Synthesis, structure, and optical properties of an alternating calix[4]arene-based meta-linked phenylene ethynylene copolymer

Novel alternating copolymers comprising biscalix[4]arene-p-phenylene ethynylene and m-phenylene ethynylene units (CALIX-m-PPE) were synthesized using the Sonogashira-Hagihara cross-coupling polymerization. Good isolated yields (60-80%) were achieved for the polymers that show M-n ranging from 1.4 x 10(4) to 5.1 x 10(4) gmol(-1) (gel permeation chromatography analysis), depending on specific polymerization conditions. The structural analysis of CALIX-m-PPE was performed by H-1, C-13, C-13-H-1 heteronuclear single quantum correlation (HSQC), C-13-H-1 heteronuclear multiple bond correlation (HMBC), correlation spectroscopy (COSY), and nuclear overhauser effect spectroscopy (NOESY) in addition to Fourier transform-Infrared spectroscopy and microanalysis allowing its full characterization. Depending on the reaction setup, variable amounts (16-45%) of diyne units were found in polymers although their photophysical properties are essentially the same. It is demonstrated that CALIX-m-PPE does not form ground-or excited-state interchain interactions owing to the highly crowded environment of the main-chain imparted by both calix[4]arene side units which behave as insulators inhibiting main-chain pi-pi staking. It was also found that the luminescent properties of CALIX-m-PPE are markedly different from those of an all-p-linked phenylene ethynylene copolymer (CALIX-p-PPE) previously reported. The unexpected appearance of a low-energy emission band at 426 nm, in addition to the locally excited-state emission (365 nm), together with a quite low fluorescence quantum yield (Phi = 0.02) and a double-exponential decay dynamics led to the formulation of an intramolecular exciplex as the new emissive species.

Grid structure impact in sparse point representation of derivatives

In the Sparse Point Representation (SPR) method the principle is to retain the function data indicated by significant interpolatory wavelet coefficients, which are defined as interpolation errors by means of an interpolating subdivision scheme. Typically, a SPR grid is coarse in smooth regions, and refined close to irregularities. Furthermore, the computation of partial derivatives of a function from the information of its SPR content is performed in two steps. The first one is a refinement procedure to extend the SPR by the inclusion of new interpolated point values in a security zone. Then, for points in the refined grid, such derivatives are approximated by uniform finite differences, using a step size proportional to each point local scale. If required neighboring stencils are not present in the grid, the corresponding missing point values are approximated from coarser scales using the interpolating subdivision scheme. Using the cubic interpolation subdivision scheme, we demonstrate that such adaptive finite differences can be formulated in terms of a collocation scheme based on the wavelet expansion associated to the SPR. For this purpose, we prove some results concerning the local behavior of such wavelet reconstruction operators, which stand for SPR grids having appropriate structures. This statement implies that the adaptive finite difference scheme and the one using the step size of the finest level produce the same result at SPR grid points. Consequently, in addition to the refinement strategy, our analysis indicates that some care must be taken concerning the grid structure, in order to keep the truncation error under a certain accuracy limit. Illustrating results are presented for 2D Maxwell's equation numerical solutions.

Foreign languages in the primary school

Of vital importance to the successful implementation of the teaching of FLs in the 1st Cycle...

Lichens as biomonitors at indoor environments of primary schools

A biomonitoring study, using transplanted lichens Flavoparmelia caperata, was conducted to assess the indoor air quality in primary schools in urban (Lisbon) and rural (Ponte de Sor) Portuguese sites. The lichens exposure period occurred between April and June 2010 and two types of environments of the primary schools were studied: classrooms and outdoor/courtyard. Afterwards, the lichen samples were processed and analyzed by instrumental neutron activation analysis (INAA) to assess a total of 20 chemical elements. Accumulated elements in the exposed lichens were assessed and enrichment factors (EF) were determined. Indoor and outdoor biomonitoring results were compared to evaluate how biomonitors (as lichens) react at indoor environments and to assess the type of pollutants that are prevalent in those environments.

Seasonal variation of total particulate matter and children respiratory diseases at Lisbon primary schools using passive methods

In this work, 14 primary schools of Lisbon city, Portugal, followed a questionnaire of the ISAAC - International Study of Asthma and Allergies in Childhood Program, in 2009/2010. The questionnaire contained questions to identify children with respiratory diseases (wheeze, asthma and rhinitis). Total particulate matter (TPM) was passively collected inside two classrooms of each of 14 primary schools. Two types of filter matrices were used to collect TPM: Millipore (IsoporeTM) polycarbonate and quartz. Three campaigns were selected for the measurement of TPM: Spring, Autumn and Winter. The highest difference between the two types of filters is that the mass of collected particles was higher in quartz filters than in polycarbonate filters, even if their correlation is excellent. The highest TPM depositions occurred between October 2009 and March 2010, when related with rhinitis proportion. Rhinitis was found to be related to TPM when the data were grouped seasonally and averaged for all the schools. For the data of 2006/2007, the seasonal variation was found to be related to outdoor particle deposition (below 10 μm).

Indoor air quality in primary schools

Clean air is a basic requirement of life. The Indoor Air Quality (IAQ) has been the object of several studies due to an increasing concern within the scientific community on the effects of indoor air quality upon health, especially as people tend to spend more time indoors than outdoors. The quality of air inside homes, offices, schools or other private and public buildings is an essential determinant of healthy life and people’s well-being. People can be exposed to contaminants by inhalation, ingestion and dermal contact. In the past, scientists have paid much attention to the study of exposure to outdoor air contaminants, because they have realised the seriousness of outdoor air pollution problems. However, each indoor microenvironment has unique characteristics, determined by the local outdoor air, specific building characteristics and indoor activities. Indeed, hazardous substances are emitted from buildings, construction materials and indoor equipment or due to human activities indoors.

From unthinned continent to ocean: The deep structure of the West Iberia passive continental margin at 38 degrees N

The crustal and lithospheric mantle structure at the south segment of the west Iberian margin was investigated along a 370 km long seismic transect. The transect goes from unthinned continental crust onshore to oceanic crust, crossing the ocean-continent transition (OCT) zone. The wide-angle data set includes recordings from 6 OBSs and 2 inland seismic stations. Kinematic and dynamic modeling provided a 2D velocity model that proved to be consistent with the modeled free-air anomaly data. The interpretation of coincident multi-channel near-vertical and wide-angle reflection data sets allowed the identification of four main crustal domains: (i) continental (east of 9.4 degrees W); (ii) continental thinning (9.4 degrees W-9.7 degrees W): (iii) transitional (9.7 degrees W-similar to 10.5 degrees W); and (iv) oceanic (west of similar to 10.5 degrees W). In the continental domain the complete crustal section of slightly thinned continental crust is present. The upper (UCC, 5.1-6.0 km/s) and the lower continental crust (LCC, 6.9-7.2 km/s) are seismically reflective and have intermediate to low P-wave velocity gradients. The middle continental crust (MCC, 6.35-6.45 km/s) is generally unreflective with low velocity gradient. The main thinning of the continental crust occurs in the thinning domain by attenuation of the UCC and the LCC. Major thinning of the MCC starts to the west of the LCC pinchout point, where it rests directly upon the mantle. In the thinning domain the Moho slope is at least 13 degrees and the continental crust thickness decreases seaward from 22 to 11 km over a similar to 35 km distance, stretched by a factor of 1.5 to 3. In the oceanic domain a two-layer high-gradient igneous crust (5.3-6.0 km/s; 6.5-7.4 km/s) was modeled. The intra-crustal interface correlates with prominent mid-basement, 10-15 km long reflections in the multi-channel seismic profile. Strong secondary reflected PmP phases require a first order discontinuity at the Moho. The sedimentary cover can be as thick as 5 km and the igneous crustal thickness varies from 4 to 11 km in the west, where the profile reaches the Madeira-Tore Rise. In the transitional domain the crust has a complex structure that varies both horizontally and vertically. Beneath the continental slope it includes exhumed continental crust (6.15-6.45 km/s). Strong diffractions were modeled to originate at the lower interface of this layer. The western segment of this transitional domain is highly reflective at all levels, probably due to dykes and sills, according to the high apparent susceptibility and density modeled at this location. Sub-Moho mantle velocity is found to be 8.0 km/s, but velocities smaller than 8.0 km/s confined to short segments are not excluded by the data. Strong P-wave wide-angle reflections are modeled to originate at depth of 20 km within the lithospheric mantle, under the eastern segment of the oceanic domain, or even deeper at the transitional domain, suggesting a layered structure for the lithospheric mantle. Both interface depths and velocities of the continental section are in good agreement to the conjugate Newfoundland margin. A similar to 40 km wide OCT having a geophysical signature distinct from the OCT to the north favors a two pulse continental breakup.

Enhanced short wavelength response in laser-scanned-photodiode image sensor using an a-SiC : H/a-Si : H tandem structure

We report in this paper the recent advances we obtained in optimizing a color image sensor based on the laser-scanned-photodiode (LSP) technique. A novel device structure based on a a-SiC:H/a-Si:H pin/pin tandem structure has been tested for a proper color separation process that takes advantage on the different filtering properties due to the different light penetration depth at different wavelengths a-SM and a-SiC:H. While the green and the red images give, in comparison with previous tested structures, a weak response, this structure shows a very good recognition of blue color under reverse bias, leaving a good margin for future device optimization in order to achieve a complete and satisfactory RGB image mapping. Experimental results about the spectral collection efficiency are presented and discussed from the point of view of the color sensor applications. The physics behind the device functioning is explained by recurring to a numerical simulation of the internal electrical configuration of the device.

Novel structure for large area image sensing

This work presents preliminary results in the study of a novel structure for a laser scanned photodiode (LSP) type of image sensor. In order to increase the signal output, a stacked p-i-n-p-i-n structure with an intermediate light-blocking layer is used. The image and the scanning beam are incident through opposite sides of the sensor and their absorption is kept in separate junctions by an intermediate light-blocking layer. As in the usual LSP structure the scanning beam-induced photocurrent is dependent on the local illumination conditions of the image. The main difference between the two structures arises from the fact that in this new structure the image and the scanner have different optical paths leading to an increase in the photocurrent when the scanning beam is incident on a region illuminated on the image side of the sensor, while a decreasing in the photocurrent was observed in the single junction LSP. The results show that the structure can be successfully used as an image sensor even though some optimization is needed to enhance the performance of the device.

Intervenções em estruturas antigas

O presente relatório de estágio, definido como Trabalho Final de Mestrado, surge como resultado de um estágio profissional realizado no âmbito do Mestrado em Engenharia Civil do Instituto Superior de Engenharia de Lisboa, e tem como objectivos primordiais, expor as actividades realizadas e reflectir os conhecimentos adquiridos durante o período de estágio. Após uma formação académica maioritariamente vocacionada para os aspectos teóricos e de natureza científica, tornou-se fundamental ao estagiário garantir um contacto real com a profissão de Engenheiro Civil antes do ingresso no mercado de trabalho. Foi com base nesse pressuposto que a opção do Trabalho Final de Mestrado incidiu sobre a realização de um estágio curricular em detrimento das restantes possibilidades. O período de estágio iniciou-se a 14 de Março de 2011 e incidiu sobre a área de Conservação, Restauro e Reabilitação de edifícios com valor patrimonial, sendo feito referência no capítulo 2 aos princípios importantes da intervenção neste tipo de edifícios. O capítulo 3 faz uma abordagem geral do que são as coberturas servindo de complemento ao capítulo 4, onde são abordados e analisados os processos e métodos construtivos envolvidos, contemplando a evolução construtiva da cobertura do Cruzeiro, no Convento de Cristo em Tomar. Nos restantes capítulos, 5 e 6, é feita a caracterização e constituição da estrutura de um edifício da segunda metade do século XVIII, e a análise estrutural feita ao edifício no Antigo Convento do Santíssimo Sacramento, em Lisboa, respectivamente. O capítulo 4 é complementado pelo Anexo A, sendo utilizado como referência ao esquema da estrutura artesanal encontrada na cobertura do Cruzeiro.

Verificação da segurança da estrutura de um efifício localizado em Faro, utlizando os eurocódigos estruturais

Desde há alguns anos que têm vindo a ser mobilizados esforços para a elaboração de uma regulamentação técnica unificada aplicável a nível Europeu, os Eurocódigos Estruturais, a qual visa estabelecer uma harmonização da regulamentação a utilizar na construção civil, promovendo a eliminação de anteriores barreiras técnicas. Actualmente, no âmbito Nacional, encontramo-nos numa fase de transição da regulamentação técnica em vigor para o dimensionamento de Edifícios em Betão Armado, do Regulamento de Segurança e Acções para Estruturas de Betão Armado (RSA) e Regulamento de Estruturas de Betão Armado e Pré-Esforçado (REBAP) para os Eurocódigos Estruturais, sendo que neste período de transição se verifica a coexistência de ambos devido à ainda não publicação em Diário da República da nova regulamentação a adoptar. No presente trabalho procura-se verificar a segurança da estrutura de um edifício com laje fungiforme, situado em Faro, projectado segundo a regulamentação nacional em vigor (RSA/REBAP), através da aplicação dos Eurocódigos Estruturais, nomeadamente o EC0, EC1, EC2 e EC8. Este tipo de edifícios, em que a laje fungiforme é utilizada como elemento sísmico primário, não é totalmente abordada no EC8, a verificação de segurança será então efectuada considerando duas abordagens de análise distintas. Numa primeira abordagem de análise adopta-se a estrutura como sendo da Classe de Ductilidade Baixa (DCL) considerando todos os elementos como sísmicos primários, e numa segunda abordagem de análise assume-se uma maior ductilidade da estrutura (DCM) classificando alguns elementos como sísmicos secundários.

Deformação miocárdica em atletas de diferentes modalidades – Um estudo por 2D Speckle Tracking: projecto de investigação

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

Influence of growth temperature and carrier flux on the structure and transport properties of highly oriented CrO2 on Al2O3 (0001)

In this work we report on the structure and magnetic and electrical transport properties of CrO2 films deposited onto (0001) sapphire by atmospheric pressure (AP)CVD from a CrO3 precursor. Films are grown within a broad range of deposition temperatures, from 320 to 410 degrees C, and oxygen carrier gas flow rates of 50-500 seem, showing that it is viable to grow highly oriented a-axis CrO2 films at temperatures as low as 330 degrees C i.e., 60-70 degrees C lower than is reported in published data for the same chemical system. Depending on the experimental conditions, growth kinetic regimes dominated either by surface reaction or by mass-transport mechanisms are identified. The growth of a Cr2O3 interfacial layer as an intrinsic feature of the deposition process is studied and discussed. Films synthesized at 330 degrees C keep the same high quality magnetic and transport properties as those deposited at higher temperatures.

OC/EC ratio observations in Europe: Re-thinking the approach for apportionment between primary and secondary organic carbon

This study explores a large set of OC and EC measurements in PM(10) and PM(2.5) aerosol samples, undertaken with a long term constant analytical methodology, to evaluate the capability of the OC/EC minimum ratio to represent the ratio between the OC and EC aerosol components resulting from fossil fuel combustion (OC(ff)/EC(ff)). The data set covers a wide geographical area in Europe, but with a particular focus upon Portugal, Spain and the United Kingdom, and includes a great variety of sites: urban (background, kerbside and tunnel), industrial, rural and remote. The highest minimum ratios were found in samples from remote and rural sites. Urban background sites have shown spatially and temporally consistent minimum ratios, of around 1.0 for PM(10) and 0.7 for PM(2.5).The consistency of results has suggested that the method could be used as a tool to derive the ratio between OC and EC from fossil fuel combustion and consequently to differentiate OC from primary and secondary sources. To explore this capability, OC and EC measurements were performed in a busy roadway tunnel in central Lisbon. The OC/EC ratio, which reflected the composition of vehicle combustion emissions, was in the range of 03-0.4. Ratios of OC/EC in roadside increment air (roadside minus urban background) in Birmingham, UK also lie within the range 03-0.4. Additional measurements were performed under heavy traffic conditions at two double kerbside sites located in the centre of Lisbon and Madrid. The OC/EC minimum ratios observed at both sites were found to be between those of the tunnel and those of urban background air, suggesting that minimum values commonly obtained for this parameter in open urban atmospheres over-predict the direct emissions of OC(ff) from road transport. Possible reasons for this discrepancy are explored. (C) 2011 Elsevier Ltd. All rights reserved.

A qualidade das salas de berçários nos concelhos de Setubal e de Palmela

Tendo por principal objetivo contribuir para o estudo da qualidade das creches dos Concelhos de Setúbal e de Palmela, com este trabalho pretende-se (1) avaliar e descrever a qualidade de 30 salas de berçário através da aplicação da Escala de Avaliação do Ambiente de Creche – Edição Revista (Infant/Toddler Environment Rating Scale – Revised Edition [ITERS-R], Harms, Cryer, & Clifford, 2006), (2) avaliar e descrever as práticas de socialização dos prestadores de cuidados responsáveis pelas 30 salas de berçário através da aplicação da Escala de Interação do Prestador de Cuidados (Caregiver Interaction Scale [CIS], Arnett, 1989), (3) estudar a associação entre as práticas de socialização dos profissionais e a qualidade das salas de berçário, (4) estudar associações entre a qualidade das salas de berçário e as práticas de socialização dos profissionais e algumas variáveis de estrutura (rácio adulto/criança, tamanho do grupo, educação, formação e experiência dos prestadores de cuidados). Tendo em conta que os estudos efetuados em Portugal revelam qualidade inadequada e mínima nas salas de creche, os resultados obtidos no presente estudo sugerem que as salas observadas possuem qualidade entre o mínimo e o bom. Embora o presente estudo apresente resultados superiores, verificou-se que os itens que apresentam maiores fragilidades (áreas deficitárias), assim como os itens que expressam maior qualidade (áreas fortes) parecem convergir com os resultados das investigações já efetuadas, com efeito os itens relacionados com as subescalas Atividades e Rotinas de cuidados pessoais são os que apresentam os resultados mais preocupantes. A subescala Interação foi a que apresentou resultados superiores e as práticas de socialização dos prestadores de cuidados revelaram ser excelentes. Verificou-se, igualmente, que as salas orientadas por educadores de infância, assim como, as salas em que o principal prestador de cuidados era educador de infância revelaram qualidade superior do que salas orientadas por assistentes operacionais (auxiliares de ação educativa). Este efeito chama a atenção para a importância da formação e qualificação dos profissionais de educação, assim como, para a necessidade de se alterarem as políticas educativas, nomeadamente no que diz respeito à obrigatoriedade de existirem educadores de infância nas salas de berçário. - ABSTRACT With the main objective of contributing to the study of quality of infant/toddler center-based child care in the Counties of Setúbal and Palmela, this work aims to (1) assess and describe the quality of 30 infant classrooms by applying the Infant/Toddler Environment Rating Scale-Revised Edition ([ITERS-R], Harms, Cryer, & Clifford, 2006), (2) assess and describe the socialization practices of caregivers responsible for 30 infant classrooms by applying the Caregiver Interaction Scale ([CIS], Arnett, 1989), (3) study the association between the socialization practices of professionals and the quality of infant classrooms, (4) to study associations between the quality of infant classrooms and the socialization practices of professionals and some structure variables (ratio adult/child group size, education, training, and experience of carers). Considering that the studies carried out in Portugal reveal minimum or inadequate quality in infant/toddler center-based child care, the results of this study suggest that, in accordance with ITERS-R, the quality of the infant classrooms observed varies between minimum and good. Although the present study reports higher quality scores, it was found that items which present the biggest weaknesses (deficit areas) as well as the items which express higher quality (strengths) appear to converge with the results of the investigations already carried out, since the items related with subscales Activities and Personal Care Routines are those with the most worrisome results. The Interaction subscale from ITERS-R proved to be the one with higher scores, and socialization practices of caregivers proved to be excellent. It was also found that the rooms oriented by early childhood teachers, as well as the rooms in which the primary care provider was also guided by childhood teachers showed higher quality than when guided by operational assistants (educational activities assistants). This effect draws attention to the importance of the education professionals training and qualification, as well as the need for altering the educational policies, in particular as regards the obligation to ensure the existence of early childhood teachers in infant classrooms.