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.

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.

Asymmetric synthesis of N-aryl aziridines

The reactions of a variety of N-arylhydroxamates as nitrogen transfer reagents to acryloyl derivatives of (−)-8-phenylmenthol, (−)-quinine and (−)-Oppolzer’s sultam acting as Michael acceptors was studied. Poor to modest diastereoselection was observed in the formation of aziridines. The absolute structure of one of the pure diastereomers secured from Oppolzer’s auxiliary was established by X-ray crystallography and hence the absolute configuration of the derived methyl-N-phenylaziridine-2-carboxylate could be assigned. Whilst only poor facial selectivity was observed for chiral hydroxamic acid prepared from dehydroabietic acid, moderate to good enantioselection of aziridines could be achieved with the chiral quaternary salts based on cinchona alkaloids, especially with that of cinchonine. A model is presented to explain the origin of enantioselection and a mechanism is proposed for the aziridination reaction.

Palaeomagnetism, rock magnetism and AMS of the Cabo Magmatic Province, NE Brazil, and the opening of South Atlantic

P>Reconstruction of the South Atlantic opening has long been a matter of debate and several models have been proposed. One problem in tracing properly the Atlantic history arises from the existence of a long interval without geomagnetic reversals, the Cretaceous Normal Superchron, for which ages are difficult to assign. Palaeomagnetism may help in addressing this issue if high-quality palaeomagnetic poles are available for the two drifting continental blocks, and if precise absolute ages are available. In this work we have investigated the Cabo Magmatic Province, northeastern Brazil, recently dated at 102 +/- 1 Ma (zircon fission tracks, Ar39/Ar40). All volcanic and plutonic rocks showed stable thermal and AF demagnetization patterns, and exhibit primary magnetic signatures. AMS data also support a primary origin for the magnetic fabric and is interpreted to be contemporaneous of the rock formation. The obtained pole is located at 335.9 degrees E/87.9 degrees S (N = 24; A(95) = 2.5; K = 138) and satisfies modern quality criteria, resulting in a reference pole for South America at similar to 100 Ma. This new pole also gives an insight to test and discuss the kinematic models currently proposed for the South Atlantic opening during mid-Cretaceous.

Stratification of the earth beneath the Azores from P and S receiver functions

Seismic recordings of IRIS/IDA/GSN station CMLA and of several temporary stations in the Azores archipelago are processed with P and S receiver function (PRF and SRF) techniques. Contrary to regional seismic tomography these methods provide estimates of the absolute velocities and of the Vp/Vs ratio up to a depth of similar to 300 km. Joint inversion of PRFs and SRFs for a few data sets consistently reveals a division of the subsurface medium into four zones with a distinctly different Vp/Vs ratio: the crust similar to 20 km thick with a ratio of similar to 1.9 in the lower crust, the high-Vs mantle lid with a strongly reduced VpNs velocity ratio relative to the standard 1.8, the low-velocity zone (LVZ) with a velocity ratio of similar to 2.0, and the underlying upper-mantle layer with a standard velocity ratio. Our estimates of crustal thickness greatly exceed previous estimates (similar to 10 km). The base of the high-Vs lid (the Gutenberg discontinuity) is at a depth of-SO km. The LVZ with a reduction of S velocity of similar to 15% relative to the standard (IASP91) model is terminated at a depth of similar to 200 km. The average thickness of the mantle transition zone (TZ) is evaluated from the time difference between the S410p and SKS660p, seismic phases that are robustly detected in the S and SKS receiver functions. This thickness is practically similar to the standard IASP91 value of 250 km. and is characteristic of a large region of the North Atlantic outside the Azores plateau. Our data are indicative of a reduction of the S-wave velocity of several percent relative to the standard velocity in a depth interval from 460 to 500 km. This reduction is found in the nearest vicinities of the Azores, in the region sampled by the PRFs, but, as evidenced by SRFs, it is missing at a distance of a few hundred kilometers from the islands. We speculate that this anomaly may correspond to the source of a plume which generated the Azores hotspot. Previously, a low S velocity in this depth range was found with SRF techniques beneath a few other hotspots.

Exercício físico e cancro da mama: uma revisão

Introdução – Os efeitos fisiológicos da atividade física e do treino são atualmente motivo de extensa investigação cujos resultados mostraram já de forma incontroversa os seus benefícios em diferentes condições clínicas. Diferentes estudos mostraram já os efeitos benéficos do exercício regular de intensidade leve a moderada na diminuição do risco de cancro, bem como na aptidão física de indivíduos portadores de cancro, submetidos ou não a cirurgia. A prescrição do exercício mais adequado para a sua maior eficácia na melhoria da aptidão física e para a diminuição da fadiga não é, no entanto, ainda consensual. O objetivo deste estudo foi o de rever o conhecimento atual sobre os benefícios do exercício físico em sobreviventes de cancro da mama, bem como sistematizar as linhas orientadoras atuais para a prescrição do exercício físico na referida população. Metodologia – Recorreu-se a uma revisão da literatura, tendo como base as palavras-chave: cancro da mama, sobreviventes de cancro da mama, risco de cancro, exercício físico, atividade física e treino, dando preferência a estudos que, na classificação de Oxford, correspondessem aos níveis I (ensaios clínicos randomizados e revisões sistemáticas) e II de evidência científica (ensaios clínicos não randomizados). Conclusão – Embora se reconheça que o exercício físico é benéfico para a população em geral e existam linhas orientadoras para a prescrição do exercício físico em indivíduos com cancro, estas não são ainda absolutamente consensuais, necessitando sempre de individualização no treino. A investigação em torno das questões que envolvem a adequada prescrição do exercício físico em indivíduos com ou em risco de desenvolver cancro é primordial. ABSTRACT - Introduction – Physiological effects of physical activity and training are currently subject of extensive research which has already showed uncontroversial benefits in different clinical conditions. Different studies have already shown the beneficial effects of mild to moderate regular exercise in decreasing cancer risk and increasing physical fitness of individuals suffering from cancer, undergoing surgery or not. However, the appropriate exercise prescription for greater efficacy in improving physical fitness and decreasing fatigue is not yet consensus. The aim of this study was to review current knowledge about the benefits of exercise on breast cancer survivors and systematize the existing guidelines for prescribing exercise in this population. Methodology – A literature review was conducted based on the keywords: breast cancer, breast cancer survivors, cancer risk, physical exercise, physical activity and training, giving preference to studies in the classification of Oxford corresponded to level I (randomized clinical trials and systematic reviews) and II (no randomized clinical trials) scientific evidence. Conclusion – Although it is recognized that exercise is beneficial for general population and that there are guidelines for exercise prescription for individuals with cancer, there is no absolute agreement and they constantly require individual adaptations in training. Research on issues involving the correct prescription of exercise for individuals with or at risk of developing cancer is vital.

Grip strength: are dinamometers equivalent? JAMAR vs E-Link

Levels of risk for future disability can be assessed with grip strength. This assessment is of fundamental importance for establishing prevention strategies. It also allows verifying relationships with functional capacity of individuals. Most studies on grip strength use the JAMAR Hydraulic dynamometer that provides the value of isometric force obtained during the performance of grip movement and is considered the “gold standard” for measurement of grip strength. However, there are different dynamometers available commercially, such as portable computerized dynamometer E-Link (Biometrics), which provides the value of maximum force (peak force) in addition to other variables as the rate of fatigue for hand strength, among others. Of our knowledge, there are no studies that allow us to accept or not and compare values obtained with both devices and perhaps use them interchangeably. The aim of this study was to evaluate the absolute agreement between the measurements of grip strength (peak force or maximum force in kg) obtained from two different devices (portable dynamometers): a computerized (E-Link, Biometrics) and one hydraulic (JAMAR).

Experimental Measurements and Correlation of the Solubility of Three Primary Amides in Supercritical CO2: Acetanilide, Propanamide, and Butanamide

Solubilities of three primary amides, namely, acetanilide, propanamide, and butanamide, in supercritical carbon dioxide were measured at T = (308.2, 313.2, and 323.2) K over the pressure range (9.0 to 40.0) MPa by a flow type apparatus. The solubility behavior of the three solids shows an analogous trend with a crossover region of the respective isotherms between (12 to 14) MPa. The solubility of each amide, at the same temperature and pressure, decreases from propanamide to acetanilide. Pure compound properties required for the modeling were estimated, and the solubilities of the amides were correlated by using the Soave-Redlich-Kwong cubic equation of state with an absolute average relative deviation (AARD) from (1.3 to 6.1) %.

Structural characterization of Co‐Re superlattices

Co‐Re superlattices were prepared with nominal periodicities of 65–67 Å and varying bilayer composition. The structural characterization was made by x‐ray diffraction and Rutherford backscattering spectrometry (RBS). First, second, and third order satellites are observed in the x‐ray diffractogram at 2θ values and with intensities close to those predicted by simulation. This confirms the coherence of the superlattice. RBS measurements combined with RUMP simulations give information on interface sharpness and the absolute thicknesses of the Co and Re layers. Discrepancies between the experimental and simulated diffractograms are found for Co thicknesses below 18 Å.

Controlo da qualidade dosimétrico no serviço de radioterapia do Hospital CUF Descobertas (HCD): importância do controlo da qualidade do sector da física e resultados da auditoria ESTRO-EQUAL

A calibração e o controlo da qualidade de um acelerador linear são passos muito importantes num serviço de Radioterapia, para garantir a qualidade dos tratamentos prestados. O sector da Física da Unidade de Radioterapia do Hospital Cuf Descobertas implementou um rigoroso Programa de controlo de qualidade ao equipamento produtor de radiação e aos equipamentos medidores de radiação, de acordo com o Dec-Lei 180/2002 e com os protocolos internacionais. Para tal, foram implementados procedimentos, criadas folhas de cálculo, instruções de trabalho e impressos. Foram ainda implementados testes aos equipamentos com periodicidade definida: controlo de qualidade diário e controlo de qualidade após intervenções (manutenções preventivas e correctivas). No decorrer do ano de 2005, o sector da Física colaborou activamente com toda a equipa da Radioterapia na implementação da Norma ISO 9001:2000 no serviço, contribuindo com o seu know how na implementação desta, numa área tão importante como a da garantia da qualidade dos feixes de radiação e das respectivas calibrações em dose. Numa procura de melhoria contínua da qualidade dos serviços prestados aos pacientes, decorre ainda uma auditoria externa da EQUAL-ESTRO*, intercomparação postal com dosímetros termoluminescentes. A qualidade dos feixes de energias utilizados diariamente é analisada, tanto ao nível das calibrações absolutas de cada um dos feixes de fotões e de electrões, como ao nível dos cálculos de dose obtidos com o sistema de planimetria XiO da CMS. Os resultados das duas primeiras fases da intercomparação, relativa aos dois feixes de fotões de 6 MV e 15 MV e feixes de electrões de 4 MeV, 8 MeV e 12 MeV, foram considerados pela EQUAL-ESTRO num nível óptimo (desvio máximo na dose medida em relação à dose de referência |d| ≤ 3%).

FMRI 3D registration based on Fourier space subsets using neural networks

In this work, we present a neural network (NN) based method designed for 3D rigid-body registration of FMRI time series, which relies on a limited number of Fourier coefficients of the images to be aligned. These coefficients, which are comprised in a small cubic neighborhood located at the first octant of a 3D Fourier space (including the DC component), are then fed into six NN during the learning stage. Each NN yields the estimates of a registration parameter. The proposed method was assessed for 3D rigid-body transformations, using DC neighborhoods of different sizes. The mean absolute registration errors are of approximately 0.030 mm in translations and 0.030 deg in rotations, for the typical motion amplitudes encountered in FMRI studies. The construction of the training set and the learning stage are fast requiring, respectively, 90 s and 1 to 12 s, depending on the number of input and hidden units of the NN. We believe that NN-based approaches to the problem of FMRI registration can be of great interest in the future. For instance, NN relying on limited K-space data (possibly in navigation echoes) can be a valid solution to the problem of prospective (in frame) FMRI registration.

A new bridge between leptonic CP violation and leptogenesis

Flavour effects due to lepton interactions in the early Universe may have played an important role in the generation of the cosmological baryon asymmetry through leptogenesis. If the only source of high-energy CP violation comes from the left-handed leptonic sector, then it is possible to establish a bridge between flavoured leptogenesis and low-energy leptonic CP violation. We explore this connection taking into account our present knowledge about low-energy neutrino parameters and the matter-antimatter asymmetry observed in the Universe. In this framework, we find that leptogenesis favours a hierarchical light neutrino mass spectrum, while for quasi-degenerate and inverted hierarchical neutrino masses there is a very narrow allowed window. The absolute neutrino mass scale turns out to be m less than or similar to 0.1 eV. (c) 2007 Elsevier B.V. All rights reserved.

A gestão e o controlo do grupo de crianças

Relatório da Prática Profissional Supervisionada Mestrado em Educação Pré-Escolar

Organização e tratamento de dados recolhidos nas rotinas das crianças na sala dos quatro anos

Dissertação apresentada à escola Superior de Educação de Lisboa para obtenção de grau de mestre em Educação Matemática na Educação Pré-Escolar e nos 1º e 2º Ciclos do Ensino Básico

Uma análise das diferenças em termos da cultura e dos interesses profissionais a partir do projeto de substituiçao das IAS 39: Financial Instruments - Recognition and Measurement

Mestrado em Contabilidade