzing the transit light curve it is possible to infer the physical properties of starspots, such as size, intensity, position and temperature. By detecting the same spot on consecutive transits, it is possible to obtain additional information such as the stellar rotation period in the planetary transit latitude, differential rotation, and magnetic activity cycles. Transit observations of CoRoT-18 and Kepler-17 were used to implement this model.

Análise wavelet em curvas de luz estelares de sistemas binários da missão espacial CoRoT

Binary systems are key environments to study the fundamental properties of stars. In this work, we analyze 99 binary systems identified by the CoRoT space mission. From the study of the phase diagrams of these systems, our sample is divided into three groups: those whose systems are characterized by the variability relative to the binary eclipses; those presenting strong modulations probably due to the presence of stellar spots on the surface of star; and those whose systems have variability associated with the expansion and contraction of the surface layers. For eclipsing binary stars, phase diagrams are used to estimate the classification in regard to their morphology, based on the study of equipotential surfaces. In this context, to determine the rotation period, and to identify the presence of active regions, and to investigate if the star exhibits or not differential rotation and study stellar pulsation, we apply the wavelet procedure. The wavelet transform has been used as a powerful tool in the treatment of a large number of problems in astrophysics. Through the wavelet transform, one can perform an analysis in time-frequency light curves rich in details that contribute significantly to the study of phenomena associated with the rotation, the magnetic activity and stellar pulsations. In this work, we apply Morlet wavelet (6th order), which offers high time and frequency resolution and obtain local (energy distribution of the signal) and global (time integration of local map) wavelet power spectra. Using the wavelet analysis, we identify thirteen systems with periodicities related to the rotational modulation, besides the beating pattern signature in the local wavelet map of five pulsating stars over the entire time span.

Análise wavelet em curvas de luz estelares de sistemas binários da missão espacial CoRoT

Binary systems are key environments to study the fundamental properties of stars. In this work, we analyze 99 binary systems identified by the CoRoT space mission. From the study of the phase diagrams of these systems, our sample is divided into three groups: those whose systems are characterized by the variability relative to the binary eclipses; those presenting strong modulations probably due to the presence of stellar spots on the surface of star; and those whose systems have variability associated with the expansion and contraction of the surface layers. For eclipsing binary stars, phase diagrams are used to estimate the classification in regard to their morphology, based on the study of equipotential surfaces. In this context, to determine the rotation period, and to identify the presence of active regions, and to investigate if the star exhibits or not differential rotation and study stellar pulsation, we apply the wavelet procedure. The wavelet transform has been used as a powerful tool in the treatment of a large number of problems in astrophysics. Through the wavelet transform, one can perform an analysis in time-frequency light curves rich in details that contribute significantly to the study of phenomena associated with the rotation, the magnetic activity and stellar pulsations. In this work, we apply Morlet wavelet (6th order), which offers high time and frequency resolution and obtain local (energy distribution of the signal) and global (time integration of local map) wavelet power spectra. Using the wavelet analysis, we identify thirteen systems with periodicities related to the rotational modulation, besides the beating pattern signature in the local wavelet map of five pulsating stars over the entire time span.

Algorithms for super-resolution of images based on Sparse Representation and Manifolds

lmage super-resolution is defined as a class of techniques that enhance the spatial resolution of images. Super-resolution methods can be subdivided in single and multi image methods. This thesis focuses on developing algorithms based on mathematical theories for single image super­ resolution problems. lndeed, in arder to estimate an output image, we adopta mixed approach: i.e., we use both a dictionary of patches with sparsity constraints (typical of learning-based methods) and regularization terms (typical of reconstruction-based methods). Although the existing methods already per- form well, they do not take into account the geometry of the data to: regularize the solution, cluster data samples (samples are often clustered using algorithms with the Euclidean distance as a dissimilarity metric), learn dictionaries (they are often learned using PCA or K-SVD). Thus, state-of-the-art methods still suffer from shortcomings. In this work, we proposed three new methods to overcome these deficiencies. First, we developed SE-ASDS (a structure tensor based regularization term) in arder to improve the sharpness of edges. SE-ASDS achieves much better results than many state-of-the- art algorithms. Then, we proposed AGNN and GOC algorithms for determining a local subset of training samples from which a good local model can be computed for recon- structing a given input test sample, where we take into account the underlying geometry of the data. AGNN and GOC methods outperform spectral clustering, soft clustering, and geodesic distance based subset selection in most settings. Next, we proposed aSOB strategy which takes into account the geometry of the data and the dictionary size. The aSOB strategy outperforms both PCA and PGA methods. Finally, we combine all our methods in a unique algorithm, named G2SR. Our proposed G2SR algorithm shows better visual and quantitative results when compared to the results of state-of-the-art methods.

Avaliação do impacto das condições de operação na qualidade do sinal : processamento de dados de reflexão sísmica de multicanal

Através do processamento de dados sísmicos convertem-se registos de campo em secções sísmicas com significado geológico, que revelam informações e ajudam a delinear as camadas geológicas do subsolo e identificar estruturas soterradas. Portanto, a interpretação dos dados sísmicos só é boa se o processamento também o for. Este trabalho é resultado de um estágio curricular na empresa de prospecção geofísica GeoSurveys, que consistiu principalmente em processar 18 linhas de dados de sísmica de reflexão multicanal de alta resolução adquiridas na ilha de Pulau Tekong em Singapura, que têm como finalidade investigação do solo da baia desta mesma ilha. Estes dados foram cedidos à GeoSurveys para fins académicos, caso em que se inclui esta dissertação. Para atingir os objectivos propostos que consistiam em avaliar o impacto das condições de operação na qualidade do sinal sísmico e interpretação das linhas, fez-se o processamento das linhas utilizando um fluxo processamento padrão utilizado na empresa, com recurso ao software Radex Pro. Este fluxo de processamento tem como mais-valia o método de correcções estáticas, o UHRS trim statics, além das técnicas habituais utilizadas para melhorar a resolução das secções sísmicas como é o caso da desconvolução, a atenuação de ruído através do stacking, correcções de NMO, e migração, entre outras técnicas. A interpretação das linhas sísmicas processadas foi feita no software Kingdom Suite (IHS), através da distinção da configuração interna dos reflectores em cada secção sísmica, estabelecendo deste modo as principais unidades sismo-estratigráficas e identificando as zonas de interface que delimitam os horizontes principais. Foi feito ainda um estudo geológico sumário da área de pesquisa e da evolução geodinâmica da região.

Chemical characterization and evaluation of biological activity of Cynara cardunculus extractable compounds

The Mediterranean species Cynara cardunculus L. is recognized in the traditional medicine, for their hepatoprotective and choleretic effects. Biomass of C. cardunculus L. var. altilis (DC), or cultivated cardoon, may be explored not only for the production of energy and pulp fibers, but also for the extraction of bioactive compounds. The chemical characterization of extractable components, namely terpenic and phenolic compounds, may valorize the cultivated cardoon plantation, due to their antioxidant, antitumoral and antimicrobial activities. In this study, the chemical composition of lipophilic and phenolic fractions of C. cardunculus L. var. altilis (DC), cultivated in the south of Portugal (Baixo Alentejo region) was characterized in detail, intending the integral valorization of its biomass. The biological activity of cultivated cardoon extracts was evaluated in terms of antioxidant, human tumor cell antiproliferative and antibacterial effects. Gas chromatography-mass spectrometry (GC-MS) was used for the chemical analysis of lipophilic compounds. Sixty-five lipophilic compounds were identified, from which 1 sesquiterpene lactone and 4 pentacyclic triterpenes were described, for the first time, as cultivated cardoon components, such as: deacylcynaropicrin, acetates of β- and α-amyrin, lupenyl acetate and ψ-taraxasteryl acetate. Sesquiterpene lactones were the major family of lipophilic components of leaves (≈94.5 g/kg), mostly represented by cynaropicrin (≈87.4 g/kg). Pentacyclic triterpenes were also detected, in considerably high contents, in the remaining parts of cultivated cardoon, especially in the florets (≈27.5 g/kg). Taraxasteryl acetate was the main pentacyclic triterpene (≈8.9 g/kg in florets). High pressure liquid chromatography-mass spectrometry (HPLC-MS) was utilized for the chemical analysis of phenolic compounds. Among the identified 28 phenolic compounds, eriodictyol hexoside was reported for the first time as C. cardunculus L. component, and 6 as cultivated cardoon components, namely 1,4-di-O-caffeoylquinic acid, naringenin 7-O-glucoside, naringenin rutinoside, naringenin, luteolin acetylhexoside and apigenin acetylhexoside. The highest content of the identified phenolic compounds was observed in the florets (≈12.6 g/kg). Stalks outer part contained the highest hydroxycinnamic acids abundance (≈10.3 g/kg), and florets presented the highest flavonoids content (≈10.3 g/kg). The antioxidant activity of phenolic fraction was examined through 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging assay. Stalks outer part, and receptacles and bracts extracts demonstrated the highest antioxidant effect on DPPH (IC50 of 34.35 μg/mL and 35.25 μg/mL, respectively). (cont.) abstract (cont.) The DPPH scavenging effect was linearly correlated with the total contents of hydroxycinnamic acids (r = -0.990). The in vitro antiproliferative activity of cultivated cardoon lipophilic and phenolic extracts was evaluated on a human tumor cells line of triple-negative breast cancer (MDA-MB-231), one of the most refractory human cancers to conventional therapeutics. After 48 h of exposition, leaves lipophilic extract showed higher inhibitory effect (IC50 = 10.39 μg/mL) than florets lipophilic extract (IC50 = 315.22 μg/mL), upon MDA-MB-231 cellular viability. Pure compound of cynaropicrin, representative of the main compound identified in leaves lipophilic extract, also prevented the cell proliferation of MDA-MB-231 (IC50 = 17.86 μM). MDA-MB-231 cells were much more resistant to the 48 h- treatment with phenolic extracts of stalks outer part (IC50 = 3341.20 μg/mL) and florets (IC50 > 4500 μg/mL), and also with the pure compound of 1,5-di-O-caffeoylquinic acid (IC50 = 1741.69 μM). MDA-MB-231 cells were exposed, for 48 h, to the respective IC50 concentrations of leaves lipophilic extract and pure compound of cynaropicrin, in order to understand their ability in modelling cellular responses, and consequently important potentially signaling pathways for the cellular viability decrease. Leaves lipophilic extract increased the caspase-3 enzymatic activity, contrarily to pure compound of cynaropicrin. Additionally, leaves lipophilic extract and pure compound of cynaropicrin caused G2 cell cycle arrest, possibly by upregulating the p21Waf1/Cip1 and the accumulation of phospho-Tyr15-CDK1 and cyclin B1. The inhibitory effects of leaves lipophilic extract and cynaropicrin pure compound, against the MDA-MB-231 cell proliferation, may also be related to the downregulation of phospho-Ser473-Akt. The antibacterial activity of cultivated cardoon lipophilic and phenolic extracts was assessed, for the first time, on two multidrug-resistant bacteria, such as the Gram-negative Pseudomonas aeruginosa PAO1 and the Gram-positive methicillin-resistant Staphylococcus aureus (MRSA), two of the main bacteria responsible for health care-associated infections. Accordingly, the minimum inhibitory concentrations (MIC) were determined. Lipophilic and phenolic extracts of florets did not have antibacterial activity on P. aeruginosa PAO1 and MRSA (MIC > 2048 μg/mL). Leaves lipophilic extract did not prevent the P. aeruginosa PAO1 growth, but pure compound of cynaropicrin was slightly active (MIC = 2048 μg/mL). Leaves lipophilic extract and pure compound of cynaropicrin blocked MRSA growth (MIC of 1024 and 256 μg/mL, respectively). The scientific knowledge revealed in this thesis, either by the chemical viewpoint, or by the biological viewpoint, contributes for the valorization of C. cardunculus L. var. altilis (DC) biomass. Cultivated cardoon has potential to be exploited as source of bioactive compounds, in conciliation with other valorization pathways, and Portuguese traditional cheeses manufacturing.

Caracterização geológica e geofísica da área do porto da Figueira da Foz

No âmbito de um projeto realizado para a Administração Portuária do Porto da Figueira da Foz, foram recolhidos dados geofísicos no offshore da costa da Figueira da Foz, utilizando um sistema combinado de sonar de varrimento lateral e de sísmica de alta resolução com o objetivo de compreender a distribuição de sedimentos ao longo do fundo marinho e assim entender melhor a sua origem. Os dados de varrimento lateral foram processados, analisados e representados em mosaicos recorrendo ao software integrado TRINTON Prespective. Foram colhidas 10 amostras de sedimentos de fundo que foram analisadas do ponto de vista granulométrico e que foram usadas para a calibração dos mosaicos do sonar de varrimento lateral de modo a produzir um mapa semi-quantitativo de classificação dos sedimentos de fundo. Os dados de reflexão sísmica foram processados e analisados através dos softwares SPW e RadExPro. Os mapas de sonar de varrimento lateral produzidos (mosaicos) mostram uma relação entre o tamanho de grão e composição dos depósitos de plataforma interna e os processos geológicos que ocorrem na zona costeira adjacente. Também se verifica uma relação entre a orientação da costa e a sua consequente exposição às ondas incidentes, e como isso afeta e altera a distribuição do tamanho grão. Neste contexto, a interpretação combinada dos mosaicos do sonar de varrimento lateral com os dados de granulometria e a batimetria dos sedimentos permitiram uma cartografia interpretativa detalhada da morfologia do mar, uma melhor compreensão do controlo da linha costeira na propagação das ondas e correntes e, por conseguinte, na transferência de sedimento no litoral. Os dados de sísmica permitem ainda verificar a espessura das várias camadas geológicas em profundidade.

(E)-2-[2-(2-Aminofenil)vinil]-1-metilquinolin-4(1H)-ona como precursor de novos compostos heterociclicos

Esta dissertação reporta a síntese de novos derivados de 4-quinolonas com potencial atividade biológica e está dividida em 3 capítulos. No primeiro capítulo é feita uma breve introdução aos compostos do tipo 4quinolona, azepina e indol, focando a nomenclatura, atividade biológica e métodos de síntese mais comuns deste tipo de compostos, e é apresentada a nomenclatura dos compostos sintetizados ao longo deste trabalho. No segundo capítulo são descritas as metodologias desenvolvidas para obtenção dos compostos pretendidos. Foram sintetizados novos derivados de 4-quinolonas via reações de N-metilação seguida de ciclização in situ da (E)-N(2-acetilfenil)-3-(2-nitrofenil)acrilamida, via reações de redução da 1-metil-2-[2(2-nitrofenil)vinil]quinolin-4(1H)-ona e reações de halogenação da 1-metil-2-[2(2-nitrofenil)vinil]quinolin-4(1H)-ona e da 2-[2-(2-aminofenil)vinil]-1metilquinolin-4(1H)-ona. Posteriormente, fizeram-se estudos de reatividade da 1-metil-2-[2-(2-nitrofenil)vinil]quinolin-4(1H)-ona e da 2-[2-(2-aminofenil)vinil]-3bromo-1-metilquinolin-4(1H)-ona. Na reação de redução in situ seguida de ciclização intramolecular da 1-metil-2-[2-(2-nitrofenil)vinil]quinolin-4(1H)-ona obteve-se a 2-(1H-indol-2-il)-1-metilquinolin-4(1H)-ona. Partindo da 2-[2-(2aminofenil)vinil]-3-bromo-1-metilquinolin-4(1H)-ona via reações de BuchwaldHartwig obteve-se a 11-metil-5H-benzo[6,7]azepino[3,2-b]quinolin-6(11H)-ona. Novas N-[2-(2-(3-bromo-1-metil-4-oxo-1,4-di-hidroquinolin-2il)vinil)fenil]alquilamidas foram obtidas via reações de acilação da 2-[2-(2aminofenil)vinil]-3-bromo-1-metilquinolin-4(1H)-ona em piridina seca usando diferentes cloretos de acilo. Numa tentativa de ciclização intramolecular da N[2-(2-(3-bromo-1-metil-4-oxo-1,4-di-hidroquinolin-2-il)vinil)fenil]-hexanamida via reação de Ullmann intramolecular foi obtida a 2-(1-hexanoil-1H-indol-2-il)-1metilquinolin-4(1H)-ona. Após a descrição detalhada das metodologias de síntese são apresentadas as principais conclusões deste trabalho e perspectivas futuras. Por último, no terceiro capítulo, são apresentados os procedimentos experimentais usados para obtenção dos compostos sintetizados e os dados relativos à sua caracterização estrutural, que foi sendo discutida ao longo do segundo capítulo. Os compostos sintetizados foram caracterizados por espetroscopia de ressonância magnética nuclear monodimensional (1H e 13C) e bidimensional (HSQC, HMBC) e por espetrometria de massa e sempre que possível por espetrometria de massa de alta resolução.

Uma contribuição para a medição de distorções harmônicas e inter-harmônicas em instalações de geração fotovoltaica

Dissertação (mestrado)— Universidade de Brasília, Faculdade de Tecnologia, Departamento de Engenharia Elétrica, 2015.

Diagnóstico de rejeição por análise de potenciais tardios em doentes transplantados ao coração

Introdução: A rejeição do transplante cardíaco leva a alterações miocárdicas que originam zonas de condução lenta e fragmentada. O ECG de alta resolução é um possível método de estratificação de risco para o diagnóstico da rejeição. Objetivo: Elaborar um Score de Risco preditor de episódios de rejeição, recorrendo aos dados do ECG alta Resolução. População e Métodos: Estudaram-se 28 pacientes transplantados ao coração. Numa primeira fase, tendo em conta o diagnóstico de Rejeição aguda, dividimos a nossa amostra em dois grupos (5 pacientes com rejeição e 23 pacientes sem rejeição). Foram recolhidos dados relativos a características clínicas, eletrocardiográficas, ecocardiográficas e hemodinâmicas dos pacientes no dia do registo. Obtiveram-se dados relativos às Biópsias anteriores, que numa segunda fase, permitiram dividir a amostra tendo em conta o diagnóstico de rejeição em pelo menos uma Biópsia realizada durante o período de seguimento (18 pacientes com rejeição e 10 sem rejeição). Resultados: Para a Rejeição aguda, (prevalência = 17.9%), verificamos que o único critério a revelar associação foi a fibrose miocárdica, evidenciando um aumento do risco de rejeição aguda 19 vezes maior quando presente no ECG. Esta variável demonstrou uma forte capacidade para discriminar os doentes com e sem rejeição (área sob a curva=0.81; p=0.03). Para a Rejeição pm1, (prevalência=64.2%), um maior número de variáveis demonstrou associação com este quadro. Formulámos um Score, constituído pelas variáveis: fibrose, LAS40 e RMS40, aplicado aos 28 elementos da nossa amostra. A associação de fibrose miocárdica (no ECG), valores crescentes da LAS40 e valores decrescentes da RMS40 (no ECG de alta resolução), tem uma excelente capacidade para distinguir os doentes com e sem rejeição (área sob a curva= 0.82; p <0.01), assumindo um ponto de corte de sensibilidade=83.3% e especificidade=60%. Conclusão: O ECG de alta resolução é uma ferramenta eficaz para distinguir os doentes com e sem rejeição. Apesar da sua utilidade estar camuflada para a Rejeição Aguda, apresenta grande valor na previsão de pelo menos um processo de rejeição tendo em conta um follow-up de 8 anos (Rejeição pm1). Julgamos ser útil a incorporação do nosso Score de Probabilidades, para o estudo dos doentes transplantados ao coração na prática clínica diária.

Síntese e caracterização de catalisadores nanométricos de LaSrNiO4 para aplicação em dessulfurização de tiofeno

The mixed metal oxides constitute an important class of catalytic materials widely investigated in different fields of applications. Studies of rare earth nickelates have been carried by several researchers in order to investigate the structural stability afforded by oxide formed and the existence of catalytic properties at room temperature. So, this study aims synthesize the nanosized catalyst of nickelate of lanthanum doped with strontium (La(1-x)SrxNiO4-d; x = 0,2 and 0,3), through the Pechini method and your characterization for subsequent application in the desulfurization of thiophene reaction. The precursor solutions were calcined at 300ºC/2h for pyrolysis of polyester and later calcinations occurred at temperatures of 500 - 1000°C. The resulting powders were characterized by thermogravimetric analysis (TG / DTG), surface area for adsorption of N2 by BET method, X-ray diffraction (XRD), scanning electron microscopy (HR_SEM) and spectrometry dispersive energy (EDS). The results of XRD had show that the perovskites obtained consist of two phases (LSN and NiO) and from 700ºC have crystalline structure. The results of SEM evidenced the obtainment of nanometric powders. The results of BET show that the powders have surface area within the range used in catalysis (5-50m2/g). The characterization of active sites was performed by reaction of desulfurization of thiophene at room temperature and 200ºC, the relation F/W equal to 0,7 mol h-1mcat -1. The products of the reaction were separated by gas chromatography and identified by the selective detection PFPD sulfur. All samples had presented conversion above 95%