DNA-based biosensor for the electrocatalytic determination of antioxidant capacity in beverages

Reactive oxygen species (ROS) are produced as a consequence of normal aerobic metabolism and are able to induce DNA oxidative damage. At the cellular level, the evaluation of the protective effect of antioxidants can be achieved by examining the integrity of the DNA nucleobases using electrochemical techniques. Herein, the use of an adenine-rich oligonucleotide (dA21) adsorbed on carbon paste electrodes for the assessment of the antioxidant capacity is proposed. The method was based on the partial damage of a DNA layer adsorbed on the electrode surface by OH• radicals generated by Fenton reaction and the subsequent electrochemical oxidation of the intact adenine bases to generate an oxidation product that was able to catalyze the oxidation of NADH. The presence of antioxidant compounds scavenged hydroxyl radicals leaving more adenines unoxidized, and thus, increasing the electrocatalytic current of NADHmeasured by differential pulse voltammetry (DPV). Using ascorbic acid (AA) as a model antioxidant species, the detection of as low as 50nMof AA in aqueous solution was possible. The protection efficiency was evaluated for several antioxidant compounds. The biosensor was applied to the determination of the total antioxidant capacity (TAC) in beverages.

Electrocatalytic evaluation of DNA damage by superoxide radical for antioxidant capacity assessment

The integrity of DNA purine bases was herein used to evaluate the antioxidant capacity. Unlike other DNA-based antioxidant sensors reported so far, the damaging agent chosen was the O 2 radical enzymatically generated by the xanthine/xanthine oxidase system. An adenine-rich oligonucleotide was adsorbed on carbon paste electrodes and subjected to radical damage in the presence/absence of several antioxidant compounds. As a result, partial damage on DNA was observed. A minor product of the radical oxidation was identified by cyclic voltammetry as a diimine adenine derivative also formed during the electrochemical oxidation of adenine/guanine bases. The protective efficiency of several antioxidant compounds was evaluated after electrochemical oxidation of the remaining unoxidized adenine bases, by measuring the electrocatalytic current of NADH mediated by the adsorbed catalyst species generated. A comparison between O 2 and OH radicals as a source of DNA lesions and the scavenging efficiency of various antioxidant compounds against both of them is discussed. Finally, the antioxidant capacity of beverages was evaluated and compared with the results obtained with an optical method.

Síntese e caracterização das propriedades fotofísicas de flavotionas

O presente trabalho descreve a síntese de 10 flavotionas e a sua caracterização espectroscópica e fotofísica, incluindo a determinação dos rendimentos quânticos de formação de tripleto e de produção de oxigénio singuleto. Os dados obtidos foram correlacionados com cálculos de orbitais moleculares de forma a racionalizar o efeito do padrão de substituição de grupo OH (hidroxilo) nas propriedades espectroscópicas e fotofísicas das flavotionas. Foi ainda estudada a fotodegradação dos compostos, isolados e identificados os fotoprodutos obtidos em diferentes meios, e proposto um mecanismo para a actuação destes compostos como fotosensitizadores. E finalmente, utilizar este conhecimento para desenvolver pesticidas activados pela absorção de luz, mais eficientes e amigos do ambiente.

Condições dentárias entre adultos brasileiros de 1986 a 2010

OBJETIVO: Identificar tendências do padrão da cárie dentária em adultos brasileiros. MÉTODOS: Foram utilizados dados provenientes de levantamentos epidemiológicos realizados pelo Ministério da Saúde nos anos de 1986, 2003 e 2010. A experiência de cárie, expressa pelo índice CPOD (dentes permanentes cariados, perdidos e obturados), e a saúde dentária, expressa pelo índice OH-D (dentes hígidos + obturados) relativo ao número de dentes funcionais, foram comparadas em amostras aleatórias de residentes de 35 a 44 anos de idade em cada região brasileira. As diferenças nas condições dentárias entre os anos foram estimadas por meio da razão dos valores dos índices, empregando-se análise de regressão de Poisson ajustada pela idade. RESULTADOS: Houve reduções no índice CPOD e aumento no índice OH-D em todas as regiões no período de 1986 a 2010. A região Norte, que tinha o pior padrão em 1986, apresentou o maior ganho em termos de dentição funcional. CONCLUSÕES: Tem ocorrido uma transição da saúde bucal para melhor nos adultos brasileiros. É plausível que a adição de flúor à água e ao creme dental, maior incorporação de serviços restauradores e a melhoria nos indicadores de desenvolvimento humano decorrentes de políticas públicas estejam relacionados a essa melhora.

Biodiesel production over lithium modified lime catalysts: activity and deactivation

Biodiesel production by methanolysis of semi-refined rapeseed oil was studied over lime based catalysts. In order to improve the catalysts basicity a commercial CaO material was impregnated with aqueous solution of lithium nitrate (Li/Ca = 03 atomic ratio). The catalysts were calcined at 575 degrees C and 800 degrees C, for 5 h, to remove nitrate ions before reaction. The XRD patterns of the fresh catalysts, including the bare CaO, showed lines ascribable to CaO and Ca(OH)(2). The absence of XRD lines belonging to Li phases confirms the efficient dispersion of Li over CaO. In the tested condition (W-cat/W-oil = 5%; CH3OH/oil = 12 molar ratio) all the fresh catalysts provided similar biodiesel yields (FAME >93% after 4 h) but the bare CaO catalyst was more stable. The activity decay of the Li modified samples can be related to the enhanced, by the higher basicity, calcium diglyceroxide formation during methanolysis which promotes calcium leaching. The calcination temperature for Li modified catalysts plays an important role since encourages the crystals sinterization which appears to improve the catalyst stability. (C) 2013 Elsevier B.V. All rights reserved.

Dinuclear Mn (II,II) complexes: magnetic properties and microwave assisted oxidation of alcohols

A series of six new mixed-ligand dinuclear Mn(II, II) complexes of three different hydrazone Schiff bases (H3L1, H3L2 and H3L3), derived from condensation of the aromatic acid hydrazides benzohydrazide, 2-aminobenzohydrazide or 2-hydroxybenzohydrazide, with 2,3-dihydroxy benzaldehyde, respectively, is reported. Reactions of Mn(NO3)(2) center dot 4H(2)O with the H3L1-3 compounds, in the presence of pyridine (1 : 1 : 1 mole ratio), in methanol at room temperature, yield [Mn(H2L1)(py)(H2O)](2)(NO3)(2) center dot 2H(2)O (1 center dot 2H(2)O), [Mn(H2L2)(py)(CH3OH)](2)(NO3)(2) center dot 4H(2)O (2 center dot 4H(2)O) and [Mn(H2L3)(py)(H2O)](2)(NO3)(2) (3) respectively, whereas the use of excess pyridine yields complexes with two axially coordinated pyridine molecules at each Mn(II) centre, viz. [Mn(H2L1)(py)(2)] 2(NO3)(2) center dot H2O (4 center dot H2O), [Mn(H2L2)(py) H-O (6 center dot 2CH(3)OH), respectively. In all the complexes, the (H2L1-3)-ligand coordinates in the keto form. Complexes 1 center dot 2H(2)O, 2 center dot 4H(2)O, 4 center dot H2O, 5 center dot 2H(2)O and 6 center dot 2CH(3)OH are characterized by single crystal X-ray diffraction analysis. The complexes 1, 2 and 6, having different coordination environments, have been selected for variable temperature magnetic susceptibility measurements to examine the nature of magnetic interaction between magnetically coupled Mn(II) centres and also for exploration of the catalytic activity towards microwave assisted oxidation of alcohols. A yield of 81% (acetophenone) is obtained using a maximum of 0.4% molar ratio of catalyst relative to the substrate in the presence of TEMPO and in aqueous basic solution, under mild conditions.

Conservação de negativos em triacetato de celulose

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Conservação e Restauro (Área de Fotografia)

An SEM investigation of the pozzolanic activity of a waste catalyst oil refinery

The most active phase of the fluid catalytic cracking (FCC) catalyst, used in oil refinery, is zeolite-Y which is an aluminosilicate with a high internal and external surface area responsible for its high reactivity. Waste FCC catalyst is potentially able to be reused in cement-based materials - as an additive - undergoing a pozzolanic reaction with calcium hydroxide (Ca(OH)2) formed during cement hydration [1-3]. This reaction produces additional strength-providing reaction products i.e., calcium silicate hydrate (C-S-H) and hydrous calcium aluminates (C-A-H) which exact chemical formula and structure are still unknown. Partial replacement of cement by waste FCC catalyst has two key advantages: (1) lowering of cement production with the associated pollution reduction as this industry represents one of the largest sources of man-made CO2 emissions, and (2) improving the mechanical properties and durability of cement-based materials. Despite these advantages, there is a lack of fundamental knowledge on pozzolanic reaction mechanisms as well as spatial distribution of porosity and solid phases interactions at the microstructural level and consequently their relationship with macroscopical engineering properties of catalyst/cement blends. Within this scope, backscattered electron (BSE) images acquired in a scanning electron microscope (SEM) equipped with Energy-Dispersive Spectroscopy (EDS) and by X-ray diffraction were used to investigate chemical composition of hydration products and to analyse spatial information of the microstructure of waste FCC catalyst blended cement mortars. For this purpose mortars with different levels of cement substitution by waste catalyst as well as with different hydration ages, were prepared. The waste FCC catalyst used is produced by the Portuguese refinery company Petrogal S.A.

Reactivity of bulky tris(Phenylpyrazolyl) methanesulfonate copper(I) complexes towards small unsaturated molecules

Reaction of the tris(3-phenylpyrazolyl)methane sulfonate species (Tpms(Ph))Li with the copper(I) complex [Cu(MeCN)(4)][PF6] affords [Cu(Tpms(Ph))(MeCN)] 1. The latter, upon reaction with equimolar amounts of cyclohexyl-(CyNC) or 2,6-dimethylphenyl (XylNC) isocyanides, or excess CO, furnishes the corresponding Cu(I)complexes [Cu(Tpms(Ph))(CNR)] (R = Cy 2, Xyl 3) or [Cu(Tpms(Ph))(CO)] 4. The ligated isocyanide in 2 or 3 (or the acetonitrile ligand in 1)is displaced by 3-iminoisoindolin-1-one to afford 5, the first copper(I) complex containing an 3-iminoisoindolin-1-one ligand. The ligated acetonitrile in 1 undergoes nucleophilic attack by methylamine to give the amidine complex [Cu(Tpms(Ph)){MeC(NH)NHMe}] 6, whereas only the starting materials were recovered from the attempted corresponding reactions of 2 and 3 with methylamine. Complexes 1 or 6 form the trinuclear hydroxo-copper(II)species [(mu-Cu){Cu(mu-OH) (2)(Tpms(Ph))}(2)] 7 upon air oxidation in moist methanol. In all the complexes the scorpionate ligand facially caps the metal in the N,N,O-coordination mode.

Caracterização do crescimento de filmes ultra-finos e nano-estruturas em superfícies

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Física, especialidade de Engenharia de Superfícies, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Gestão de resíduos produzidos num sistema de drenagem e tratamento de águas residuais

O presente trabalho centra-se na gestão de resíduos produzidos no sistema de drenagem e tratamento de águas residuais do município de Vila Nova de Gaia. A entidade onde decorreu o trabalho é uma empresa responsável pela distribuição de água e pela drenagem e tratamento de águas residuais. A empresa está certificada pela norma NP EN ISO 14001, desde 2001, sendo então um dos objectivos o enquadramento da gestão dos resíduos em estudo na referida norma, acompanhando os requisitos da mesma com vista ao seu total cumprimento. Outros dos objectivos foi estudar qual a opção de tratamento mais adequada a aplicar ao resíduo no seu local de armazenamento temporário com vista a minorar os seus impactes ambientais. De acordo com a caracterização analítica do resíduo e com os aspetos legais aplicáveis, foram também analisados os destinos finais possíveis e ambientalmente adequados ao resíduo. A medida proposta para a minimização de impactes no local de armazenamento temporário do resíduo foi a estabilização com cal nos leitos de secagem, disponíveis numa antiga ETAR de loteamento. O doseamento de cal a aplicar ao resíduo será de 10 kg de cal apagada comercial (Ca (OH)2) por uma tonelada de resíduo fresco com um período mínimo de secagem de 2 meses. Outra das medidas de minimização de impactes selecionada foi a implantação de uma cortina arbórea ao redor da instalação. Sendo o resíduo em estudo muito heterogéneo, constituído principalmente por areias, terras e gradados, a valorização foi equacionada mas não foram encontrados alternativas viáveis. O destino final considerado como mais adequado tendo em conta todas as características do resíduo e eluato, analisadas de acordo com o previsto no Decreto-Lei n.º 183/2009 de 10 de Agosto, foi o aterro para resíduos não perigosos. Foi também objecto do estudo a identificação e análise de todos os aspectos ambientais relacionados com a gestão de resíduos e a avaliação da sua significância. Dos aspectos ambientais identificados como significativos, destacam-se aqueles que ocorrem presentemente, os resíduos armazenados (gradados/limpeza de redes), e os que podem ocorrer em situações de emergência, fuga/derrame de óleos/combustíveis e cheiros/odores. De forma a minimizar os aspectos ambientais identificados, e de acordo com a norma NP EN ISO 14001, foram propostas ações que constam de um programa de gestão elaborado para este trabalho, onde se definem os objectivos, metas e prazos. As principais medidas propostas no programa de gestão foram: Estabilização com cal (inicial e reforço se necessário); melhoria do espaço envolvente; análise de questões de saúde ocupacional/segurança; adjudicação de prestação de serviços da recolha por operador licenciado; implantação da cortina arbórea; registo no SIRAPA; criação de planos de emergência ambiental e de segurança.

Portuguese strategy for occupational safety and health 2008-2012 for public administration : priorites for action, progress in the implementation of the proposed measures and their impact on occupational safety outcomes

Apresentação realizada no OH&S Forum 2011 - International Forum on Occupational Health and Safety: Policies, profiles and services, na Finlândia de, 20 a 22 Junho de 2011.

Destruction of the tar present in syngas by combustion in porous media

The cleaning of syngas is one of the most important challenges in the development of technologies based on gasification of biomass. Tar is an undesired byproduct because, once condensed, it can cause fouling and plugging and damage the downstream equipment. Thermochemical methods for tar destruction, which include catalytic cracking and thermal cracking, are intrinsically attractive because they are energetically efficient and no movable parts are required nor byproducts are produced. The main difficulty with these methods is the tendency for tar to polymerize at high temperatures. An alternative to tar removal is the complete combustion of the syngas in a porous burner directly as it leaves the particle capture system. In this context, the main aim of this study is to evaluate the destruction of the tar present in the syngas from biomass gasification by combustion in porous media. A gas mixture was used to emulate the syngas, which included toluene as a tar surrogate. Initially, CHEMKIN was used to assess the potential of the proposed solution. The calculations revealed the complete destruction of the tar surrogate for a wide range of operating conditions and indicated that the most important reactions in the toluene conversion are C6H5CH3 + OH <-> C6H5CH2 + H2O, C6H5CH3 + OH <-> C6H4CH3 + H2O, and C6H5CH3 + O <-> OC6H4CH3 + H and that the formation of toluene can occur through C6H5CH2 + H <-> C6H5CH3. Subsequently, experimental tests were performed in a porous burner fired with pure methane and syngas for two equivalence ratios and three flow velocities. In these tests, the toluene concentration in the syngas varied from 50 to 200 g/Nm(3). In line with the CHEMKIN calculations, the results revealed that toluene was almost completely destroyed for all tested conditions and that the process did not affect the performance of the porous burner regarding the emissions of CO, hydrocarbons, and NOx.

Reabilitação térmica e acústica de edifícios antigos

Dissertação de Natureza Científica para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Edificações

Pozzolanic activity of oil-refining catalyst: evaluation by electron and atomic microscopy

The reuse of waste fluid catalytic cracking (FCC) catalyst as partial surrogate for cement can reduce the environmental impact of both the oil-refinery and cement production industries [1,2]. FCC catalysts can be considered as pozzolanic materials since in the presence of water they tend to chemically react with calcium hydroxide to produce compounds possessing cementitious properties [3,4]. In addition, partial replacement of cement with FCC catalysts can enhance the performance of pastes and mortars, namely by improving their compressive strength [5,6]. In the present work the reaction of waste FCC catalyst with Ca(OH)2 has been investigated after a curing time of 28 days by scanning electron microscopy (SEM) with electron backscattered signal (BSE) combined with X-ray energy dispersive spectroscopy (EDS) carried out with a JEOL JSM 7001F instrument operated at 15 kV coupled to an INCA pentaFetx3 Oxford spectrometer. The polished cross-sections of FCC particles embedded in resin have also been evaluated by atomic force microscopy (AFM) in contact mode (CM) using a NanoSurf EasyScan 2 instrument. The SEM/EDS results revealed that an inward migration of Ca occurred during the reaction. A weaker outward migration of Si and Al was also apparent (Fig. 1). The migration of Ca was not homogeneous and tended to follow high-diffusivity paths within the porous waste FCC catalyst particles. The present study suggests that the porosity of waste FCC catalysts is key for the migration/reaction of Ca from the surrounding matrix, playing an important role in the pozzolanic activity of the system. The topography images and surface roughness parameters obtained by atomic force microscopy can be used to infer the local porosity in waste FCC catalyst particles (Fig. 2).