53 research outputs found

    Asymptotics of polynomial solutions of a class of generalized Lamé differential equations

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    In this paper we study the asymptotic behavior of sequences of Heine-Stieltjes and Van Vleck polynomials for a class of generalized Lamé differential equations connected with certain equilibrium problems on the unit circle.The research of A.M.F. and P.M.G. was partially supported by the Ministry of Science and Technology (MCYT) of Spain through the grant BFM2001-3878-C02-02, and by Junta de Andalucía through Grupo de Investigación FQM 0229. A.M.F. acknowledges also the support of the European Research Network on Constructive Complex Approximation (NeCCA), INTAS 03-51-6637, and of NATO Collaborative Linkage Grant “Orthogonal Polynomials: Theory, Applications and Generalizations,” ref. PST.CLG.979738. The research of R.O. was partially supported by grants from Spanish MCYT (Research Project BFM2001-3411) and Gobierno Autónomo de Canarias (Research Project PI2002/136)

    Nanofabrication and Electrochemical Characterization of Self-Assembled Monolayers Sandwiched between Metal Nanoparticles and Electrode Surfaces

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    Nanoscience and nanotechnology have reached the syllabi of many upper-division undergraduate and master-level courses all over the world. There is therefore a growing need for practical exercises that illustrate the fabrication, characterization, properties, and applications of nanomaterials. Here we describe an advanced-level laboratory experiment in which students had the opportunity to fabricate surfaces modified by ordered monolayers and nanostructured materials. The surface modification was quantified by means of a quartz crystal microbalance, while the electrochemical properties of the nanoarchitectures were assessed using cyclic voltammetry experiments. Electron transfer across self-assembled monolayers mediated by gold nanoparticles was presented as a topic for discussion, and consideration of potential practical applications of the observed phenomena (catalytic and electrocatalytic processes, as well as development of optical, (opto)electronic, and photovoltaic devices with enhanced properties) was proposed as a further reading exercise

    All-Carbon Electrode Molecular Electronic Devices Based on Langmuir–Blodgett Monolayers

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    Nascent molecular electronic devices, based on monolayer Langmuir–Blodgett films sandwiched between two carbonaceous electrodes, have been prepared. Tightly packed monolayers of 4-((4-((4-ethynylphenyl)ethynyl)phenyl)ethynyl)benzoic acid are deposited onto a highly oriented pyrolytic graphite electrode. An amorphous carbon top contact electrode is formed on top of the monolayer from a naphthalene precursor using the focused electron beam induced deposition technique. This allows the deposition of a carbon top-contact electrode with well-defined shape, thickness, and precise positioning on the film with nm resolution. These results represent a substantial step toward the realization of integrated molecular electronic devices based on monolayers and carbon electrodes

    Electrografting of BTSE: Zn films for advanced steel-aluminum joining by plastic deformation

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    This article presents the application of an adhesion promoting highly crosslinked ultrathin organic-inorganic hybrid layer applied to steel which promotes the subsequent joining process based on plastic deformation. The tensile shear results show that a significant increase of the bond strength between low-alloy steel (DC04) and aluminum (AW1050A H111), upon cold-pressure welding (CPW), could be achieved. Electrografting of an ultra-thin film of 1,2-bis(triethoxysilyl)ethane (BTSE) films on the steel surface was done from ethanolic solutions containing zinc ions. Based on surface spectroscopic analysis it is shown that silanol moieties present in the organosilane deposits can form stable chemical bonds with both the iron oxide covered steel and the aluminum oxide covered aluminum alloy. The successful modification of metal oxide surfaces with BTSE has been demonstrated via SEM-EDX, AFM, PM-IRRAS, and XPS measurements. In addition, electrochemical analysis of the BTSE:Zn films showed that the films lead to very good corrosion properties even at low thicknesses

    pH control of conductance in a pyrazolyl Langmuir–Blodgett monolayer

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    In this contribution pyrazole is identified as an excellent anchor group that forms high quality films under pH controlled conditions, allowing the modulation of the electrical properties with a more efficient electronic coupling in basic conditions.</p

    ‘‘Naked’’ gold nanoparticles supported on HOPG: melanin functionalization and catalytic activity

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    Reductive electrodesorption has been used to produce ‘‘naked’’ gold nanoparticles (AuNPs) 3 nm in size on HOPG from different thiolate-capped AuNPs. The clean AuNPs transform the electrocatalytic inert HOPG into an active surface for hydrogen peroxide electroreduction, causing a lowering of the cathodic overpotential of 0.25 V with respect to the Au(111) surface. Compared to the plain gold substrates, the nanostructures promote only a slight increase in the hydrogen evolution reaction. In a second modification step a 1 nm thick melanin–iron coating is electrochemically formed around the AuNPs. This ultrathin melanin–iron coating largely improves the catalytic activity of the bare AuNPs for both hydrogen peroxide electroreduction and hydrogen evolution reaction. This strategy, which integrates electrochemistry and nanotechnology, can be applied to the preparation of efficient ‘‘naked’’ AuNPs and organic-iron capped AuNPs catalysts.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicada

    The influence of semantic and phonological factors on syntactic decisions: An event-related brain potential study

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    During language production and comprehension, information about a word's syntactic properties is sometimes needed. While the decision about the grammatical gender of a word requires access to syntactic knowledge, it has also been hypothesized that semantic (i.e., biological gender) or phonological information (i.e., sound regularities) may influence this decision. Event-related potentials (ERPs) were measured while native speakers of German processed written words that were or were not semantically and/or phonologically marked for gender. Behavioral and ERP results showed that participants were faster in making a gender decision when words were semantically and/or phonologically gender marked than when this was not the case, although the phonological effects were less clear. In conclusion, our data provide evidence that even though participants performed a grammatical gender decision, this task can be influenced by semantic and phonological factors

    A new view of electrochemistry at highly oriented pyrolytic graphite

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    Major new insights on electrochemical processes at graphite electrodes are reported, following extensive investigations of two of the most studied redox couples, Fe(CN)64–/3– and Ru(NH3)63+/2+. Experiments have been carried out on five different grades of highly oriented pyrolytic graphite (HOPG) that vary in step-edge height and surface coverage. Significantly, the same electrochemical characteristic is observed on all surfaces, independent of surface quality: initial cyclic voltammetry (CV) is close to reversible on freshly cleaved surfaces (>400 measurements for Fe(CN)64–/3– and >100 for Ru(NH3)63+/2+), in marked contrast to previous studies that have found very slow electron transfer (ET) kinetics, with an interpretation that ET only occurs at step edges. Significantly, high spatial resolution electrochemical imaging with scanning electrochemical cell microscopy, on the highest quality mechanically cleaved HOPG, demonstrates definitively that the pristine basal surface supports fast ET, and that ET is not confined to step edges. However, the history of the HOPG surface strongly influences the electrochemical behavior. Thus, Fe(CN)64–/3– shows markedly diminished ET kinetics with either extended exposure of the HOPG surface to the ambient environment or repeated CV measurements. In situ atomic force microscopy (AFM) reveals that the deterioration in apparent ET kinetics is coupled with the deposition of material on the HOPG electrode, while conducting-AFM highlights that, after cleaving, the local surface conductivity of HOPG deteriorates significantly with time. These observations and new insights are not only important for graphite, but have significant implications for electrochemistry at related carbon materials such as graphene and carbon nanotubes
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