9 resultados para Patterend Wall Surfaces

em Instituto Politécnico do Porto, Portugal


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Mestrado em Engenharia Electrotécnica e de Computadores

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A nanohybrid electrochemical transducer surface was developed using carbon and gold nanomaterials. The strategy relayed on casting multiwalled carbon nanotubes or carbon nanofibers onto a screen-printed carbon electrode surface, followed by in situ generation of gold nanoparticles by electrochemical deposition of ionic gold, in a reproducible manner. These transducers, so fabricated, were characterized using both electrochemical and microscopic techniques. Biofunctionality was evaluated using the streptavidin-biotin interaction system as the biological reaction model. These platforms allow to achieve low detection limits (in the order of pmoles), are reproducible and stable at least for a month after their preparation, being a perfect candidate to be used as transducer of different sensor devices.

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The electrooxidative behavior of pravastatin (PRV) in aqueous media was studied by square-wave voltammetry at a glassycarbon electrode (GCE) and at a screen-printed carbon electrode (SPCE). Maximum peak current intensities in a pH 5.0 buffer were obtained at +1.3 V vs. AgCl/Ag and +1.0 V vs. Ag for the GCE and SPCE surface respectively. Validation of the developed methodologies revealed good performance characteristics and confirmed their applicability to the quantification of PRV in pharmaceutical products, without significant sample pretreatment. A comparative analysis between the two electrode types showed that SPCEs are preferred as an electrode surface because of their higher sensitivity and the elimination of the need to clean the electrode’s surface for its renewal, which frequently is, if not always, the rate-limiting step in voltammetric analysis.

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The interest in the development of climbing robots has grown rapidly in the last years. Climbing robots are useful devices that can be adopted in a variety of applications, such as maintenance and inspection in the process and construction industries. These systems are mainly adopted in places where direct access by a human operator is very expensive, because of the need for scaffolding, or very dangerous, due to the presence of an hostile environment. The main motivations are to increase the operation efficiency, by eliminating the costly assembly of scaffolding, or to protect human health and safety in hazardous tasks. Several climbing robots have already been developed, and other are under development, for applications ranging from cleaning to inspection of difficult to reach constructions. A wall climbing robot should not only be light, but also have large payload, so that it may reduce excessive adhesion forces and carry instrumentations during navigation. These machines should be capable of travelling over different types of surfaces, with different inclinations, such as floors, walls, or ceilings, and to walk between such surfaces (Elliot et al. (2006); Sattar et al. (2002)). Furthermore, they should be able of adapting and reconfiguring for various environment conditions and to be self-contained. Up to now, considerable research was devoted to these machines and various types of experimental models were already proposed (according to Chen et al. (2006), over 200 prototypes aimed at such applications had been developed in the world by the year 2006). However, we have to notice that the application of climbing robots is still limited. Apart from a couple successful industrialized products, most are only prototypes and few of them can be found in common use due to unsatisfactory performance in on-site tests (regarding aspects such as their speed, cost and reliability). Chen et al. (2006) present the main design problems affecting the system performance of climbing robots and also suggest solutions to these problems. The major two issues in the design of wall climbing robots are their locomotion and adhesion methods. With respect to the locomotion type, four types are often considered: the crawler, the wheeled, the legged and the propulsion robots. Although the crawler type is able to move relatively faster, it is not adequate to be applied in rough environments. On the other hand, the legged type easily copes with obstacles found in the environment, whereas generally its speed is lower and requires complex control systems. Regarding the adhesion to the surface, the robots should be able to produce a secure gripping force using a light-weight mechanism. The adhesion method is generally classified into four groups: suction force, magnetic, gripping to the surface and thrust force type. Nevertheless, recently new methods for assuring the adhesion, based in biological findings, were proposed. The vacuum type principle is light and easy to control though it presents the problem of supplying compressed air. An alternative, with costs in terms of weight, is the adoption of a vacuum pump. The magnetic type principle implies heavy actuators and is used only for ferromagnetic surfaces. The thrust force type robots make use of the forces developed by thrusters to adhere to the surfaces, but are used in very restricted and specific applications. Bearing these facts in mind, this chapter presents a survey of different applications and technologies adopted for the implementation of climbing robots locomotion and adhesion to surfaces, focusing on the new technologies that are recently being developed to fulfill these objectives. The chapter is organized as follows. Section two presents several applications of climbing robots. Sections three and four present the main locomotion principles, and the main "conventional" technologies for adhering to surfaces, respectively. Section five describes recent biological inspired technologies for robot adhesion to surfaces. Section six introduces several new architectures for climbing robots. Finally, section seven outlines the main conclusions.

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For diffeomorphisms on surfaces with basic sets, we show the following type of rigidity result: if a topological conjugacy between them is differentiable at a point in the basic set then the conjugacy has a smooth extension to the surface. These results generalize the similar ones of D. Sullivan, E. de Faria and ours for one-dimensional expanding dynamics.

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Selenium modified ruthenium electrocatalysts supported on carbon black were synthesized using NaBH4 reduction of the metal precursor. Prepared Ru/C electrocatalysts showed high dispersion and very small averaged particle size. These Ru/C electrocatalysts were subsequently modified with Se following two procedures: (a) preformed Ru/carbon catalyst was mixed with SeO2 in xylene and reduced in H2 and (b) Ru metal precursor was mixed with SeO2 followed by reduction with NaBH4. The XRD patterns indicate that a pyrite-type structure was obtained at higher annealing temperatures, regardless of the Ru:Se molar ratio used in the preparation step. A pyrite-type structure also emerged in samples that were not calcined; however, in this case, the pyrite-type structure was only prominent for samples with higher Ru:Se ratios. The characterization of the RuSe/C electrocatalysts suggested that the Se in noncalcined samples was present mainly as an amorphous skin. Preliminary study of activity toward oxygen reduction reaction (ORR) using electrocatalysts with a Ru:Se ratio of 1:0.7 indicated that annealing after modification with Se had a detrimental effect on their activity. This result could be related to the increased particle size of crystalline RuSe2 in heat-treated samples. Higher activity of not annealed RuSe/C catalysts could also be a result of the structure containing amorphous Se skin on the Ru crystal. The electrode obtained using not calcined RuSe showed a very promising performance with a slightly lower activity and higher overpotential in comparison with a commercial Pt/C electrode. Single wall carbon nanohorns (SWNH) were considered for application as ORR electrocatalysts' supports. The characterization of SWNH was carried out regarding their tolerance toward strong catalyzed corrosion conditions. Tests indicated that SWNH have a three times higher electrochemical surface area (ESA) loss than carbon black or Pt commercial electrodes.

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Using low cost portable devices that enable a single analytical step for screening environmental contaminants is today a demanding issue. This concept is here tried out by recycling screen-printed electrodes that were to be disposed of and by choosing as sensory element a low cost material offering specific response for an environmental contaminant. Microcystins (MCs) were used as target analyte, for being dangerous toxins produced by cyanobacteria released into water bodies. The sensory element was a plastic antibody designed by surface imprinting with carefully selected monomers to ensure a specific response. These were designed on the wall of carbon nanotubes, taking advantage of their exceptional electrical properties. The stereochemical ability of the sensory material to detect MCs was checked by preparing blank materials where the imprinting stage was made without the template molecule. The novel sensory material for MCs was introduced in a polymeric matrix and evaluated against potentiometric measurements. Nernstian response was observed from 7.24 × 10−10 to 1.28 × 10−9 M in buffer solution (10 mM HEPES, 150 mM NaCl, pH 6.6), with average slopes of −62 mVdecade−1 and detection capabilities below 1 nM. The blank materials were unable to provide a linear response against log(concentration), showing only a slight potential change towards more positive potentials with increasing concentrations (while that ofthe plastic antibodies moved to more negative values), with a maximum rate of +33 mVdecade−1. The sensors presented good selectivity towards sulphate, iron and ammonium ions, and also chloroform and tetrachloroethylene (TCE) and fast response (<20 s). This concept was successfully tested on the analysis of spiked environmental water samples. The sensors were further applied onto recycled chips, comprehending one site for the reference electrode and two sites for different selective membranes, in a biparametric approach for “in situ” analysis.

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A novel artificial antibody for troponin T (TnT) was synthesized by molecular imprint (MI) on the surface of multiwalled carbon nanotubes (MWCNT). This was done by attaching TnT to the MWCNT surface, and filling the vacant spaces by polymerizing under mild conditions acrylamide (monomer) in N,N′-methylenebisacrylamide (cross-linker) and ammonium persulphate (initiator). After removing the template, the obtained biomaterial was able to rebind TnT and discriminate it among other interfering species. Stereochemical recognition of TnT was confirmed by the non-rebinding ability displayed by non-imprinted (NI) materials, obtained by imprinting without a template. SEM and FTIR analysis confirmed the surface modification of the MWCNT. The ability of this biomaterial to rebind TnT was confirmed by including it as electroactive compound in a PVC/plasticizer mixture coating a wire of silver, gold or titanium. Anionic slopes of 50 mV decade−1 were obtained for the gold wire coated with MI-based membranes dipped in HEPES buffer of pH 7. The limit of detection was 0.16 μg mL−1. Neither the NI-MWCNT nor the MWCNT showed the ability to recognize the template. Good selectivity was observed against creatinine, sucrose, fructose, myoglobin, sodium glutamate, thiamine and urea. The sensor was tested successfully on serum samples. It is expected that this work opens new horizons on the design of new artificial antibodies for complex protein structures.