Ex Situ Scanning Electrochemical Microscopy (SECM) Investigation of Bismuth- and Bismuth/Lead Alloy Film-Modified Gold Electrodes in Alkaline Medium

Scanning electrochemical microscopy (SECM) in feedback mode was employed to characterise the reactivity and microscopic peculiarities of bismuth and bismuth/lead alloys plated onto gold disk substrates in 0.1 molL(-1) NaOH solutions. Methyl viologen was used as redox mediator, while a platinum microelectrode was employed as the SECM tip. The metal films were electrodeposited ex situ from NaOH solutions containing either bismuth ions only or both bismuth and lead ions. Approach curves and SECM images indicated that the metal films were conductive and locally reactive with oxygen to provide Bi(3+) and Pb(2+) ions. The occurrence of the latter chemical reactions was verified by local anodic stripping voltammetry (ASV) at the substrate solution interface by using a mercury-coated platinum SECM tip. The latter types of measurements allowed also verifying that lead was not uniformly distributed onto the bismuth film electrode substrate. These findings were confirmed by scanning electron microscopy images. The surface heterogeneity produced during the metal deposition process, however, did not affect the analytical performance of the bismuth coated gold electrode in anodic stripping voltammetry for the determination of lead in alkaline media, even in aerated aqueous solutions. Under the latter conditions, stripping peak currents proportional to lead concentration with a satisfactory reproducibility (within 5% RSD) were obtained.

Local Structure and Photochromic Response in Ormosils Containing Dodecatungstophosphoric Acid

Two hybrid materials based on dodecatungstophosphoric acid (HPW) dispersed in ormosils modified with 3-aminopropiltrietoxysilane (APTS) or with N-(3-(trimethoxysilyl)-propyl)-ethylene-diamine (TSPEN) show reversible photochromic response induced by irradiation in the 200-390 nm UV range. A set of solid-state nuclear magnetic resonance (NMR) techniques was used to analyze the structural properties of the main components of these hybrids (the HPW polyanion, the inorganic matrix, and the organic functionalities). For the ormosils, the use of (29)Si NMR, {(1)H}-(29)Si cross-polarization, and {(1)H}-(29)Si HETCOR revealed a homogeneous distribution of silicon species Q ``, T(2), and T(3) for the APTS hybrid, contrasting with the separation of T(3) species in the TSPEN hybrid. The combination of (31)P NMR, {(1)H}-(31)P cross-polarization and (31)P-{(1)H} spin-echo double resonance (SEDOR) revealed the dispersion of the HPW ions in the ormosil, occupying sites with a high number of close protons (>50). Differences in the molecular dynamics at room temperature, inferred from SEDOR experiments, indicate a state of restricted mobility of the HPW ion and the surrounding molecular groups in the TSPEN hybrid. This behavior is consistent with the presence of more amino groups in the TSPEN, acting as chelating groups to the HPW ion. This hybrid, with the strong chelate interaction of the diamine group, shows the most intense photochromic response, in agreement with the charge transfer models proposed to explain the photochromic effect. Electronic reflectance spectroscopy in irradiated samples revealed the presence of one-electron and two-electron reduced polyanions. The one-electron reduced species could be detected also by (31)P NMR spectroscopy immediately after UV irradiation.

Autodeterminação local e desenvolvimento: uma análise da dinâmica social no município de São Roque de Minas

In this thesis, the basic research of Chase and Simon (1973) is questioned, and we seek new results by analyzing the errors of experts and beginners chess players in experiments to reproduce chess positions. Chess players with different levels of expertise participated in the study. The results were analyzed by a Brazilian grandmaster, and quantitative analysis was performed with the use of statistical methods data mining. The results challenge significantly, the current theories of expertise, memory and decision making in this area, because the present theory predicts piece on square encoding, in which players can recognize the strategic situation reproducing it faithfully, but commit several errors that the theory can¿t explain. The current theory can¿t fully explain the encoding used by players to register a board. The errors of intermediary players preserved fragments of the strategic situation, although they have committed a series of errors in the reconstruction of the positions. The encoding of chunks therefore includes more information than that predicted by current theories. Currently, research on perception, trial and decision is heavily concentrated on the idea of 'pattern recognition'. Based on the results of this research, we explore a change of perspective. The idea of 'pattern recognition' presupposes that the processing of relevant information is on 'patterns' (or data) that exist independently of any interpretation. We propose that the theory suggests the vision of decision-making via the recognition of experience.

Investigation in SrTiO3-CaTiO3-PbTiO3 ternary thin films by dielectric proprieties and Raman spectroscopy

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Short-Term Multinodal Load Forecasting Using a Modified General Regression Neural Network

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Modified stabilization method for the tibial tuberosity advancement technique: a biomechanical study

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Mechanical resistance of the modified stabilization method for the tibial tuberosity advancement technique: ex vivo experimental study in dogs

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

In Vitro Study of Fracture Load and Fracture Pattern of Ceramic Crowns: A Finite Element and Fractography Analysis

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Predação de ninhos artificiais em uma ilha na Mata Atlântica: testando o local e o tipo de ovo

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Biodiversity conservation in human-modified Amazonian forest landscapes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Collision of positronium with atoms, molecules and ions using a modified coupled-channel framework

Scattering of positronium (Ps) from atoms (H, He, Ne, Ar), molecule (H(2)) and ion (He(+)) have been investigated using a coupled-channel (CC) formalism with a regularised non-local exchange potential. The advantage of using such a regularized exchange potential in the close-coupling formalism and the normalizability aspect of the solution at low energies with a minimum effective coupling are discussed. Results for the elastic and total scattering cross-sections, resonance and binding energies in Ps-H, and pick-off annihilation results in Ps-He are found to be in excellent agreement with measurements and variational predictions. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Weak-field approximation of effective gravitational theory with local Galilean invariance

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

On an Non-Ideal Global and Local Energy Transfer, Using an Electro-Magneto and Magneto-Rheological Dampers

In this paper, we investigated the nonlinear vibrations of a Non-ideal (NIS) electromechanical absorber (NEVA), taking into account a modified mathematical model of (MR) Damper. We observed the presence of the Sornmerfeld effect (it is the steady state frequencies of the DC motor, which it will usually increasing as more power (Voltage) is given to it, in a step-by-step fashion. When a resonance condition it is reached, the better part of this energy it is consumed to generate large amplitude vibrations of the foundation, without sensible change of the motor frequency). The obtained results, by using numerical and analytical simulations, were discussed, in details.

STM probing of local oscillations of the Fano-Kondo effect: a Doniach-Sunjic approach for the Kondo peak

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Structural and phenomenological characterization of the thermoreversible sol-gel transition of a zirconyl aqueous precursor modified by sulfuric acid

The thermoreversible sol-gel transition is well-known in biological and organic polymeric systems but has not been reported for inorganic systems. In this paper we put in evidence a thermoreversible sol-gel transition for zirconyl chloride aqueous solutions modified by sulfuric acid in the ratio 3:1 Zr:SO4. The synthesis conditions are detailed and a variety of experimental techniques (turbidimetry, dynamic rheology, and EXAFS) have been employed for investigating the thermal reversibility and the chemical structure of this new material. Turbidimetric measurements performed for solutions containing different concentrations of precursor have evidenced that the sol-gel transformation temperature increases from 50 to 80 degrees C as the concentration of zirconyl chloride decreases from 0.22 to 0.018 mol L-1. A more detailed study has been done for the sample with [Zr] = 0.156 mol L-1, in which the sol-gel-sol transformation has been repeated several times by a cyclic variation of the temperature. The mechanical properties of this sample, evaluated by measuring the storage and the loss moduli, show a change from liquid like to viscoelastic to elastic behavior during the sol-gel transition and vice versa during the gel-sol one. In situ EXAFS measurements performed at the Zr K-edge show that no change of the local order around Zr occurs during the sol-gel-sol transition, in agreement with the concept of physical gel formation. We have proposed for the structure of the precursor an inner core made of hydroxyl and oxo groups bridging together zirconium atoms surrounded in surface by complexing sulfate ligands, the sulfate groups act as a protective layer, playing a key role in the linking propagation among primary particles during sol-gel-sol transition.