Photolabile protection for amino acids: studies on the release from novel benzoquinolone cages

The synthesis of a novel fused nitrogen heterocycle, benzoquinolone, for evaluation as a photocleavable protecting group is described for the first time, by coupling to model amino acids (alanine, phenylalanine and glutamic acid). Conversion of the phenylalanine ester conjugate to the thionated derivative was accomplished by reaction with Lawesson’s reagent. Photocleavage studies of the carbonyl and thiocarbonyl benzoquinolone conjugates in various solvents and at different wavelengths (300, 350 and 419 nm) showed that the most interesting result was obtained at 419 nm for the thioconjugate, revealing that the presence of the thiocarbonyl group clearly improved the photolysis rates, giving practicable irradiations times for the release of the amino acids (less than 1 minute).

Regeneração de misturas betuminosas recicladas pela utilização de betumes modificados

Atualmente, a reciclagem de materiais assume uma importância crescente para a Sociedade, e em particular no que diz respeito ao sector da construção. Nas infraestruturas rodoviárias caminha-se no mesmo sentido, uma vez que a reutilização de materiais nas misturas betuminosas permite fazer frente ao gradual aparecimento duma grande diversidade de resíduos, sendo ainda possível reduz ir os custos de produção. De facto, a reutilização de materiais nas misturas betuminosas permite a redução dos custos, a redução do impacto ambiental, e a necessidade de utilização de novos agregados e ligantes betuminosos, constituindo um ciclo fechado de vida do material. O presente artigo tem como objetivo apresentar as vantagens da utilização de betumes modificados comerciais e produzidos em laboratório na regeneração ou na melhoria do desempenho de misturas betuminosas com elevadas taxas de reciclagem. Os materiais utilizados no estudo foram material fresado (50%), agregados novos, polímeros e betumes. Na modificação dos betumes base foram utilizados polímeros virgens (SBS) e reciclados (EVA), sendo ainda utilizado um betume modificado comercial. Os ensaios laboratoriais demonstram que a utilização de betumes modificados como materiais regeneradores melhora significativamente o desempenho das misturas à deformação permanente, por comparação com uma mistura betuminosa reciclada de referência com um rejuvenescedor comercial. No que diz respeito à sensibilidade à água todas as misturas produzidas com estes betumes regeneradores demonstram um excelente resultado. Porém, a mistura produzida com o betume modificado comercial destaca-se das restantes pela maior capacidade em resistir a este fenómeno. Considera-se que de uma forma geral os resultados obtidos neste trabalho trouxeram novas perspetivas no que respeita ao processo de regeneração dos betumes presentes no material fresado e na reciclagem de misturas betuminosas

Logic programming and artificial neural networks in breast cancer detection

About 90% of breast cancers do not cause or are capable of producing death if detected at an early stage and treated properly. Indeed, it is still not known a specific cause for the illness. It may be not only a beginning, but also a set of associations that will determine the onset of the disease. Undeniably, there are some factors that seem to be associated with the boosted risk of the malady. Pondering the present study, different breast cancer risk assessment models where considered. It is our intention to develop a hybrid decision support system under a formal framework based on Logic Programming for knowledge representation and reasoning, complemented with an approach to computing centered on Artificial Neural Networks, to evaluate the risk of developing breast cancer and the respective Degree-of-Confidence that one has on such a happening.

Estudo de materiais fibrosos para aplicação em modelos cerebrais

Neste trabalho, multifilamentos ocos de polipropileno foram estudados com o objetivo de construir um fantoma cerebral adequado à validação e controlo de qualidade de uma modalidade de imagem clínica inovadora: High-Definition Fiber Tractography. Foram investigadas e discutidas a análise à secção transversal e a redução da área de multifilamentos ocos de polipropileno, através de estiramento. De acordo com os resultados experimentais, a dimensão da secção transversal dos multifilamentos é proporcional à massa linear dos mesmos, existindo uma irregularidade, relativamente, à forma deste tipo de materiais.

Effect of NaCl additive on solute-solvent interactions in aqueous polyethylene glycol-sodium sulfate two-phase systems

Abstract Partition behavior of eight small organic compounds and six proteins was examined in poly(ethylene glycol)-8000-sodium sulfate aqueous two-phase systems containing 0.215 M NaCl and 0.5 M osmolyte (sorbitol, sucrose, TMAO) and poly(ethylene glycol)-10000-sodium sulfate-0.215 M NaCl system, all in 0.01 M sodium phosphate buffer, pH 6.8. The differences between the solvent properties of the coexisting phases (solvent dipolarity/polarizability, hydrogen bond donor acidity, and hydrogen bond acceptor basicity) were characterized with solvatochromic dyes using the solvatochromic comparison method. Differences between the electrostatic properties of the phases were determined by analysis of partitioning of sodium salts of dinitrophenylated (DNP-) amino acids with aliphatic alkyl side-chain. The partition coefficients of all compounds examined (including proteins) were described in terms of solute-solvent interactions. The results obtained in the study show that solute-solvent interactions of nonionic organic compounds and proteins in polyethylene glycol-sodium sulfate aqueous two-phase system change in the presence of NaCl additive.

Perspectivas sobre info-exclusão no ciberespaço lusófono

Os países de língua oficial portuguesa revelam, no seu conjunto, uma heterogeneidade económica, social, educativa e geográfica que afecta o modo como se efectiva o acesso à internet e à escolarização nestes países. Nesta comunicação, pretende-se reflectir sobre duas questões centrais que se colocam quando se discute o conceito de infoexclusão. Por um lado, questiona-se se estarão criadas as condições culturais, infraestruturais e sociais que permitam o acesso e a utilização informada dos serviços de internet nestes países; por outro lado, interroga-se sobre a existência, nos países da Comunidade dos Países de Língua Portuguesa (CPLP), de condições materiais e culturais que lhes permita desfrutar das potencialidades do mundo digital. Pretende-se apresentar, neste trabalho, alguns dados relativos aos índices de desenvolvimento humano nestes países, aos níveis de escolaridade e de literacia, reflectindo sobre os mesmos, apresentando também os dados disponíveis respeitantes ao número de utilizadores e subscritores dos serviços de internet. Os dados analisados indicam que existem grandes assimetrias no que diz respeito ao nível de desenvolvimento humano nestes países. Observam-se profundas desigualdades ligadas à pobreza e à educação, que contribuem de modo significativo para a presença de baixos níveis de desenvolvimento humano em alguns países da CPLP.

Portuguese publication in the aim of regional science: a study of articles published in RPER from 2003 to 2015

This paper is a study of the full content of articles published by RPER, the Portuguese Review of Regional Studies, from the time it was launched in 2003 until the first quarter of 2015. RPER is a journal edited by the Portuguese section of the European Regional Science Association, which was established in the first half of the 1980s. The Association (APDR) and the journal are the result of contributions by researchers and technicians from different scientific fields, including mainly Economics, Geography, Sociology, Engineering and Architecture. The main focus of these contributions is the socio-economic life of concrete sites, and the way this life is conditioned by resources and capabilities, the historical and cultural heritage and institutions. Content analysis was undertaken to identify the main subjects chosen during the total period under analysis, the nature of the articles published (theoretical or empirical) and the main analytical framework used. The analysis also covers sub-periods to investigate major trends found in terms of subjects chosen and analytical methods, questioning the rationale behind them. The paper concludes with a few notes regarding the social echo the research received and an identification of the main limitations of the research. In the first part of the article, we conduct a summary review of the genesis and evolution of Regional Science at international level to serve as a basis for the empirical approach developed.

Angular distributions in tt¯H(H→bb¯) reconstructed events at the LHC

The associated production of a Higgs boson and a top-quark pair, tt¯H, in proton-proton collisions is addressed in this paper for a center of mass energy of 13TeV at the LHC. Dileptonic final states of tt¯H events with two oppositely charged leptons and four jets from the decays t→bW+→bℓ+νℓ, t¯→b¯W−→b¯ℓ−ν¯ℓ and h→bb¯, are used. Signal events, generated with MadGraph5_aMC@NLO, are fully reconstructed by applying a kinematic fit. New angular distributions of the decay products as well as angular asymmetries are explored in order to improve discrimination of tt¯H signal events over the dominant irreducible background contribution, tt¯bb¯. Even after the full kinematic fit reconstruction of the events, the proposed angular distributions and asymmetries are still quite different in the tt¯H signal and the dominant background (tt¯bb¯).

On the Hill estimator: a comparison of methods

Extreme value theory (EVT) deals with the occurrence of extreme phenomena. The tail index is a very important parameter appearing in the estimation of the probability of rare events. Under a semiparametric framework, inference requires the choice of a number k of upper order statistics to be considered. This is the crux of the matter and there is no definite formula to do it, since a small k leads to high variance and large values of k tend to increase the bias. Several methodologies have emerged in literature, specially concerning the most popular Hill estimator (Hill, 1975). In this work we compare through simulation well-known procedures presented in Drees and Kaufmann (1998), Matthys and Beirlant (2000), Beirlant et al. (2002) and de Sousa and Michailidis (2004), with a heuristic scheme considered in Frahm et al. (2005) within the estimation of a different tail measure but with a similar context. We will see that the new method may be an interesting alternative.

Off-line simulation inspires insight: a neurodynamics approach to efficient robot task learning

There is currently an increasing demand for robots able to acquire the sequential organization of tasks from social learning interactions with ordinary people. Interactive learning-by-demonstration and communication is a promising research topic in current robotics research. However, the efficient acquisition of generalized task representations that allow the robot to adapt to different users and contexts is a major challenge. In this paper, we present a dynamic neural field (DNF) model that is inspired by the hypothesis that the nervous system uses the off-line re-activation of initial memory traces to incrementally incorporate new information into structured knowledge. To achieve this, the model combines fast activation-based learning to robustly represent sequential information from single task demonstrations with slower, weight-based learning during internal simulations to establish longer-term associations between neural populations representing individual subtasks. The efficiency of the learning process is tested in an assembly paradigm in which the humanoid robot ARoS learns to construct a toy vehicle from its parts. User demonstrations with different serial orders together with the correction of initial prediction errors allow the robot to acquire generalized task knowledge about possible serial orders and the longer term dependencies between subgoals in very few social learning interactions. This success is shown in a joint action scenario in which ARoS uses the newly acquired assembly plan to construct the toy together with a human partner.

Simulation of OWES with five-Level converter linked to the grid: Harmonic assessment

This paper deals with a computing simulation for an offshore wind energy system taking into account the influence of the marine waves action throughout the floating platform. The wind energy system has a variable-speed turbine equipped with a permanent magnet synchronous generator and a full-power five level converter, injecting energy into the electric grid through a high voltage alternate current link. A reduction on the unbalance of the voltage in the DC-link capacitors of the five-level converter is proposed by a strategic selection of the output voltage vectors. The model for the drive train of the wind energy system is a two mass model, including the dynamics of the floating platform. A case study is presented and the assessment of the quality of the energy injected into the electric grid is discussed.

Simulation of a rectifier malfunction on a offshore wind system with HVDC transmission

A new integrated mathematical model for the simulation of an offshore wind system having a rectifier input voltage malfunction at one phase is presented in this paper. The mathematical model considers an offshore variable-speed wind turbine on a floating platform, equipped with a permanent magnet synchronous generator using full-power three-level converter to inject energy into the electric network, through a high voltage direct current transmission submarine cable. The model for the drive train is a discrete three mass, incorporating the dynamic of the moving surface. A case study is presented to access conclusion about the malfunction.

A inclusividade dos espaços de lazer infantil

Cada vez mais as ruas são vistas como lugares com perigos desconhecidos e com influências desagradáveis fazendo com que os adultos temam deixar os seus filhos brincarem nas mesmas. Neste sentido, a existência de espaços de lazer infantis torna-se cada vez mais importante. Este trabalho tem como objetivo descrever a fase empírica inicial realizada no âmbito de um projeto de doutoramento. Procura-se fazer uma primeira observação e reflexão, não sistemática, sobre a forma como um conjunto diverso de espaços (localizados em aeroportos, hospitais, escolas, centro comerciais e espaços independentes) satisfazem ou não os sete princípios de um parque infantil inclusivo (Christensen, 2010). A observação e a análise tiveram como principal preocupação olhar atentamente as questões comunicacionais uma vez que é um ponto fulcral para a continuidade do projeto. Isto é, compreender a importância das questões comunicacionais e a inclusividade dos espaços. Este processo foi realizado através do método observacional auxiliado por uma grelha estruturada consoante as categorias definidas por Mazzilli (2007): a afetiva, a funcional/atividades e a perceptiva/espaço visual.

Photoactivation of butyric acid from 6-aminobenzocoumarin cages

A new benzocoumarin bearing an amino group is proposed as a photocleavable protecting group for carboxylic acids. The novel heterocycle, 6-amino-4-chloromethyl-2-oxo-2H-naphtho[1,2-b]pyran was used in the preparation of ester conjugates of butyric acid, and of the corresponding mono- and di-methylated or ethylated derivatives. The photolability of the ester conjugates was studied by irradiation at selected wavelengths in methanol/HEPES buffer (80:20) solutions, and the release of butyric acid was followed with HPLC/UV and 1H NMR monitoring. Release of the carboxylic acid was faster for the monoalkylated derivatives (approximately within 20 min), at the longer wavelengths of irradiation (350 and 419 nm). The photophysics of the heterocyclic conjugates was also evaluated by both steady state and time-resolved methods.

Testing Nelder-Mead based repulsion algorithms for multiple roots of nonlinear systems via a two-level factorial design of experiments

This paper addresses the challenging task of computing multiple roots of a system of nonlinear equations. A repulsion algorithm that invokes the Nelder-Mead (N-M) local search method and uses a penalty-type merit function based on the error function, known as 'erf', is presented. In the N-M algorithm context, different strategies are proposed to enhance the quality of the solutions and improve the overall efficiency. The main goal of this paper is to use a two-level factorial design of experiments to analyze the statistical significance of the observed differences in selected performance criteria produced when testing different strategies in the N-M based repulsion algorithm. The main goal of this paper is to use a two-level factorial design of experiments to analyze the statistical significance of the observed differences in selected performance criteria produced when testing different strategies in the N-M based repulsion algorithm.