Phenanthroimidazoles as fluorimetric and colourimetric chemosensors in aqueous solution

2,4,5-Triaryl-imidazoles are versatile compounds with application in medicine, due to their biological activity, and materials sciences, for their interesting optical properties. These properties can be tuned by careful selection of substituents at positions 2, 4 and 5: replacement of the aryl group by an heterocyclic group results in larger π-conjugated systems with improved optical properties for application in nonlinear optics, OLEDs, DNA intercalators, and chemosensors. Moreover, it is expected that introducing more conjugation and rigidity into the resulting system will further improve its properties. The development of chromo/fluorescent probes that are capable of detecting ions with high sensitivity and selectivity in aqueous media is currently a topic of strong interest and the design of heteroditopic receptors that contain two or more different binding sites for the simultaneous complexation of cationic and anionic guests is a emerging field of supramolecular chemistry. In this communication, we report the synthesis of new phenanthroimidazoles substituted at position 2 with arylthienyl or arylfuryl moieties possessing substituents of different electronic character, in order to tune the chromo/fluoro response in the presence of relevant anions and metal cations. Their photophysical properties and chemosensory ability were studied in acetonitrile and mixtures of acetonitrile and water, and selective detection of cyanide was achieved in aqueous mixtures for some of the derivatives.

Phenanthroimidazole derivatives as fluorimetric chemosensors in aqueous medium

In recent years the research of sensors with good sensitivity and good selectivity in aqueous medium has been of great interest. Chemosensors soluble in aqueous media are very interesting, because of the importance in revealing a number of biological processes, disease states and environmental pollutions. 2,4,5-Triaryl-imidazoles are versatile compounds with application in medicine, due to their biological activity, and materials sciences, for their interesting optical properties. These properties can be tuned by careful selection of substituents at positions 2, 4 and 5: replacement of the aryl group by a heterocyclic group results in larger π-conjugated systems with improved optical properties for application in nonlinear optics, OLEDs, DNA intercalators, and chemosensors. In this communication, we report the synthesis of new phenanthroimidazoles, substituted at position 2 with (hetero)aryl groups of different electronic character, in order to evaluate their photophysical properties and chemosensory ability. The new derivatives were characterized by the usual techniques and a detailed photophysical study was undertaken. The evaluation of the compounds as fluorimetric chemosensors was carried out by performing titrations in acetonitrile and acetonitrile/water in the presence of relevant organic and inorganic anions, and of alkaline, alkaline-earth and transition metal cations.

Audit quality: does gender composition of audit firms matter?

Using a sample of Portuguese audit firms and their client companies, this study examines the association between gender composition of the partnership structure oaudit firms and audit quality. Audit quality is measured through the earnings quality of audit clients. We find that gender diversity in the partnership structure of audit firms, per se, has no association with audit quality. In turn, we find significant evidence that a predominant presence of female Certified Public Accountants (CPAs) in partner positions in audit firms is associated with higher audit quality. In particular, the results indicate that audit firms with female-dominated partnership structures are negatively related with aggressive accounting practices in audit clients.

Inteligência como dispositivo de poder

O objetivo do presente estudo, é compreender a inscrição individual e social de discursos usados por alunas, em diferentes posições de classe social, para explicar os seus sucessos académicos. Foram entrevistadas 19 alunas portuguesas do 11º ano de escolaridade provenientes das classes trabalhadora e alta, com elevado rendimento académico. A Análise Foucaudiana do Discurso aponta para a importância da posição de classe na construção dos sujeitos relativamente à sua conceção de inteligência e ao sucesso escolar. A inteligência funciona assim como um dispositivo de poder que regula as relações entre sujeitos de diferentes classes sociais.

Cidadania, imigração e nacionalidade na União Europeia

Projeto de mestrado em Políticas Comunitárias e Cooperação Territorial

Bimodal information increases spontaneous interpersonal synchronization of goal directed upper limb movements

When interacting with each other, people often synchronize spontaneously their movements, e.g. during pendulum swinging, chair rocking[5], walking [4][7], and when executing periodic forearm movements[3].Although the spatiotemporal information that establishes the coupling, leading to synchronization, might be provided by several perceptual systems, the systematic study of different sensory modalities contribution is widely neglected. Considering a) differences in the sensory dominance on the spatial and temporal dimension[5] , b) different cue combination and integration strategies [1][2], and c) that sensory information might provide different aspects of the same event, synchronization should be moderated by the type of sensory modality. Here, 9 naïve participants placed a bottle periodically between two target zones, 40 times, in 12 conditions while sitting in front of a confederate executing the same task. The participant could a) see and hear, b) see , c) hear the confederate, d) or audiovisual information about the movements of the confederate was absent. The couple started in 3 different relative positions (i.e., in-phase, anti-phase, out of phase). A retro-reflective marker was attached to the top of the bottles. Bottle displacement was captured by a motion capture system. We analyzed the variability of the continuous relative phase reflecting the degree of synchronization. Results indicate the emergence of spontaneous synchronization, an increase with bimodal information, and an influence of the initial phase relation on the particular synchronization pattern. Results have theoretical implication for studying cue combination in interpersonal coordination and are consistent with coupled oscillator models.

Structural, optical and magnetic properties of pulsed laser deposited Co-doped ZnO films

Zn1−xCoxO films with different Co concentrations (with x=0.00, 0.10, 0.15, and 0.30) were grown by pulsed laser deposition (PLD) technique. The structural and optical properties of the films were investigated by grazing incidence X-ray diffraction (GIXRD), Raman spectroscopy and photoluminescence (PL). The magnetic properties were measured by conventional magnetometry using a SQUID and simulated by ab-initio calculations using Korring–Khon–Rostoker (KKR) method combined with coherent potential approximation (CPA). The effect of Co-doping on the GIXRD and Raman peaks positions, shape and intensity is discussed. PL studies demonstrate that Co-doping induces a decrease of the bandgap energy and quenching of the UV emission. They also suggest the presence of Zn interstitials when x≥0.15. The 10% Co-doped ZnO film shows ferromagnetism at 390 K with a spontaneous magnetic moment ≈4×10−5 emu and coercive field ≈0.17 kOe. The origin of ferromagnetism is explained based on the calculations using KKR method.

Arquitecturas imaginárias. Espaço real e ilusório no Barroco português

Tese de Doutoramento em Arquitectura / Cultura Arquitectónica.

Combining non-dominance, objective-order and spread metric to extend firefly algorithm to multi-objective optimization

In this paper, we propose an extension of the firefly algorithm (FA) to multi-objective optimization. FA is a swarm intelligence optimization algorithm inspired by the flashing behavior of fireflies at night that is capable of computing global solutions to continuous optimization problems. Our proposal relies on a fitness assignment scheme that gives lower fitness values to the positions of fireflies that correspond to non-dominated points with smaller aggregation of objective function distances to the minimum values. Furthermore, FA randomness is based on the spread metric to reduce the gaps between consecutive non-dominated solutions. The obtained results from the preliminary computational experiments show that our proposal gives a dense and well distributed approximated Pareto front with a large number of points.

Narrative change in Gloria Films: Comparing various processes of therapeutic innovation

Aims: The present study focuses on the analysis of novelty emergence in classic Gloria Films with Rogers, Perls, and Ellis to understand how the same client formulated her own problem and if and how change occurred in those three sessions. Method: The Innovative Moments Coding System was applied to track innovative moments (IMs) and their themes. Results: The session with Rogers showed more diversity in disclosed problems and themes of IMs, as well as a higher proportion of reflection IMs. The session with Perls demonstrated a high proportion of protest IMs. The session with Ellis showed less innovation than other sessions. The changes found were based mostly on reflection and protest IMs in three sessions. Conclusion: Narrative innovations occurred in the three single sessions. The type of dominant innovation is consistent with the therapeutic model and the IMs model. The exploration of the IMs’ themes allowed a more precise identification of Gloria's new narrative positions and their development throughout those sessions.

Direito Eleitoral e inelegibilidades por desvio de conduta: reflexões a partir da experiência brasileira

Dissertação de mestrado em Direito Administrativo

Representações e reinterpretações do caminhar: caso de estudo da Rua das Dunas em Castelo do Neiva, Viana do Castelo

Dissertação de mestrado integrado em Arquitectura (área de especialização em Cidade e Território)

Sistema inteligente para análise do posicionamento de árbitros de futebol

Dissertação de mestrado em Sistemas de Informação

Peptaibolin analogues by incorporation of α,α-dialkylglycines: synthesis and study of their membrane permeating ability

Analogues of Peptaibolin, a peptaibol with antibiotic activity, incorporating α,α-dialkylglycines (Deg, Dpg, and Ac6c) at selected positions were synthesised by MW-SPPS and fully characterized. A control analogue incorporating L-alanine was also prepared. The native peptide and the analogues were studied by fluorescence spectroscopy for their membrane permeating activity. Small unilamellar vesicles (SUVs) of egg phosphatidylcholine/ cholesterol (70:30) containing an encapsulated fluorescence probe (6-carboxyfluorescein) were used as membrane models. The assays of carboxyfluorescein release from SUVs upon peptide addition showed that Peptaibolin-Dpg and Peptaibolin-Ac6c are the most active peptides. These results indicate that the structure of the α,α-dialkylglycines is crucial for the membrane permeating ability of these Peptaibolin analogues.

Da luta contra o crime aos riscos. As consequências extra prisionais da reclusão feminina

Entre o leque de políticas penais atualmente disponíveis e legitimadas na contenção da criminalidade, a reclusão constitui a forma predominante para sancionar transgressores. Procurando alargar o debate sobre as penas de prisão, este artigo explora, através de entrevistas com 20 mulheres reclusas, os processos de reconfiguração e reestruturação das responsabilidades femininas na decorrência da reclusão de mulheres e analisa as implicações socioeconómicas da ausência feminina nos agregados domésticos. Os resultados evidenciam que a reclusão de mulheres desencadeia ou agrava posições de vulnerabilidade social e instabilidade económica, afetando sobretudo crianças, mulheres e idosos.