A dramatic effect of double bond configuration in N-oxy-3-aza Cope rearrangements: a simple synthesis of functionalised allenes

The first examples of low temperature N-oxy-3-aza Cope rearrangements, leading to functionalised allenes are described, where the Z-configuration of the enaminic double bond in the rearranging system proves critical.

Automatic assignment of absolute configuration from 1D NMR data

Opposite enantiomers exhibit different NMR properties in the presence of an external common chiral element, and a chiral molecule exhibits different NMR properties in the presence of external enantiomeric chiral elements. Automatic prediction of such differences, and comparison with experimental values, leads to the assignment of the absolute configuration. Here two cases are reported, one using a dataset of 80 chiral secondary alcohols esterified with (R)-MTPA and the corresponding 1H NMR chemical shifts and the other with 94 13C NMR chemical shifts of chiral secondary alcohols in two enantiomeric chiral solvents. For the first application, counterpropagation neural networks were trained to predict the sign of the difference between chemical shifts of opposite stereoisomers. The neural networks were trained to process the chirality code of the alcohol as the input, and to give the NMR property as the output. In the second application, similar neural networks were employed, but the property to predict was the difference of chemical shifts in the two enantiomeric solvents. For independent test sets of 20 objects, 100% correct predictions were obtained in both applications concerning the sign of the chemical shifts differences. Additionally, with the second dataset, the difference of chemical shifts in the two enantiomeric solvents was quantitatively predicted, yielding r2 0.936 for the test set between the predicted and experimental values.

Desenvolvimento do sistema de tracção de um veículo eléctrico ecológico com travagem regenerativa

Nesta dissertação descreve-se uma metodologia de dimensionamento do sistema de tracção para equipar um veículo eléctrico ecológico (VEECO) com inclusão de um sistema de travagem regenerativa. Apresenta-se uma perspectiva geral de diversas topologias de sistemas de tracção utilizadas nos veículos eléctricos e realiza-se a sua comparação através do estudo e análise dos acionamentos electromecânicos que podem ser utilizados nesses sistemas de tracção eléctrica. Utilizando ferramentas de simulação numérica, estuda-se o modelo matemático de um veículo eléctrico com travagem regenerativa. A partir deste modelo matemático é adoptado uma possível configuração para o seu sistema de tracção eléctrica e são obtidas características teóricas de desempenho do veículo eléctrico, através da análise de testes padrão ao veículo. Em banco de ensaios, constrói-se um sistema de tracção eléctrica que permite a validação experimental do modelo matemático do veículo eléctrico. Para a construção deste banco de ensaios foram concebidos os sistemas de tracção eléctrica, de carga mecânica e de controlo e monitorização do banco de ensaios. A validação experimental realiza-se através dos mesmos testes padrão ao veículo eléctrico, como o teste NEDC (New European Driving Cycle), o teste de aceleração entre 0 e 100km/h e o teste de gradeabilidade. Desenvolve-se o dimensionamento do sistema de tracção eléctrica a equipar o VEECO, através da componente de modelação paramétrica do modelo matemático do veículo eléctrico. Com esta metodologia é adoptado um conjunto de variáveis paramétricas relacionadas com os elementos que constituem o sistema de tracção eléctrica do VEECO. Estuda-se a influência destas variáveis paramétricas nas características de desempenho pretendidas para o VEECO. Como resultado da análise de modelação paramétrica é apresentada uma solução para o sistema de tracção eléctrica do VEECO que cumpre a execução do NEDC, apresenta um tempo de aceleração entre 0 e 100km/h inferior a 10 segundos, supera uma gradeabilidade de 10% e uma autonomia de 200 km. O sistema de tracção do VEECO também permite realizar a travagem regenerativa com rendimento até 33%. Possui controlo de tracção e anti bloqueio da roda motora, através de uma unidade de controlo que permite reduzir a potência transmitida ao veio, quando a velocidade da roda de tracção difere do valor de referência da velocidade do veículo. Os conhecimentos adquiridos através do processo de investigação e desenvolvimento, para a realização da presente dissertação permitem apresentar perspectivas de desenvolvimento futuro com aplicação nos sistemas de tracção de veículos eléctricos rodoviários.

New p-i-n Si : H imager configuration for spatial resolution improvement

Amorphous glass/ZnO-Al/p(a-Si:H)/i(a-Si:H)/n(a-Si1-xCx:H)/Al imagers with different n-layer resistivities were produced by plasma enhanced chemical vapour deposition technique (PE-CVD). An image is projected onto the sensing element and leads to spatially confined depletion regions that can be readout by scanning the photodiode with a low-power modulated laser beam. The essence of the scheme is the analog readout, and the absence of semiconductor arrays or electrode potential manipulations to transfer the information coming from the transducer. The influence of the intensity of the optical image projected onto the sensor surface is correlated with the sensor output characteristics (sensitivity, linearity blooming, resolution and signal-to-noise ratio) are analysed for different material compositions (0.5 < x < 1). The results show that the responsivity and the spatial resolution are limited by the conductivity of the doped layers. An enhancement of one order of magnitude in the image intensity signal and on the spatial resolution are achieved at 0.2 mW cm(-2) light flux by decreasing the n-layer conductivity by the same amount. A physical model supported by electrical simulation gives insight into the image-sensing technique used.

Modelling of n-stage Blumlein stacked lines for bipolar pulse generation

A Blumlein line is a particular Pulse Forming Line, PFL, configuration that allows the generation of high-voltage sub-microsecond square pulses, with the same voltage amplitude as the dc charging voltage, into a matching load. By stacking n Blumlein lines one can multiply in theory by n the input dc voltage charging amplitude. In order to understand the operating behavior of this electromagnetic system and to further optimize its operation it is fundamental to theoretically model it, that is to calculate the voltage amplitudes at each circuit point and the time instant that happens. In order to do this, one needs to define the reflection and transmission coefficients where impedance discontinuity occurs. The experimental results of a fast solid-state switch, which discharges a three stage Blumlein stack, will be compared with theoretical ones.

Syntheses, Molecular Structures, Electrochemical Behavior, Theoretical Study, and Antitumor Activities of Organotin(IV) Complexes Containing 1-(4-Chlorophenyl)-1-cyclopentanecarboxylato Ligands

The organotin(IV) compounds [Me2Sn(L)(2)] (1), [Et(2)sn(L)(2)] (2), [(Bu2Sn)-Bu-n(L)(2)] (3), [(n)Oct(2)Sn(L)(2)] (4), [Ph2Sn(L)(2)] (5), and [PhOSnL](6) (6) have been synthesized from the reactions of 1-(4-chlorophenyl)-1-cyclopentanecarboxylic acid (HL) with the corresponding diorganotin(IV) oxide or dichloride. They were characterized by IR and multinuclear NMR spectroscopies, elemental analysis, cyclic voltammetry, and, for 2, 3, 4 and 6, single crystal X-ray diffraction analysis. While 1-5 are mononuclear diorganotin (IV) compounds, the X-ray diffraction of 6 discloses a hexameric drumlike structure with a prismatic Sn6O6 core. All these complexes undergo irreversible reductions and were screened for their in vitro antitumor activities toward HL-60, BGC-823, Bel-7402, and KB human cancer cell lines. Within the mononuclear compounds, the most active ones (3, 5) are easiest to reduce (least cathodic reduction potentials), while the least active ones (1, 4) are the most difficult to reduce. Structural rearrangements (i.e., Sn-O bond cleavages and trans-to-cis isomerization) induced by reduction, which eventually can favor the bioactivity, are disclosed by theoretical/electrochemical studies.

Theoretical Analysis of Multimodal Four-Wave Mixing in Optical Microwires

Optical fiber microwires (OFMs) are nonlinear optical waveguides that support several spatial modes. The multimodal generalized nonlinear Schrodinger equation (MM-GNLSE) is deduced taking into account the linear and nonlinear modal coupling. A detailed theoretical description of four-wave mixing (FWM) considering the modal coupling is developed. Both, the intramode and the intermode phase-matching conditions is calculated for an optical microwire in a strong guiding regime. Finally, the FWM dynamics is studied and the amplitude evolution of the pump beams, the signal and the idler are analyzed.

O conselho geral: um desafio estratégico à autonomia

Nos últimos vinte e cinco anos o tema da autonomia e da administração e gestão escolar tem ocupado um lugar relevante na agenda política dos sucessivos Governos da República e na preocupação dos diferentes parceiros educativos. Rara tem sido a maioria política que resiste a dar o seu contributo sobre esta matéria, com o objetivo sempre confesso de outorgar maior autonomia às escolas. No enquadramento teórico da nossa investigação começamos por abordar a emergência do conceito de autonomia, nas suas diferentes dimensões e nos seus distintos significados. Não esquecemos também a analise das questões relacionadas com a problemática, cada vez mais atual da regulação múltipla. Analisamos de seguida a evolução da legislação portuguesa, operada a partir da publicação da Lei de Bases do Sistema Educativo com especial destaque às propostas de configuração dos órgãos de Direção e de Gestão das escolas e das competências atribuídas a cada um deles produzido pela CRSE e pelos decretos-leis 43/89, 172/91, 115-A/98 e 75/2008. A investigação empírica teve como objeto de análise dois agrupamentos localizados em concelhos distintos da Área Metropolitana de Lisboa, e procurou determinar se o conselho geral de cada uma dessas unidades orgânicas, assume na totalidade as competências que lhe são conferidas pelo quadro legislativo em vigor, e nessa medida como se articula com os outros órgãos da direção no processo de tomada de decisão. Simultaneamente fizemos o contraponto com a imagem que os intervenientes na gestão intermédia de cada um dos agrupamentos construíram sobre o seu conselho geral e das relações de poder que se estabelecem no interior de cada uma das organizações. Para corresponder aos pressupostos da nossa investigação entrevistaram-se os diretores e os presidentes dos conselhos gerais e facultámos questionários aos docentes que desempenhavam cargos nos dois agrupamentos. Concluímos, em função do que pudemos analisar, que embora o conselho geral veja o seu papel na organização da escola formalmente reconhecido não consegue desempenhar na totalidade as funções que lhe são incumbidas, já que defronta o poder real do diretor e o poder oculto do conselho pedagógico, encontrando dificuldades em libertar-se do reino das sombras.

Planeamento de rede LTE de baixo custo com uso de repetidor

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia de Electrónica e Telecomunicações

A fluorescente bicyclic Calix[4] Arene-Oxacyclophane with planar chirality: Resolution, chiroptical, properties, and absolute configuration.

A new inherently chiral calix[4]arene ICC 1 has been disclosed. The dissymmetry of 1 is generated from a chirality plane in the quinol moiety of a 1,3-bridged bicyclic calix[4]arene. ICC 1 has been resolved by enantioselective HPLC, and the chiroptical properties of both isolated antipodes (pS)-1 and (pR)-1 confirm their enantiomeric nature. The absolute configuration of the (pS)-1/(pR)-1 enantiomeric pair was established through time-dependent density functional theory (TDDFT) calculations of electronic circular dichroism (CD) spectra. (C) 2014 Elsevier Ltd. All rights reserved.

Acylated cyanoimido-complexes trans-[Mo(NCN){NCN(O)R}(DPPE)(2)]Cl and their reactons with electrophiles: Chemical, electrochemical and theoretical study

Treatment of a dichloromethane solution of trans-[Mo(NCN){NCNC(O)R}(dppe)(2)]Cl [R = Me (1a), Et (1b)] (dppe = Ph2PCH2CH2PPh2) with HBF4, [Et3O][BF4] or EtC(O)Cl gives trans-[Mo(NCN)Cl-(dppe)(2)]X [X = BF4 (2a) or Cl (2b)] and the corresponding acylcyanamides NCN(R')C(O)Et (R' = H, Et or C(O)Et). X-ray diffraction analysis of 2a (X = BF4) reveals a multiple-bond coordination of the cyanoimide ligand. Compounds 1 convert to the bis(cyanoimide) trans-[Mo(NCN)(2)(dppe)(2)] complex upon reaction with an excess of NaOMe (with formation of the respective ester). In an aprotic medium and at a Pt electrode, compounds 1 (R = Me, Et or Ph) undergo a cathodically induced isomerization. Full quantitative kinetic analysis of the voltammetric behaviour is presented and allows the determination of the first-order rate constants and the equilibrium constant of the trans to cis isomerization reaction. The mechanisms of electrophilic addition (protonation) to complexes 1 and the precursor trans[Mo(NCN)(2)(dppe)(2)], as well as the electronic structures, nature of the coordination bonds and electrochemical behaviour of these species are investigated in detail by theoretical methods which indicate that the most probable sites of the proton attack are the oxygen atom of the acyl group and the terminal nitrogen atom, respectively.

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.

Electrorheology study of a series of LC cyanobiphenyls: Experimental and theoretical treatment

In this work we study the electro-rheological behaviour of a series of four liquid crystal (LC) cyanobiphenyls with a number of carbon atoms in the alkyl group, ranging from five to eight (5CB–8CB). We present the flow curves for different temperatures and under the influence of an external electric field, ranging from 0 to 3 kV/mm, and the viscosity as a function of the temperature, for the same values of electric field, obtained for different shear rates. Theoretical interpretation of the observed behaviours is proposed in the framework of the continuum theory of Leslie–Ericksen for low molecular weight nematic LCs. In our analysis, the director alignment angle is only a function of the ratio between the shear rate and the square of the electric field – boundary conditions are neglected. By fitting the theoretical model to the experimental data, we are able to determine some viscosity coefficients and the dielectric anisotropy as a function of temperature. To interpret the behaviour of the flow curves near the nematic–isotropic transitions, we apply the continuum theory of Olmsted–Goldbart, which extends the theory of Leslie–Ericksen to the case where the degree of alignment of the LC molecules can also vary.