9 resultados para charge-transfer complexes

em Instituto Politécnico do Porto, Portugal


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Titanium films have been deposited on stainless steel metal sheets using dc magnetron sputtering technique at different substrate temperatures. The structure of the titanium films strongly depend on the substrate temperature. The titanium film deposited at the substrate temperature lower than 300 ◦C has a loose flat sheet grains structure and the titanium film prepared at the substrate temperature higher than 500 ◦C has a dense nubby grains structure. The DSSC assembled using stainless steel sheet coated with titanium film deposited at high substrate temperature has a low charge transfer resistance in the TiO2/Ti interface and results in a high conversion efficiency. The DSSC assembled using stainless steel sheet coated with titanium film deposited at temperature higher than 500 ◦C has higher conversion efficiency than that assembled using titanium metal sheet as the substrate. The maximum conversion efficiency, 2.26% is obtained for DSSC assembled using stainless steel sheet coated with titanium film deposited at 700 ◦C substrate temperature, which is about 70% of the conversion efficiency of the FTO reference cell used in this study.

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A novel enzymatic biosensor for carbamate pesticides detection was developed through the direct immobilization of Trametes versicolor laccase on graphene doped carbon paste electrode functionalized with Prussianblue films (LACC/PB/GPE). Graphene was prepared by graphite sonication-assisted exfoliation and characterized by transmission electron microscopy and X-ray photoelectron spectro- scopy. The Prussian blue film electrodeposited onto graphene doped carbon paste electrode allowed considerable reduction of the charge transfer resistance and of the capacitance of the device.The combined effects of pH, enzyme concentration and incubation time on biosensor response were optimized using a 23 full-factorial statistical design and response surface methodology. Based on the inhibition of laccase activity and using 4-aminophenol as redox mediator at pH 5.0,LACC/PB/GPE exhibited suitable characteristics in terms of sensitivity, intra-and inter-day repeatability (1.8–3.8% RSD), reproducibility (4.1 and 6.3%RSD),selectivity(13.2% bias at the higher interference: substrate ratios tested),accuracy and stability(ca. twenty days)for quantification of five carbamates widely applied on tomato and potato crops.The attained detection limits ranged between 5.2×10−9 mol L−1(0.002 mg kg−1 w/w for ziram)and 1.0×10−7 mol L−1 (0.022 mg kg−1 w/w for carbofuran).Recovery values for the two tested spiking levels ranged from 90.2±0.1%(carbofuran)to 101.1±0.3% (ziram) for tomato and from 91.0±0.1%(formetanate)to 100.8±0.1%(ziram)for potato samples.The proposed methodology is appropriate to enable testing pesticide levels in food samples to fit with regulations and food inspections.

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This work proposes a novel approach for a suitable orientation of antibodies (Ab) on an immunosensing platform, applied here to the determination of 8-hydroxy-2′-deoxyguanosine (8OHdG), a biomarker of oxidative stress that has been associated to chronic diseases, such as cancer. The anti-8OHdG was bound to an amine modified gold support through its Fc region after activation of its carboxylic functions. Non-oriented approaches of Ab binding to the platform were tested in parallel, in order to show that the presented methodology favored Ab/Ag affinity and immunodetection of the antigen. The immunosensor design was evaluated by quartz-crystal microbalance with dissipation, atomic force microscopy, electrochemical impedance spectroscopy (EIS) and square-wave voltammetry. EIS was also a suitable technique to follow the analytical behavior of the device against 8OHdG. The affinity binding between 8OHdG and the antibody immobilized in the gold modified platform increased the charge transfer resistance across the electrochemical set-up. The observed behavior was linear from 0.02 to 7.0 ng/mL of 8OHdG concentrations. The interference from glucose, urea and creatinine was found negligible. An attempt of application to synthetic samples was also successfully conducted. Overall, the presented approach enabled the production of suitably oriented Abs over a gold platform by means of a much simpler process than other oriented-Ab binding approaches described in the literature, as far as we know, and was successful in terms of analytical features and sample application.

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With accelerated market volatility, faster response times and increased globalization, business environments are going through a major transformation and firms have intensified their search for strategies which can give them competitive advantage. This requires that companies continuously innovate, to think of new ideas that can be transformed or implemented as products, processes or services, generating value for the firm. Innovative solutions and processes are usually developed by a group of people, working together. A grouping of people that share and create new knowledge can be considered as a Community of Practice (CoP). CoP’s are places which provide a sound basis for organizational learning and encourage knowledge creation and acquisition. Virtual Communities of Practice (VCoP's) can perform a central role in promoting communication and collaboration between members who are dispersed in both time and space. Nevertheless, it is known that not all CoP's and VCoP's share the same levels of performance or produce the same results. This means that there are factors that enable or constrain the process of knowledge creation. With this in mind, we developed a case study in order to identify both the motivations and the constraints that members of an organization experience when taking part in the knowledge creating processes of VCoP's. Results show that organizational culture and professional and personal development play an important role in these processes. No interviewee referred to direct financial rewards as a motivation factor for participation in VCoPs. Most identified the difficulty in aligning objectives established by the management with justification for the time spent in the VCoP. The interviewees also said that technology is not a constraint.

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Paper accepted for the OKLC 2009 - International Conference on Organizational Learning, Knowledge and Capabilities (26-28th, April 2009, Amsterdam, the Netherlands).

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O presente trabalho pretendeu desenvolver e testar um sensor óptico para detectar ciclamato de sódio, um adoçante artificial utilizado nas bebidas em geral. A primeira abordagem neste sentido baseou-se na preparação de um sensor óptico através da formação de complexos corados entre o ciclamato e várias espécies metálicas, nomeadamente Hg(II), Ba(II), Fe(II), Ag(II), Pb(II), Cd(II), Mn (II), Ni(II), Cu(II), Co(II), Sn(II) e Mg(II). Perante a ausência de resultados satisfatórios optou-se por explorar a acção do ciclamato de sódio na transferência/partilha de um corante entre duas fases líquidas imiscíveis. As fases líquidas utilizadas foram a água e o clorofórmio. Testaram-se várias famílias de corantes mas só uma classe se mostrou com as características apropriadas para o objectivo pretendido. Dentro dessa família de corantes, seleccionou-se aquele que, à partida, garantiu o melhor desempenho. O sensor foi testado em diferentes condições de pH e também na presença de potenciais interferentes de forma a estabelecer as melhores condições de utilização. O método mostrou-se bastante simples de executar, rápido na obtenção de resultados e com boas características para ser avaliado visualmente, mas sempre de acordo com os critérios de objectividade que um trabalho deste tipo requer. Além o disso permitiu ser calibrado de uma forma rápida e simples, características essenciais para a aplicação deste método na despistagem de ciclamato em análises de rotina. O método desenvolvido foi ainda aplicado à análise de vinho dopado com diferentes concentrações de ciclamato de sódio. Destes testes verificou-se a necessidade de optimização do método através da introdução de outras substâncias na fase não aquosa diminuindo a vulnerabilidade do sensor a outros interferentes. Como conclusão, o método correspondeu às expectativas, mostrando-se viável para aplicação à análise de vinhos, ainda com uma margem significativa de desenvolvimento no sentido de o tornar mais fiável e preciso.

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The knowledge-based society we live in has stressed the importance of human capital and brought talent to the top of most wanted skills, especially to companies who want to succeed in turbulent environments worldwide. In fact, streams, sequences of decisions and resource commitments characterize the day-to-day of multinational companies (MNCs). Such decision-making activities encompass major strategic moves like internationalization and new market entries or diversification and acquisitions. In most companies, these strategic decisions are extensively discussed and debated and are generally framed, formulated, and articulated in specialized language often developed by the best minds in the company. Yet the language used in such deliberations, in detailing and enacting the implementation strategy is usually taken for granted and receives little if any explicit attention (Brannen & Doz, 2012) an can still be a “forgotten factor” (Marschan et al. 1997). Literature on language management and international business refers to lack of awareness of business managers of the impact that language can have not only in communication effectiveness but especially in knowledge transfer and knowledge management in business environments. In the context of MNCs, management is, for many different reasons, more complex and demanding than that of a national company, mainly because of diversity factors inherent to internationalization, namely geographical and cultural spaces, i.e, varied mindsets. Moreover, the way of functioning, and managing language, of the MNC depends on its vision, its values and its internationalization model, i.e on in the way the MNE adapts to and controls the new markets, which can vary essentially from a more ethnocentric to a more pluricentric focus. Regardless of the internationalization model followed by the MNC, communication between different business units is essential to achieve unity in diversity and business sustainability. For the business flow and prosperity, inter-subsidiary, intra-company and company-client (customers, suppliers, governments, municipalities, etc..) communication must work in various directions and levels of the organization. If not well managed, this diversity can be a barrier to global coordination and create turbulent environments, even if a good technological support is available (Feely et al., 2002: 4). According to Marchan-Piekkari (1999) the tongue can be both (i) a barrier, (ii) a facilitator and (iii) a source of power. Moreover, the lack of preparation for the barriers of linguistic diversity can lead to various costs, including negotiations’ failure and failure on internationalization.. On the other hand, communication and language fluency is not just a message transfer procedure, but above all a knowledge transfer process, which requires extra-linguistic skills (persuasion, assertiveness …) in order to promote credibility of both parties. For this reason, MNCs need a common code to communicate and trade information inside and outside the company, which will require one or more strategies, in order to overcome possible barriers and organization distortions.

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This study aimed to carry out experimental work to obtain, for Newtonian and non-Newtonian fluids, heat transfer coefficients, at constant wall temperature as boundary condition, in fully developed laminar flow inside a helical coil. The Newtonian fluids studied were aqueous solutions of glycerol, 25%, 36%, 43%, 59% and 78% (w/w) and the non-Newtonian fluids aqueous solutions of carboxymethylcellulose (CMC), a polymer, with concentrations 0.1%, 0.2%, 0.3%, 0.4% and 0.6% (w/w) and aqueous solutions of xanthan gum (XG), another polymer, with concentrations 0.1% and 0.2% (w/w). According to the rheological study performed, the polymer solutions had shear thinning behavior and different values of elasticity. The helical coil used has internal diameter, curvature ratio, length and pitch, respectively: 0.004575 m, 0.0263, 5.0 m and 11.34 mm. The Nusselt numbers for the CMC solutions are, on average, slightly higher than those for Newtonian fluids, for identical Prandtl and generalized Dean numbers. As outcome, the viscous component of the shear thinning polymer tends to potentiate the mixing effect of the Dean cells. The Nusselt numbers of the XG solutions are significant lower than those of the Newtonian solutions, for identical Prandtl and generalized Dean numbers. Therefore, the elastic component of the polymer tends to diminish the mixing effect of the Dean cells. A global correlation, for Nusselt number as a function of Péclet, generalized Dean and Weissenberg numbers for all Newtonian and non-Newtonian solutions studied, is presented.

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The aim of this study is to optimize the heat flow through the pultrusion die assembly system on the manufacturing process of a specific glass-fiber reinforced polymer (GFRP) pultrusion profile. The control of heat flow and its distribution through whole die assembly system is of vital importance in optimizing the actual GFRP pultrusion process. Through mathematical modeling of heating-die process, by means of Finite Element Analysis (FEA) program, an optimum heater selection, die position and temperature control was achieved. The thermal environment within the die was critically modeled relative not only to the applied heat sources, but also to the conductive and convective losses, as well as the thermal contribution arising from the exothermic reaction of resin matrix as it cures or polymerizes from the liquid to solid condition. Numerical simulation was validated with basis on thermographic measurements carried out on key points along the die during pultrusion process.