Towards a reliable technology for antioxidant capacity and oxidative damage evaluation: Electrochemical (bio)sensors

To counteract and prevent the deleterious effect of free radicals the living organisms have developed complex endogenous and exogenous antioxidant systems. Several analytical methodologies have been proposed in order to quantify antioxidants in food, beverages and biological fluids. This paper revises the electroanalytical approaches developed for the assessment of the total or individual antioxidant capacity. Four electrochemical sensing approaches have been identified, based on the direct electrochemical detection of antioxidant at bare or chemically modified electrodes, and using enzymatic and DNA-based biosensors.

Selective recognition in potentiometric transduction of amoxicillin by molecularly imprinted materials

The indiscriminate use of antibiotics in foodproducing animals has received increasing attention as a contributory factor in the international emergence of antibiotic- resistant bacteria (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004). Numerous analytical methods for quantifying antibacterial residues in edible animal products have been developed over years (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004; Botsoglou and Fletouris in Handbook of food analysis, residues and other food component analysis, Marcel Dekker, Ghent, 2004). Being Amoxicillin (AMOX) one of those critical veterinary drugs, efforts have been made to develop simple and expeditious methods for its control in food samples. In literature, only one AMOX-selective electrode has been reported so far. In that work, phosphotungstate:amoxycillinium ion exchanger was used as electroactive material (Shoukry et al. in Electroanalysis 6:914–917, 1994). Designing new materials based on molecularly imprinted polymers (MIPs) which are complementary to the size and charge of AMOX could lead to very selective interactions, thus enhancing the selectivity of the sensing unit. AMOXselective electrodes used imprinted polymers as electroactive materials having AMOX as target molecule to design a biomimetic imprinted cavity. Poly(vinyl chloride), sensors of methacrylic acid displayed Nernstian slopes (60.7 mV/decade) and low detection limits (2.9×10-5 mol/L). The potentiometric responses were not affected by pH within 4–5 and showed good selectivity. The electrodes were applied successfully to the analysis of real samples.

New sensing materials of molecularly-imprinted polymers for the selective recognition of Chlortetracycline

As a result of the stressful conditions in aquaculture facilities there is a high risk of bacterial infections among cultured fish. Chlortetracycline (CTC) is one of the antimicrobials used to solve this problem. It is a broad spectrum antibacterial active against a wide range of Gram-positive and Gram-negative bacteria. Numerous analytical methods for screening, identifying, and quantifying CTC in animal products have been developed over the years. An alternative and advantageous method should rely on expeditious and efficient procedures providing highly specific and sensitive measurements in food samples. Ion-selective electrodes (ISEs) could meet these criteria. The only ISE reported in literature for this purpose used traditional electro-active materials. A selectivity enhancement could however be achieved after improving the analyte recognition by molecularly imprinted polymers (MIPs). Several MIP particles were synthesized and used as electro-active materials. ISEs based in methacrylic acid monomers showed the best analytical performance according to slope (62.5 and 68.6 mV/decade) and detection limit (4.1×10−5 and 5.5×10−5 mol L−1). The electrodes displayed good selectivity. The ISEs are not affected by pH changes ranging from 2.5 to 13. The sensors were successfully applied to the analysis of serum, urine and fish samples.

Influence of crystallite size of nanophased hydroxyapatite on fibronectin and osteonectin adsorption and on MC3T3-E1 osteoblast adhesion and morphology

The characteristic topographical features (crystallite dimensions, surface morphology and roughness) of bioceramics may influence the adsorption of proteins relevant to bone regeneration. This work aims at analyzing the influence of two distinct nanophased hydroxyapatite (HA) ceramics, HA725 and HA1000 on fibronectin (FN) and osteonectin (ON) adsorption and MC3T3-E1 osteoblast adhesion and morphology. Both substrates were obtained using the same hydroxyapatite nanocrystals aggregates and applying the sintering temperatures of 725ºC and 1000ºC, respectively. The two proteins used in this work, FN as an adhesive glycoprotein and ON as a counter-adhesive protein, are known to be involved in the early stages of osteogenesis (cell adhesion, mobility and proliferation). The properties of the nanoHA substrates had an important role in the adsorption behavior of the two studied proteins and clearly affected the MC3T3- E1 morphology, distribution and metabolic activity. HA1000 surfaces presenting slightly larger grain size, higher root-mean-square roughness (Rq), lower surface area and porosity, allowed for higher amounts of both proteins adsorbed. These substrates also revealed increased number of exposed FN cell-binding domains as well as higher affinity for osteonectin. Regarding the osteoblast adhesion results, improved viability and cell number were found for HA1000 surfaces as compared to HA725 ones, independently of the presence or type of adsorbed protein. Therefore the osteoblast adhesion and metabolic activity seemed to be more sensitive to surfaces morphology and roughness than to the type of adsorbed proteins.

Man-tailored biomimetic sensor of molecularly imprinted materials for the potentiometric measurement of oxytetracycline

A novel biomimetic sensor for the potentiometric transduction of oxytetracycline is presented. The artificial host was imprinted in methacrylic acid and/or acrylamide based polymers. Different amounts of molecularly imprinted and non-imprinted polymers were dispersed in different plasticizing solvents and entrapped in a poly(vinyl chloride) matrix. Only molecularly imprinted based sensors allowed a potentiometric transduction, suggesting the existence of host–guest interactions. These sensors exhibited a near-Nernstian response in steady state evaluations; slopes and detection limits ranged 42–63 mV/decade and 2.5–31.3 µg/mL, respectively. Sensors were independent from the pH of test solutions within 2–5. Good selectivity was observed towards glycine, ciprofloxacin, creatinine, acid nalidixic, sulfadiazine, cysteine, hydroxylamine and lactose. In flowing media, the biomimetic sensors presented good reproducibility (RSD of ±0.7%), fast response, good sensitivity (65 mV/decade), wide linear range (5.0×10−5 to 1.0×10−2 mol/L), low detection limit (19.8 µg/mL), and a stable baseline for a 5×10−3M citrate buffer (pH 2.5) carrier. The sensors were successfully applied to the analysis of drugs and urine. This work confirms the possibility of using molecularly imprinted polymers as ionophores for organic ion recognition in potentiometric transduction.

Flow-injection potentiometric method for the routine determination of chloride: application to bread analysis

Bread is consumed worldwide by man, thus contributing to the regular ingestion of certain inorganic species such as chloride. It controls the blood pressure if associated to a sodium intake and may increase the incidence of stomach ulcer. Its routine control should thus be established by means of quick and low cost procedures. This work reports a double- channel flow injection analysis (FIA) system with a new chloride sensor for the analysis of bread. All solutions are prepared in water and necessary ionic strength adjustments are made on-line. The body of the indicating electrode is made from a silver needle of 0.8 mm i.d. with an external layer of silver chloride. These devices were constructed with different lengths. Electrodes of 1.0 to 3.0 cm presented better analytical performance. The calibration curves under optimum conditions displayed Nernstian behaviour, with average slopes of 56 mV decade-1, with sampling rates of 60 samples h-1. The method was applied to analyze several kinds of bread, namely pão de trigo, pão integral, pão de centeio, pão de mistura, broa de milho, pão sem sal, pão meio sal, pão-de-leite, and pão de água. The accuracy and precision of the potentiometric method were ascertained by comparison to a spectrophotometric method of continuous segmented flow. These methods were validated against ion-chromatography procedures.

How new online communication tools and the availability of content influence the audiences and the creative process

We live in a changing world. At an impressive speed, every day new technological resources appear. We increasingly use the Internet to obtain and share information, and new online communication tools are emerging. Each of them encompasses new potential and creates new audiences. In recent years, we witnessed the emergence of Facebook, Twitter, YouTube and other media platforms. They have provided us with an even greater interactivity between sender and receiver, as well as generated a new sense of community. At the same time we also see the availability of content like it never happened before. We are increasingly sharing texts, videos, photos, etc. This poster intends to explore the potential of using these new online communication tools in the cultural sphere to create new audiences, to develop of a new kind of community, to provide information as well as different ways of building organizations’ memory. The transience of performing arts is accompanied by the need to counter that transience by means of documentation. This desire to ‘save’ events reaches its expression with the information archive of the different production moments as well as the opportunity to record the event and present it through, for instance, digital platforms. In this poster we intend to answer the following questions: which online communication tools are being used to engage audiences in the cultural sphere (specifically between theater companies in Lisbon)? Is there a new relationship with the public? Are online communication tools creating a new kind of community? What changes are these tools introducing in the creative process? In what way the availability of content and its archive contribute to the organization memory? Among several references, we will approach the two-way communication model that James E. Grunig & Todd T. Hunt (1984) already presented and the concept of mass self-communication of Manuel Castells (2010). Castells also tells us that we have moved from traditional media to a system of communication networks. For Scott Kirsner (2010), we have entered an era of digital creativity, where artists have the tools to do what they imagined and the public no longer wants to just consume cultural goods, but instead to have a voice and participate. The creativity process is now depending on the public choice as they wander through the screen. It is the receiver who owns an object which can be exchanged. Virtual reality has encouraged the receiver to abandon its position of passive observer and to become a participant agent, which implies a challenge to organizations: inventing new forms of interfaces. Therefore, we intend to find new and effective online tools that can be used by cultural organizations; the best way to manage them; to show how organizations can create a community with the public and how the availability of online content and its archive can contribute to the organizations’ memory.

Desenvolvimento de uma metodologia baseada em redes neuronais para o cálculo da energia produzida por aerogeradores

O uso da energia eólica para a produção de eletricidade apresenta na última década um crescimento apreciável. Monitorizar o desempenho dos aerogeradores torna-se um processo incontornável, quer por motivos financeiros, quer por questões operacionais. Os investimentos despendidos na construção de parques eólicos são muito consideráveis, pelo que é essencial a análise constante dos aspetos preponderantes no retorno do investimento. A maximização da energia produzida por cada aerogerador é o objetivo principal da monitorização dos parques eólicos. Os sistemas Supervisory Control and Data Acquisition (SCADAs) instalados nos parques eólicos permitem uma supervisão em tempo real relativamente ao estado e funcionamento dos aerogeradores, adquirindo uma elevada importância na avaliação dos rendimentos energéticos e anomalias de funcionamento, garantido desta forma melhorias de produtividade. O objetivo deste trabalho é estimar a energia produzida pelos aerogeradores quando ocorrem falhas de comunicação com o seu contador interno ou avaria do mesmo. A ocorrência destas situações não permite a monitorização da energia produzida durante esse período. Foram analisados dados operacionais dos aerogeradores relativos a um parque eólico localizado na zona Norte de Portugal, sendo usados os dados recolhidos pelo sistema SCADA sobre a forma de médias de 10 min referentes ao período de janeiro de 2011 a agosto 2011. O desempenho da rede neuronal depende da qualidade e quantidade do conjunto de dados usados para o treino da rede. Os dados usados devem representar de forma fiel o estado que se pretende para o equipamento. Para a obtenção do objetivo proposto foi fundamental a identificação das grandezas disponíveis a utilizar no método de cálculo da energia produzida. Os resultados obtidos com aplicação das redes neuronais no método de cálculo da energia produzida por aerogeradores demonstram que independentemente do período de indisponibilidade da informação referente à energia produzida é possível estimar o valor da mesma.

Biosensor based on multi-walled carbon nanotubes paste electrode modified with laccase for pirimicarb pesticide quantification

This study focused on the development of a sensitive enzymatic biosensor for the determination of pirimicarb pesticide based on the immobilization of laccase on composite carbon paste electrodes. Multi- walled carbon nanotubes(MWCNTs)paste electrode modified by dispersion of laccase(3%,w/w) within the optimum composite matrix(60:40%,w/w,MWCNTs and paraffin binder)showed the best performance, with excellent electron transfer kinetic and catalytic effects related to the redox process of the substrate4- aminophenol. No metal or anti-interference membrane was added. Based on the inhibition of laccase activity, pirimicarb can be determined in the range 9.90 ×10- 7 to 1.15 ×10- 5 molL 1 using 4- aminophenol as substrate at the optimum pH of 5.0, with acceptable repeatability and reproducibility (relative standard deviations lower than 5%).The limit of detection obtained was 1.8 × 10-7 molL 1 (0.04 mgkg 1 on a fresh weight vegetable basis).The high activity and catalytic properties of the laccase- based biosensor are retained during ca. one month. The optimized electroanalytical protocol coupled to the QuEChERS methodology were applied to tomato and lettuce samples spiked at three levels; recoveries ranging from 91.0±0.1% to 101.0 ± 0.3% were attained. No significant effects in the pirimicarb electro- analysis were observed by the presence of pro-vitamin A, vitamins B1 and C,and glucose in the vegetable extracts. The proposed biosensor- based pesticide residue methodology fulfills all requisites to be used in implementation of food safety programs.

Multiplexed electrochemical immunosensor for detection of celiac disease serological markers

Celiac disease (CD) is a gluten-induced autoimmune enteropathy characterized by the presence of antibodies against gliadin (AGA) and anti-tissue transglutaminase (anti-tTG) antibodies. A disposable electrochemical dual immunosensor for the simultaneous detection of IgA and IgG type AGA and antitTG antibodies in real patient’s samples is presented. The proposed immunosensor is based on a dual screen-printed carbon electrode, with two working electrodes, nanostructured with a carbon–metal hybrid system that worked as the transducer surface. The immunosensing strategy consisted of the immobilization of gliadin and tTG (i.e. CD specific antigens) on the nanostructured electrode surface. The electrochemical detection of the human antibodies present in the assayed serum samples was carried out through the antigen–antibody interaction and recorded using alkaline phosphatase labelled anti-human antibodies and a mixture of 3-indoxyl phosphate with silver ions was used as the substrate. The analytical signal was based on the anodic redissolution of enzymatically generated silver by cyclic voltammetry. The results obtained were corroborated with commercial ELISA kits indicating that the developed sensor can be a good alternative to the traditional methods allowing a decentralization of the analyses towards a point-of-care strategy.

Eletrólise da água para produção de gás de síntese

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica Ramo de Processos Químicos

Application of integer and fractional models in electrochemical systems

This paper describes the use of integer and fractional electrical elements, for modelling two electrochemical systems. A first type of system consists of botanical elements and a second type is implemented by electrolyte processes with fractal electrodes. Experimental results are analyzed in the frequency domain, and the pros and cons of adopting fractional-order electrical components for modelling these systems are compared.

Actividade ígnea pós-paleozóica no continente português (elementos para uma síntese crítica)

The Author presents a synopsis about the post-Paleozoic igneous activity in continental Portugal. Subvolcanic massifs of Sintra, Sines and Monchique and the basaltic complex of Lisbon-Mafra are interpreted. The large network of dikes and sills occuring at north of Tagus river in Lisbon- Torres Vedras region as the dikes of Algarve and also those of diapiric formation are studied and compared. Also the doleritic dikes cuting the Hesperic Massif and the Great dike of Alentejo are studied. The Author presents an attempt of petrological and geochemical correlation-among these post-Paleozoic igneous rocks. For this more than 350 chemical analysis are used in order to elaborate several diagrams and some general conclusions are derived from them. The correlation between the origin of these igneous rocks and the opening of North Atlantic and the counter-clockwise rotation of the Iberia are also tried.

Maximizing contention-free executions in multiprocessor scheduling

It is widely assumed that scheduling real-time tasks becomes more difficult as their deadlines get shorter. With deadlines shorter, however, tasks potentially compete less with each other for processors, and this could produce more contention-free slots at which the number of competing tasks is smaller than or equal to the number of available processors. This paper presents a policy (called CF policy) that utilizes such contention-free slots effectively. This policy can be employed by any work-conserving, preemptive scheduling algorithm, and we show that any algorithm extended with this policy dominates the original algorithm in terms of schedulability. We also present improved schedulability tests for algorithms that employ this policy, based on the observation that interference from tasks is reduced when their executions are postponed to contention-free slots. Finally, using the properties of the CF policy, we derive a counter-intuitive claim that shortening of task deadlines can help improve schedulability of task systems. We present heuristics that effectively reduce task deadlines for better scheduability without performing any exhaustive search.

Estratégias de Advocacy no Terceiro Setor enquanto função das Relações Públicas: campanhas de Advocacy no IMVF: um estudo de caso

Dissertação apresentada à Escola Superior de Comunicação Social como parte dos requisitos para obtenção de grau de mestre em Gestão Estratégica das Relações Públicas.