Concepção de um reactor batch multifunções

Mestrado em Engenharia Química

Contribuição para o estudo da combinação de cal com cimento no tratamento de solos

Mestrado em Engenharia Geotécnica e Geoambiente

ß-Lactams: chemical structure, mode of action and mechanisms of resistance

This synopsis summarizes the key chemical and bacteriological characteristics of β-lactams, penicillins, cephalosporins, carbanpenems, monobactams and others. Particular notice is given to first-generation to fifth-generation cephalosporins. This review also summarizes the main resistance mechanism to antibiotics, focusing particular attention to those conferring resistance to broad-spectrum cephalosporins by means of production of emerging cephalosporinases (extended-spectrum β-lactamases and AmpC β-lactamases), target alteration (penicillin-binding proteins from methicillin-resistant Staphylococcus aureus) and membrane transporters that pump β-lactams out of the bacterial cell.

Structural, physical, and chemical modifications induced by microwave heating on native agar-like galactans

Native agars from Gracilaria vermiculophylla produced in sustainable aquaculture systems (IMTA) were extracted under conventional (TWE) and microwave (MAE) heating. The optimal extracts from both processes were compared in terms of their properties. The agars’ structure was further investigated through Fourier transform infrared and NMR spectroscopy. Both samples showed a regular structure with an identical backbone, β-D-galactose (G) and 3,6-anhydro-α-L-galactose (LA) units; a considerable degree of methylation was found at C6 of the G units and, to a lesser extent, at C2 of the LA residues. The methylation degree in the G units was lower for MAEopt agar; the sulfate content was also reduced. MAE led to higher agar recoveries with drastic extraction time and solvent volume reductions. Two times lower values of [η] and Mv obtained for the MAEopt sample indicate substantial depolymerization of the polysaccharide backbone; this was reflected in its gelling properties; yet it was clearly appropriate for commercial application in soft-texture food products.

Validação da versão portuguesa do método 'Internacional Chemical Control Toolkit'

Em Portugal, como em outros países, podem ser encontrados milhares de trabalhadores com doenças e outros problemas resultantes da exposição aos compostos orgânicos voláteis (COV’s). No entanto são poucos os estudos aplicados à actividade industrial. Neste trabalho validou-se/estimou-se a exposição ocupacional a COV´s dos trabalhadores que executam a tarefa de ‘aplicação de revestimento do mobiliário’, mais conhecida por ‘acabamento de móveis’ na secção de acabamentos do sector de mobiliário de madeira, que se situa nos concelhos de Paços de Ferreira e Paredes, concelhos do Norte de Portugal. A amostra foi constituída por 17 empresas e foram avaliados 34 tarefas que corresponde ao mesmo número de trabalhadores, uma vez que eles executam essa tarefa durante as oito horas diárias de trabalho. Para avaliar a exposição dos trabalhadores foram utilizadas duas abordagens da higiene do trabalho: a pragmática, através da aplicação do método Toolkit e a tradicional com recurso a amostragens de ar e análises laboratoriais. Os resultados obtidos sugerem que o Toolkit é uma boa ferramenta para ser utilizada pelas Pequenas e Médias Empresas (PME’s), que trabalhem com substâncias em pó ou líquidas. É um método expedito e que não acarreta grandes esforços financeiros. Verificou-se ainda que a maioria dos trabalhadores estão em risco de exposição a COV’s. Sendo necessário tomar medidas de controlo.

Produção de hidrogénio através da gasificação da biomassa

A procura de uma forma limpa de combustível, aliada à crescente instabilidade de preços dos combustíveis fósseis verificada nos mercados faz com que o hidrogénio se torne num combustível a considerar devido a não resultar qualquer produto poluente da sua queima e de se poder utilizar, por exemplo, desperdícios florestais cujo valor de mercado não está inflacionado por não pertencer à cadeia alimentar humana. Este trabalho tem como objetivo simular o processo de gasificação de biomassa para produção de hidrogénio utilizando um gasificador de leito fluidizado circulante. O oxigénio e vapor de água funcionam como agentes gasificantes. Para o efeito usou-se o simulador de processos químicos ASPEN Plus. A simulação desenvolvida compreende três etapas que ocorrem no interior do gasificador: pirólise, que foi simulada por um bloco RYIELD, combustão de parte dos compostos voláteis, simulada por um bloco RSTOIC e, por fim, as reações de oxidação e gasificação do carbonizado “char”, simuladas por um bloco RPLUG. Os valores de rendimento dos compostos após a pirólise, obtidos por uma correlação proposta por Gomez-Barea, et al. (2010), foram os seguintes: 20,33% “char”, 22,59% alcatrão, 36,90% monóxido de carbono, 16,05%m/m dióxido de carbono, 3,33% metano e 0,79% hidrogénio (% em massa). Como não foi possível encontrar valores da variação da composição do gás à saída do gasificador com a variação da temperatura, para o caso de vapor de água e oxigénio, optou-se por utilizar apenas vapor na simulação de forma a comparar os seus valores com os da literatura. Às temperaturas de 700, 770 e 820ºC, para um “steam-to-biomass ratio”, (SBR) igual a 0,5, os valores da percentagem molar de monóxido de carbono foram, respetivamente, 56,60%, 55,84% e 53,85%, os valores de hidrogénio foram, respetivamente, 17,83%, 18,25% e 19,31%, os valores de dióxido de carbono foram, respetivamente, 16,40%, 16,85% e 17,93% e os valores de metano foram, respetivamente, 9,00%, 8,95% e 8,83%. Os valores da composição à saída do gasificador, à temperatura de 820ºC, para um SBR de 0,5 foram: 53,85% de monóxido de carbono, 19,31% de hidrogénio, 17,93% de dióxido de carbono e 8,83% de metano (% em moles). Para um SBR de 0,7 a composição à saída foi de 54,45% de monóxido de carbono, 19,01% de hidrogénio, 17,59% de dióxido de carbono e 8,87% de metano. Por fim, quando SBR foi igual a 1 a composição do gás à saída foi de 55,08% de monóxido de carbono, 18,69% de hidrogénio, 17,24% de dióxido de carbono e 8,90% de metano. Os valores da composição obtidos através da simulação, para uma mistura de ar e vapor de água, ER igual a 0,26 e SBR igual a 1, foram: 34,00% de monóxido de carbono, 14,65% de hidrogénio, 45,81% de dióxido de carbono e 5,41% de metano. A simulação permitiu-nos ainda dimensionar o gasificador e determinar alguns parâmetros hidrodinâmicos do gasificador, considerando que a reação “water-gas shift” era a limitante, e que se pretendia obter uma conversão de 95%. A velocidade de operação do gasificador foi de 4,7m/s e a sua altura igual a 0,73m, para um diâmetro de 0,20m.

The periodic table: contest and exhibition

The systemization and organization of ideas and concepts is an integral part of science. In chemistry, the organization of the periodic table of the chemical elements in the 1860s was one of the greatest scientific breakthroughs ever made and in fact during the 20th century it became a universally recognized scientific icon (1). The periodic table is the fundamental classificatory scheme of the elements and summarizes the realm of chemistry (2). Simply knowing the position of an element in the periodic table tells us about its properties and is usually enough to predict how the element will behave in a wide variety of different situations or reactions (1). Based on this potential mine of information, it is possible to make reliable predictions of the properties of the compounds that each element forms. Nowadays, the concept of the periodic table is starting to interact with other sciences and reports of periodic tables of amino acids (3), genetic codes (4), protein structures (5), and biology (6) can be found in the specialized literature. Symbiosis between science and art, for example, “The Periodic Table of The Elephants” (7), can also be seen. To appeal to a better understanding of the periodic table, the Instituto Superior de Engenharia do Instituto Politécnico do Porto and the Centro de Química da Universidade do Porto promoted a contest and exhibit with the goal of stimulating a wide and heterogeneous audience, ranging from young children and their parents to graduate students from several disciplines, to explore the nature of this icon. Imaginative educational activities such as contests (8–10), games (11, 12), and puzzles (13–15) provided a way to communicate with the general public with the goal of attracting students to science. This also constituted an interesting, informative, and entertaining alternative to non-interactive lectures. Simultaneously, artistic creativity was combined with scientific knowledge.

Wine and grape polyphenols — a chemical perspective

Phenolic compounds constitute a diverse group of secondary metabolites which are present in both grapes and wine. The phenolic content and composition of grape processed products (wine) are greatly influenced by the technological practice to which grapes are exposed. During the handling and maturation of the grapes several chemical changes may occur with the appearance of new compounds and/or disappearance of others, and consequent modification of the characteristic ratios of the total phenolic content as well as of their qualitative and quantitative profile. The non-volatile phenolic qualitative composition of grapes and wines, the biosynthetic relationships between these compounds, and the most relevant chemical changes occurring during processing and storage will be highlighted in this review.

β-Lactams: chemical structure, mode of action and mechanisms of resistance

This synopsis summarizes the key chemical and bacteriological characteristics of β-lactams, penicillins, cephalosporins, carbanpenems, monobactams and others. Particular notice is given to first-generation to fifth-generation cephalosporins. This reviewalso summarizes the main resistancemechanism to antibiotics, focusing particular attention to those conferring resistance to broad-spectrum cephalosporins by means of production of emerging cephalosporinases (extended-spectrum β-lactamases and AmpC β-lactamases), target alteration (penicillin-binding proteins from methicillin-resistant Staphylococcus aureus) and membrane transporters that pump β-lactams out of the bacterial cell.

Microstructure, mechanical properties and chemical degradation of brazed AISI 316 stainless steel/alumina systems

The main aims of the present study are simultaneously to relate the brazing parameters with: (i) the correspondent interfacial microstructure, (ii) the resultant mechanical properties and (iii) the electrochemical degradation behaviour of AISI 316 stainless steel/alumina brazed joints. Filler metals on such as Ag–26.5Cu–3Ti and Ag–34.5Cu–1.5Ti were used to produce the joints. Three different brazing temperatures (850, 900 and 950 °C), keeping a constant holding time of 20 min, were tested. The objective was to understand the influence of the brazing temperature on the final microstructure and properties of the joints. The mechanical properties of the metal/ceramic (M/C) joints were assessed from bond strength tests carried out using a shear solicitation loading scheme. The fracture surfaces were studied both morphologically and structurally using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction analysis (XRD). The degradation behaviour of the M/C joints was assessed by means of electrochemical techniques. It was found that using a Ag–26.5Cu–3Ti brazing alloy and a brazing temperature of 850 °C, produces the best results in terms of bond strength, 234 ± 18 MPa. The mechanical properties obtained could be explained on the basis of the different compounds identified on the fracture surfaces by XRD. On the other hand, the use of the Ag–34.5Cu–1.5Ti brazing alloy and a brazing temperature of 850 °C produces the best results in terms of corrosion rates (lower corrosion current density), 0.76 ± 0.21 μA cm−2. Nevertheless, the joints produced at 850 °C using a Ag–26.5Cu–3Ti brazing alloy present the best compromise between mechanical properties and degradation behaviour, 234 ± 18 MPa and 1.26 ± 0.58 μA cm−2, respectively. The role of Ti diffusion is fundamental in terms of the final value achieved for the M/C bond strength. On the contrary, the Ag and Cu distribution along the brazed interface seem to play the most relevant role in the metal/ceramic joints electrochemical performance.

Desenvolvimento de métodos rápidos para deteção de drogas no meio aquático

A vasta aplicação de antibióticos em sistemas de aquacultura tem conduzido ao aparecimento de espécies microbianas resistentes, devendo ser evitada ou, se possível, minimizada. A minimização implica um controlo muito rigoroso das doses aplicadas, algo que só pode ser realizado se todo o processo analítico for simples, barato e puder ser implementado no local. O presente trabalho descreve para este efeito um sistema sensor constituído por papel quimicamente modificado, cujo procedimento analítico foi semelhante à monitorização de pH através das conhecidas tiras indicadoras de pH universal. O papel foi modificado com base em reacções de monocamadas e assumiu uma coloração típica após contacto com o antibiótico. A intensidade da coloração estava também relacionada com a concentração desse antibiótico. Como prova deste conceito, o sensor proposto foi desenhado tendo em vista a monitorização de oxitetraciclina, um dos antibióticos utilizados neste contexto com elevada frequência. A modificação do papel foi baseada na alteração química das unidades de glucose na matriz sólida por reacção covalente com reagentes apropriados. Foram utilizadas duas estratégias diferentes para este efeito: uma foi baseada em reacções de tipo sol-gel e a outra em reacção de adição nucleófila. Posteriormente, o papel foi modificado com espécies metálicas capazes de mudar de cor na presença da oxitetraciclina. Estas modificações químicas foram avaliadas e optimizadas relativamente a vários parâmetros, no sentido de promover uma variação de cor intensa face à concentração de antibiótico. Procedeu-se ainda ao controlo desta modificação por técnicas de espectroscopia de infravermelho. A variação de cor foi avaliada por comparação visual, mas registada por imagem digital. Os materiais sensores preparados foram ainda caracterizados do ponto de vista do seu desempenho analítico. Incluíram-se aqui a identificação de uma relação linear entre coordenadas de cor e concentração, a atribuição de uma gama de concentrações capaz de fornecer uma resposta previsível e resposta cruzada face a outros antibióticos. Procedeu-se ainda à aplicação dos sensores numa amostra de água ambiental dopada com antibiótico. De uma forma geral, foi possível estabelecer um processo simples de modificação de papel capaz de aferir a presença e a quantidade de tetraciclinas, mais concretamente a oxitetraciclina. O processo aqui estabelecido é promissor, antevendo a concretização de uma metodologia simples, barata e local para a monitorização de anitbióticos em águas.

Incorporating sustainability into a chemical company’s modus operandi

The intent of this dissertation is to review relevant existing management systems and chemical industry initiatives to identify synergies, overlaps and gaps with Sustainability best practices, to map the barriers to the incorporation of Sustainability and formulate recommendations to facilitate execution of Sustainability practices within existing management systems. A chemical industry Sustainability survey was conducted through APEQ, the Portuguese association of chemical companies, which constitutes the first baseline on the topic for this national industry association. The commonly used international standards and the Responsible Care® (RC) initiative were cross-referenced against the United Nations Global Compact Assessment Tool. Guidance on how to incorporate Sustainability into a company‘s modus operandi was collapsed into Sustainability Playbooks. The survey revealed that 73% of the APEQ member companies that participated in the survey have a Sustainability Plan. Both large and small/medium APEQ member companies see the market not willing to pay extra for ‗greener‘ products as one of the main barriers. APEQ large enterprise see complexity of implementation and low return on investment as the other most significant barriers while small/medium enterprise respond that the difficulty to predict customer sustainability needs is the other most significant barrier. Amongst many other insights from this survey reported to APEQ, Life Cycle Assessment practices were found to have a low level of implementation and were also considered of low importance, thus identifying a very important opportunity in Sustainability practices to be addressed by APEQ. Two hundred and seventy three assessment points from United Nations Global Compact Assessment Tool plus five additional items were cross-referenced with international standard requirements. With the authorization of the intellectual property owners, the United Nations Global Compact Assessment Tool was modified to introduce actionable recommendations for each gap identified by management standard. This tool was automated to output specific recommendations for 63 possible combinations after simply selecting from a list of commonly used management standards and the RC initiative. Finally this modified tool was introduced into Playbooks for Incorporation of Sustainability at two levels: a ―Get Started Playbook‖ for beginners or small/medium size enterprise and an ―Advanced Playbook‖ as a second advancement stage or for large enterprise.

Study on the changes of soil chemical characteristics as result of prescribed fire

Every year, particularly during the summer period, the Portuguese forests are devastated by forest fire that destroys their ecosystems. So in order to prevent these forest fires, public and private authorities frequently use methods for the reduction of combustible mass as the prescribed fire and the mechanical vegetation pruning. All of these methods of prevention of forest fires alter the vegetation layer and/or soil [1-2]. This work aimed the study of the variation of some chemical characteristics of soil that suffered prescribed fire. The studied an area was located in the Serra of Cabreira (Figure 1) with 54.6 ha. Twenty sampling points were randomly selected and samples were collected with a shovel before, just after the prescribed fire, and 125 and 196 days after that event. The parameters that were studied were: pH, soil moisture, organic matter and iron, magnesium and potassium total concentration. All the analysis followed International Standard Methodologies. This work allowed to conclude that: a) after the prescribed fire; i) the pH remained practically equal to the the initial value; ii) occurred a slight increase of the average of the organic matter contents and iron total contents; b) at the end of the sampling period compared to the initial values; i) the pH didn´t change significantly; ii) the average of the contents of organic matter decreased; and iii) the average of the total contents of Fe, Mg and K increased.

Impact of prescribed fire on the chemical properties of soil

Prescribed fire is a common forest management tool used in Portugal to reduce the fuel load availability and minimize the occurrence of wildfires. In addition, the use of this technique also causes an impact to ecosystems. In this presentation we propose to illustrate some results of our project in two forest sites, both located in Northwest Portugal, where the effect of prescribed fire on soil properties were recorded during a period of 6 months. Changes in soil moisture, organic matter, soil pH and iron, were examined by Principal Component Analysis multivariate statistics technique in order to determine impact of prescribed fire on these soil properties in these two different types of soils and determine the period of time that these forest soils need to recover to their pre-fire conditions, if they can indeed recover. Although the time allocated to this study does not allow for a widespread conclusion, the data analysis clearly indicates that the pH values are positively correlated with iron values at both sites. In addition, geomorphologic differences between both sampling sites, Gramelas and Anjos, are relevant as the soils’ properties considered have shown different performances in time. The use of prescribed fire produced a lower impact in soils originated from more amended bedrock and therefore with a ticker humus covering (Gramelas) than in more rocky soils with less litter covering (Anjos) after six months after the prescribed fire occurrence.

Simulação de um processo de pirólise rápida de biomassa

Mestrado em Engenharia Química - Ramo Optimização Energética na Indústria Química