N-aminopyrroledione-hydrazonoketene-pyrazolium oxide-pyrazolone rearrangements and pyrazolone tautomerism

Flash vacuum thermolysis (FVT) of 1-(dimethylamino)pyrrole-2,3-diones 5 causes extrusion of CO with formation of transient hydrazonoketenes 7. The transient ketenes 7 are observable in the form of weak bands at 2130 (7a) or 2115 cm(-1) (7b) in the Ar matrix IR spectra resulting from either FVT or photolysis of either 5 or 1,1- dimethylpyrazolium-5- oxides 8, and these absorptions are in excellent agreement with B3LYP/6-31G* frequency calculations. Under FVT conditions the ketenes 7 cyclize to pyrazolium oxides 8, which undergo 1,4-migration of a methyl group to yield 1,4-dimethyl-3-phenylpyrazole-5(4H)-one 9a and 1,4,4-trimethyl-3-phenylpyrazole-5(4H)-one 9b. All three tautomers of 9a have been characterized, viz. the CH form 9a (most stable form in the gas phase, the solid state and solvents of low polarity), the OH form 9a' (metastable solid at room temperature) and the NH form 9a (stable in aprotic dipolar solvents). The isomeric 1,4-dimethyl-5-phenylpyrazole-3(2H)-one 12 tautomerizes to the 3-hydroxypyrazole 12'. The crystal structure of the hydrochloride 14 of 9a'/9a is reported, representing the first structurally characterised example of a protonated 5-hydroxypyrazole.

Methoxy(2-pyridyl)ketene

Matrix photolysis of 3-methoxycarbonyl-1,2,3-triazolo[1,5-a]pyridine (12) affords s-E-2-pyridylketene (4), but flash vacuum thermolysis of 12 gives methoxy(2-pyridyl)ketene (15), predominantly in the s-Z-conformation. Matrix photolysis of 15 affords 2-acetylpyridine. Copyright (C) 2003 John Wiley Sons, Ltd.

Synthesis and complexation properties of some novel lariat-crown ethers

Several new lariat-crown ethers bearing either bridged bisdioxine or tetraoxaadamantane units as chiral substituents are prepared by reacting the corresponding amino-crown ether derivatives with the dimeric alpha-oxoketene, the latter obtained by flash vacuum pyrolysis of a furan-2,3-dione precursor. Complexation properties towards differently charged metal ions are investigated by H-1 NMR titration to obtain complexation constants (K-c-values for potassium/ sodium rhodanides: 480-1100 mol dm(-3)), as well as extraction experiments to explore the metal ion transportation abilities of the new lariat crown derivatives. In particular, a significantly increased ability to transport metal ions from water into chloroform was found with spherical tetraoxaadamantyl derivatives when compared with the free amino-benzocrown ethers.

Protein film voltammetry of Rhodobacter capsulatus xanthine dehydrogenase

Xanthine dehydrogenase (XDH) from the bacterium Rhodobacter capsulatus catalyzes the hydroxylation of xanthine to uric acid with NAD(+) as the electron acceptor. R. capsulatus XDH forms an (alphabeta)(2) heterotetramer and is highly homologous to homodimeric eukaryotic XDHs. The crystal structures of bovine XDH and R. capsulatus XDH showed that the two proteins have highly similar folds; however, R. capsulatus XDH is at least 5 times more active than bovine XDH and, unlike mammalian XDH, does not undergo the conversion to the oxidase form. Here we demonstrate electrocatalytic activity of the recombinant enzyme, expressed in Escherichia coli, while immobilized on an edge plane pyrolytic graphite working electrode. Furthermore, we have determined all redox potentials of the four cofactors (Mo-VI/V, Mo-V/IV, FAD/FADH, FADH/FADH(2) and two distinct [2Fe-2S](2+/+) clusters) using a combination of potentiometric and voltammetric methods. A novel feature identified in catalytic voltammetry of XDH concerns the potential for the onset of catalysis (ca. 400 mV), which is at least 600 mV more positive than that of the highest potential cofactor. This unusual observation is explained on the basis of a pterin-associated oxidative switch during voltammetry that precedes catalysis.

Comparabilidade energética entre sistemas de ciclo de 1 andar e de 2 andares

Este trabalho faz uma análise comparativa do desempenho termodinâmico, num mesmo fluído frigorigéneo, de ciclos frigoríficos em diferentes regimes térmicos, de modo a avaliar as vantagens na utilização da compressão em dois andares sobre a compressão em andar único, para as mesmas temperaturas de evaporação e condensação, nos respectivos permutadores de calor. No estudo o escoamento do fluído é considerado sem perdas de carga, as expansões isentálpicas e as compressões isentrópicas. Os vários rendimentos têm valor unitário de modo a não particularizar o resultado. As temperaturas de regime neste trabalho são -40ºC para a evaporação do fluído e de 40ºC para a sua condensação. As temperaturas intermédias estão no intervalo situado entre -20ºC e 8ºC, com intervalos de 1ºC entre si. Os processos alvo de observação são arrefecimento intermédio (intercooler), remoção do título de vapor à pressão intermédia (flash gas removal), e a combinação dos dois num único processo, com a injecção total de fluído, para o mesmo fluído refrigerante, o NH3 Seguidamente foi analisada a opção em cascata para NH. Foram quantificados valores de COP utilizando compressão seca e compressão húmida. 3/NH3 e em dois fluidos, NH3/CO2 Constatou-se que o processo intercooler e flash gas removal em sistema combinado em compressão seca tem desempenho cerca de 15,5% superior ao ciclo de compressão num só andar, e que a compressão húmida tem melhor desempenho do que a compressão seca, nomeadamente o melhor desempenho na compressão húmida é 11,7% superior ao melhor desempenho na compressão seca.

Lightning Data Observed With Lightning Location System in Portugal

This paper presents an investigation into cloud-to-ground lightning activity over the continental territory of Portugal with data collected by the national Lightning Location System. The Lightning Location System in Portugal is first presented. Analyses about geographical, seasonal, and polarity distribution of cloud-to-ground lightning activity and cumulative probability of peak current are carried out. An overall ground flash density map is constructed from the database, which contains the information of more than five years and almost four million records. This map is compared with the thunderstorm days map, produced by the Portuguese Institute of Meteorology, and with the orographic map of Portugal. Finally, conclusions are duly drawn.

Avaliação ecocardiográfica de doentes propostos para terapêutica de ressincronização: impacto dos índices de dissincronia

Mestrado em Tecnologia de Diagnóstico e Intervenção Cardiovascular - Área de especialização: Ultrassonografia Cardiovascular.

Influência das condições de trabalho na exposição aos fumos de soldadura e efeitos na saúde

Mestrado em Segurança e Higiene do Trabalho.

Contribuição para o planeamento de emergência no concelho da Praia da Vitória: caso de estudo na freguesia da Agualva (Terceira, Açores)

Dissertação de Mestrado, Vulcanologia e Riscos Geológicos, 25 de Novembro de 2013, Universidade dos Açores.

Análise da resistência à fadiga de tubos de aço API 5CT N80 Tipo Q soldados via processo de indução magnética de alta frequência (HFIW)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Exposição a fumo de soldaduras: quais os factores de risco?

Mestrado em Segurança e Higiene no Trabalho.

Notice on a methodology for characterizing emissions of ultrafine particles/nanoparticles in microenvironments

Bearing in mind the potential adverse health effects of ultrafine particles, it is of paramount importance to perform effective monitoring of nanosized particles in several microenvironments, which may include ambient air, indoor air, and also occupational environments. In fact, effective and accurate monitoring is the first step to obtaining a set of data that could be used further on to perform subsequent evaluations such as risk assessment and epidemiologic studies, thus proposing good working practices such as containment measures in order to reduce occupational exposure. This paper presents a useful methodology for monitoring ultrafine particles/nanoparticles in several microenvironments, using online analyzers and also sampling systems that allow further characterization on collected nanoparticles. This methodology was validated in three case studies presented in the paper, which assess monitoring of nanosized particles in the outdoor atmosphere, during cooking operations, and in a welding workshop.

Concepção e instalação de tabelas multifunções para recintos desportivos cobertos

Mestrado em Engenharia Electrotécnica – Sistemas Eléctricos de Energia

Comportamento à fadiga de juntas soldadas de aços tipo 460M com fios fluxados

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

Contribuição para a caracterização da emissão de nanopartículas em processos de soldadura e avaliação de riscos decorrentes do processo

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica Ramo de processos químicos