Copper-organic frameworks assembled from in situ generated 5-(4-pyridyl) tetrazole building blocks: synthesis, structural features, topological analysis and catalytic oxidation of alcohols

Two new metal- organic compounds {[Cu-3(mu(3)-4-(p)tz)(4)(mu(2)-N-3)(2)(DMF)(2)](DMF)(2)}(n) (1) and {[Cu(4ptz) (2)(H2O)(2)]}(n) (2) {4-ptz = 5-(4-pyridyl)tetrazolate} with 3D and 2D coordination networks, respectively, have been synthesized while studying the effect of reaction conditions on the coordination modes of 4-pytz by employing the [2 + 3] cycloaddition as a tool for generating in situ the 5-substituted tetrazole ligands from 4-pyridinecarbonitrile and NaN3 in the presence of a copper(II) salt. The obtained compounds have been structurally characterized and the topological analysis of 1 discloses a topologically unique trinodal 3,5,6-connected 3D network which, upon further simplification, results in a uninodal 8-connected underlying net with the bcu (body centred cubic) topology driven by the [Cu-3(mu(2)-N-3)(2)] cluster nodes and mu(3)-4-ptz linkers. In contrast, the 2D metal-organic network in 2 has been classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology assembled from the Cu nodes and mu(2)-4-ptz linkers. The catalytic investigations disclosed that 1 and 2 act as active catalyst precursors towards the microwave-assisted homogeneous oxidation of secondary alcohols (1-phenylethanol, cyclohexanol, 2-hexanol, 3-hexanol, 2-octanol and 3-octanol) with tert-butylhydroperoxide, leading to the yields of the corresponding ketones up to 86% (TOF = 430 h(-1)) and 58% (TOF = 290 h(-1)) in the oxidation of 1-phenylethanol and cyclohexanol, respectively, after 1 h under low power ( 10 W) microwave irradiation, and in the absence of any added solvent or additive.

Building intelligence open systems (BIOS)

Os edifícios estão a ser construídos com um número crescente de sistemas de automação e controlo não integrados entre si. Esta falta de integração resulta num caos tecnológico, o que cria dificuldades nas três fases da vida de um edifício, a fase de estudo, a de implementação e a de exploração. O desenvolvimento de Building Automation System (BAS) tem como objectivo assegurar condições de conforto, segurança e economia de energia. Em edifícios de grandes dimensões a energia pode representar uma percentagem significativa da factura energética anual. Um BAS integrado deverá contribuir para uma diminuição significativa dos custos de desenvolvimento, instalação e gestão do edifício, o que pode também contribuir para a redução de CO2. O objectivo da arquitectura proposta é contribuir para uma estratégia de integração que permita a gestão integrada dos diversos subsistemas do edifício (e.g. aquecimento, ventilação e ar condicionado (AVAC), iluminação, segurança, etc.). Para realizar este controlo integrado é necessário estabelecer uma estratégia de cooperação entre os subsistemas envolvidos. Um dos desafios para desenvolver um BAS com estas características consistirá em estabelecer a interoperabilidade entre os subsistemas como um dos principais objectivos a alcançar, dado que o fornecimento dos referidos subsistemas assenta normalmente numa filosofia multi-fornecedor, sendo desenvolvidos usando tecnologias heterogéneas. Desta forma, o presente trabalho consistiu no desenvolvimento de uma plataforma que se designou por Building Intelligence Open System (BIOS). Na implementação desta plataforma adoptou-se uma arquitectura orientada a serviços ou Service Oriented Architecture (SOA) constituída por quatro elementos fundamentais: um bus cooperativo, denominado BIOSbus, implementado usando Jini e JavaSpaces, onde todos os serviços serão ligados, disponibilizando um mecanismo de descoberta e um mecanismo que notificada as entidades interessadas sobre alterações do estado de determinado componente; serviços de comunicação que asseguram a abstracção do Hardware utilizado da automatização das diversas funcionalidades do edifício; serviços de abstracção de subsistemas no acesso ao bus; clientes, este podem ser nomeadamente uma interface gráfica onde é possível fazer a gestão integrada do edifício, cliente de coordenação que oferece a interoperabilidade entre subsistemas e os serviços de gestão energética que possibilita a activação de algoritmos de gestão racional de energia eléctrica.

Supercritical CO2 extraction of secondary metabolites from Agaricus blazei: experiments and modelling

The mycelium and young fruiting bodies of Agaricus blazei were submitted to supercritical CO2 extraction, in a modified commercial flow apparatus, at temperatures from 40 to 80 ºC, pressures up to 600 bar and CO2 flow-rates from 2.0 to 9.0 g.min-1. The best extraction conditions of secondary metabolites, whereby the degree of solubilization (g extract/100 g of fungi) is the highest, was obtained with pure CO2 at 400 bar, 70 ºC and a CO2 flow rate of 5.7g.min-1. The extract in that conditions were analysed by GC-Ms. In order to increase the extraction yield of secondary metabolites, which are mostly present in glycolipid fractions, a polar compound (ethanol) was used as co-solvent in the proportions of 5 and 10 % (mol/mol). The presence of ethanol increased the yield when compared with the extraction with pure CO2. Moreover, a simple model was applied to the supercritical CO2 extraction of secondary metabolites from Agaricus blazei.

Scheduling of head-dependent cascaded reservoirs considering discharge ramping constraints and start/stop of units

This paper is on the problem of short-term hydro scheduling (STHS), particularly concerning head-dependent reservoirs under competitive environment. We propose a novel method, based on mixed-integer nonlinear programming (MINLP), for optimising power generation efficiency. This method considers hydroelectric power generation as a nonlinear function of water discharge and of the head. The main contribution of this paper is that discharge ramping constraints and start/stop of units are also considered, in order to obtain more realistic and feasible results. The proposed method has been applied successfully to solve two case studies based on Portuguese cascaded hydro systems, providing a higher profit at an acceptable computation time in comparison with classical optimisation methods based on mixed-integer linear programming (MILP).

Comparison of fungal contamination between hospitals and companies food units

A descriptive study was developed to compare air and surfaces fungal contamination in ten hospitals’ food units and two food units from companies. Fifty air samples of 250 litres through impaction method were collected from hospitals’ food units and 41 swab samples from surfaces were also collected, using a 10 by 10 cm square stencil. Regarding the two companies, ten air samples and eight surface samples were collected. Air and surface samples were collected in food storage facilities, kitchen, food plating and canteen. Outdoor air was also collected since this is the place regarded as a reference. Simultaneously, temperature, relative humidity and meal numbers were registered. Concerning air from hospitals’ food units, 32 fungal species were identified, being the two most commonly isolated genera Penicillium sp.

Air fungal contamination in ten hospitals’ food units from Lisbon

A descriptive study was developed to monitor air fungal contamination in ten food units from hospitals. Fifty air samples of 250 litres were collected through impaction method. Samples were collected in food storage facilities, kitchen, food plating, canteen and also, outside premises, since this is the place regarded as reference. Simultaneously, environmental parameters were also monitored, including temperature and relative humidity through the equipment Babouc, LSI Sistems and according to the International Standard ISO 7726.

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.

Comparison of indoor and outdoor fungi and particles in poultry units

A descriptive study was developed in order to compare indoor and outdoor air contamination caused by fungi and particles in seven poultry units. Twenty eight air samples of 25 litters were collected through the impaction method on malt extract agar. Air sampling and particles concentration measurement were done in the interior and also outside premises of the poultries’ pavilions. Regarding the fungal load in the air, indoor concentration of mold was higher than outside air in six poultry units. Twenty eight species / genera of fungi were identified indoor, being Scopulariopsis brevicaulis (40.5%) the most commonly isolated species and Rhizopus sp. (30.0%) the most commonly isolated genus. Concerning outdoor, eighteen species/genera of fungi were isolated, being Scopulariopsis brevicaulis (62.6%) also the most isolated. All the poultry farms analyzed presented indoor fungi different from the ones identified outdoors. Regarding particles’ contamination, PM2.5, PM5.0 and PM10 had a statistically significant difference (Mann-Whitney U test) between the inside and outside of the pavilions, with the inside more contaminated (p=.006; p=.005; p=.005, respectively). The analyzed poultry units are potential reservoirs of substantial amounts of fungi and particles and could therefore free them in the atmospheric air. The developed study showed that indoor air was more contaminated than outdoors, and this can result in emission of potentially pathogenic fungi and particles via aerosols from poultry units to the environment, which may post a considerable risk to public health and contribute to environmental pollution.

Occupational exposure to aflatoxin (AFB1) in poultry production

Aflatoxin B1 (AFB1) has been recognized to produce cancer in human liver. In addition, epidemiological and laboratory studies demonstrated that the respiratory system was a target for AFB1. Exposure occurs predominantly through the food chain, but inhalation represents an additional route of exposure. The present study aimed to examine AFB1 exposure among poultry workers in Portugal. Blood samples were collected from a total of 31 poultry workers from six poultry farms. In addition, a control group (n = 30) was included comprised of workers who undertook administrative tasks. Measurement of AFB1 in serum was performed by enzyme-linked immunosorbent assay (ELISA). For examining fungi contamination, air samples were collected through an impaction method. Air sampling was obtained in pavilion interior and outside the premises, since this was the place regarded as the reference location. Using molecular methods, toxicogenic strains (aflatoxin-producing) were investigated within the group of species belonging to Aspergillus flavus complex. Eighteen poultry workers (59%) had detectable levels of AFB1 with values ranging from <1 ng/ml to4.23 ng/ml and with a mean value of 2 ± 0.98ng/ml. AFB1 was not detected in the serum sampled from any of the controls. Aspergillus flavus was the fungal species third most frequently found in the indoor air samples analyzed (7.2%) and was the most frequently isolated species in air samples containing only Aspergillus genus (74.5%). The presence of aflatoxigenic strains was only confirmed in outdoor air samples from one of the units, indicating the presence of a source inside the building in at least one case. Data indicate that AFB1 inhalation represents an additional risk in this occupational setting that needs to be recognized, assessed, and prevented.

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.

Fungal contamination in swine: a potential occupational health threat

Poor air quality in a pig-confinement building may potentially place farmers at higher health risk than other workers for exposure to airborne pollutants that may reach infectious levels. The aim of this study was to assess worker exposure to fungi in indoor environments in Portuguese swine buildings. Air samples from 7 swine farms were collected at a flow rate of 140 L/min, at 1 m height, onto malt extract agar supplemented with chloramphenicol (MEA). Surfaces samples of the same indoor sites were obtained by swabbing the surfaces. Samples from the floor covering were also collected from four of seven swine farms. All collected samples were incubated at 27°C for 5-7 days. After lab processing and incubation of obtained samples, quantitative colony-forming units (CFU)/m(3), CFU/cm(2), and CFU/g and qualitative results were determined with identification of isolated fungal species. Aspergillus versicolor was the most frequent species found in air (21%), followed by Scopulariopsis brevicaulis (17%) and Penicillium sp. (14%). Aspergillus versicolor was also the most frequent species noted on surfaces (26.6%), followed by Cladosporium sp. (22.4%) and Scopulariopsis brevicaulis (17.5%). Chrysosporium was the most frequently found genera in the new floor covering (38.5%), while Mucor was the most prevalent genera (25.1%) in used floor covering. Our findings corroborate a potential occupational health threat due to fungi exposure and suggest the need for a preventive strategy.

Projeto de estruturas e fundações de um edifício de serviços

O presente trabalho é o culminar de um percurso académico cheio de aprendizagens que me preencheu por completo. A realização de um projeto de estruturas como trabalho final de mestrado (TFM) foi uma escolha fácil, pois, na minha opinião, permite fazer a transição entre os conceitos adquiridos durante o curso e os métodos utilizados no ambiente não académico. O objetivo do trabalho é realizar o projeto de estruturas e fundações de um edifício destinado a serviços. Foram aplicados os conhecimentos adquiridos ao longo de todo o curso de Engenharia Civil, em especial das Unidades Curriculares de dimensionamento de estruturas. Foi elaborado um modelo da estrutura num programa de cálculo automático: SAP2000. Assim, de acordo com os resultados fornecidos pelo programa e através da consulta dos regulamentos nacionais (REBAP e RSA) e internacionais (Eurocódigos), foi possível dimensionar todos os elementos estruturais. Os diferentes aspetos condicionantes no projeto foram devidamente analisados e discutidos, por forma a encontrar a solução que mais se adequa ao pretendido. Todas as opções tomadas são devidamente justificadas, procurando-se elaborar um trabalho detalhado e, acima de tudo, correto. É importante dizer ainda que, a permanente troca de ideias e conhecimentos entre colegas e, como é óbvio, com o orientador do trabalho, foi muito relevante na realização deste trabalho. Uma parte essencial de um projeto são, sem dúvida, as peças desenhadas. Nesse capítulo tentou-se atingir um nível de detalhe e simplicidade que permita uma interpretação inequívoca dos mesmos.

Manutenção preventiva de um edifício hospitalar

Os Hospitais, equipamentos de interesse público, são edifícios cujos desempenho e disponibilidade das suas instalações e equipamentos podem comprometer a prestação de cuidados de saúde, pelo que nestes estabelecimentos, a Manutenção Preventiva assume um papel relevante. Nesse sentido, pretendeu-se nesta dissertação definir uma estratégia específica que permita efectuar o planeamento da manutenção preventiva de um edifício hospitalar, enquanto infraestrutura para desenvolvimento da actividade clínica. Para tal, foi efectuada uma pesquisa bibliográfica, com a qual se identificaram conceitos de manutenção e requisitos a serem tidos em conta na manutenção de edifícios hospitalares. Foi efectuada uma caracterização genérica do objecto de manutenção, limitada no âmbito desta dissertação às principais componentes dos sistemas de construção e das instalações de águas e esgotos, que podem integrar um edifício hospitalar actual, atendendo às especificações e recomendações técnicas vigentes para este tipo de edifícios. Foram identificados os objectivos e requisitos de manutenção nestes edifícios, estabelecidos pelas condições de funcionamento pretendidas, pelos critérios de durabilidade exigidos pelo Dono de Obra, pelo nível de desempenho funcional requerido para as suas componentes e pelo grau de operacionalidade imposto nas suas diferentes unidades funcionais. Tendo em consideração que a criticidade de uma componente não depende só do contexto operacional da área funcional em se insere mas também das consequências que o seu estado de funcionamento pode acarretar para a unidade funcional. Foi exemplificada a análise dos modos de falha, sua criticidade e seus efeitos para hierarquização do risco associado nas componentes estudadas. As fichas exemplificativas dos planos de manutenção preventiva, que se apresentam no âmbito desta dissertação para algumas componentes básicas, integram acções e procedimentos que derivam de uma análise aos seus modos de falha e seus efeitos, bem como de recomendações técnicas exigências da regulamentação em vigor.

Sensing Cloud Optimization to Solve ED of Units with Valve-Point Effects and Multi-fuels

In this paper a solution to an highly constrained and non-convex economical dispatch (ED) problem with a meta-heuristic technique named Sensing Cloud Optimization (SCO) is presented. The proposed meta-heuristic is based on a cloud of particles whose central point represents the objective function value and the remaining particles act as sensors "to fill" the search space and "guide" the central particle so it moves into the best direction. To demonstrate its performance, a case study with multi-fuel units and valve- point effects is presented.

Projeto de AVAC e classificação energética de uma cafetaria

Trabalho Final de mestrado para obtenção do grau de Mestre em Engenharia Civil