Análise da saliva de pacientes com ardência bucal por espectroscopia de Fourier Transform Infrared (FT-IR)

Pós-graduação em Biopatologia Bucal - ICT

Rietveld refinement and optical properties of SrWO4:Eu3+ powders prepared by the non-hydrolytic sol-gel method

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Crystal growth and photoluminescence of europium-doped strontium titanate prepared by a microwave hydrothermal method

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

Development and validation of the quantitative analysis of ampicillin sodium in powder for injection by Fourier-transform infrared spectroscopy (FT-IR)

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

Morphology and properties of (Ba, Sr, Ca) titanates synthesized by microwave-assisted hydrothermal method

Ba1-xCaxTiO3, Ba1-xSrxTiO3 and Sr1-xCaxTiO3 (x = 0, 0.25, 0.50, 0.75 and 1) nanoparticles were synthesized using the microwave-assisted hydrothermal method. Samples were prepared for 40 minutes at 140°C under a pressure of 3 MPa using an adapted domestic microwave oven. The samples were characterized by X-Ray diffraction (XRD), scanning electron microscopy (FE-SEM), and Raman, photoluminescence (PL) and ultraviolet-visible (UV-Vis) spectroscopies. XRD data show that ceramic powders have crystalline phases associated with a short-range structural disorder. This structural disorder is confirmed by Raman spectral bands indicating multi-phonon processes and the presence of defects or impurities. Such defects account for a broad band in the photoluminescence spectrum in the green light (460 nm) region for all samples. Gap energy variation, obtained from UV-Vis spectra, suggest a non-uniform band structure of these titanates in accordance with the PL results. The morphology of each sample is changed with doping and varies from a spherical to cubic appearance for energy minimization.

Spectral Induced Polarization (SIP) signatures of clayey soils containing toluene

We performed laboratory experiments to investigate the sensitivity of the Spectral Induced Polarization (SIP) method to toluene contamination in clayey soils. We used mixtures of quartzitic sand and montmorillonite as soil samples, artificially contaminated with varying amounts of toluene. Care was taken to quantify the experimental uncertainty resulting from packing since such effects must be quantified if variations in SIP signatures between samples are to be reliably interpreted in terms of the effects of hydrocarbon concentration. The SIP response of all samples following addition of toluene was monitored for a period of 40 days following sample preparation. Stepwise regression was used to examine the statistical significance of correlations between (i) clay content and (ii) toluene concentration and SIP parameters. Both single-frequency real and imaginary conductivity measurements, along with the integral chargeability, normalized chargeability, DC conductivity and time constant obtained from a Debye decomposition fitting, were examined in this regression analysis. The SIP measurements show a clear time dependence following sample preparation, indicating that samples containing toluene may take significant time to reach an equilibrium electrical response. SIP measurements are significantly related to toluene content shortly after sample preparation, when the expected dependence of SIP on clay concentration is apparently suppressed. However, for the state of electrical equilibrium after 40 days (interpreted to indicate surface chemistry at equilibrium) there is no significant relation between SIP measurements and toluene content; instead SIP measurements are then significantly correlated with clay concentration. The total chargeability, normalized chargeability and relaxation time obtained from the Debye decomposition show no correlation with toluene content, indicating that this procedure, which likely integrates over multiple mechanisms, may not be suitable for understanding relationships between SIP and hydrocarbon contamination. We find only small low-frequency polarization signals observed in relation to toluene concentration (2 mrad at 0.01 Hz), which initially decreases the interfacial polarization. Unlike earlier works, our results do not support the use of the SIP method as a tool for monitoring toluene contamination in clay soils.

Fractal descriptors based on Fourier spectrum applied to texture analysis

This work proposes the development and study of a novel technique lot the generation of fractal descriptors used in texture analysis. The novel descriptors are obtained from a multiscale transform applied to the Fourier technique of fractal dimension calculus. The power spectrum of the Fourier transform of the image is plotted against the frequency in a log-log scale and a multiscale transform is applied to this curve. The obtained values are taken as the fractal descriptors of the image. The validation of the proposal is performed by the use of the descriptors for the classification of a dataset of texture images whose real classes are previously known. The classification precision is compared to other fractal descriptors known in the literature. The results confirm the efficiency of the proposed method. (C) 2012 Elsevier B.V. All rights reserved.

Calibration of a Species-Specific Spectral Vegetation Index for Leaf Area Index (LAI) Monitoring: Example with MODIS Reflectance Time-Series on Eucalyptus Plantations

The leaf area index (LAI) is a key characteristic of forest ecosystems. Estimations of LAI from satellite images generally rely on spectral vegetation indices (SVIs) or radiative transfer model (RTM) inversions. We have developed a new and precise method suitable for practical application, consisting of building a species-specific SVI that is best-suited to both sensor and vegetation characteristics. Such an SVI requires calibration on a large number of representative vegetation conditions. We developed a two-step approach: (1) estimation of LAI on a subset of satellite data through RTM inversion; and (2) the calibration of a vegetation index on these estimated LAI. We applied this methodology to Eucalyptus plantations which have highly variable LAI in time and space. Previous results showed that an RTM inversion of Moderate Resolution Imaging Spectroradiometer (MODIS) near-infrared and red reflectance allowed good retrieval performance (R-2 = 0.80, RMSE = 0.41), but was computationally difficult. Here, the RTM results were used to calibrate a dedicated vegetation index (called "EucVI") which gave similar LAI retrieval results but in a simpler way. The R-2 of the regression between measured and EucVI-simulated LAI values on a validation dataset was 0.68, and the RMSE was 0.49. The additional use of stand age and day of year in the SVI equation slightly increased the performance of the index (R-2 = 0.77 and RMSE = 0.41). This simple index opens the way to an easily applicable retrieval of Eucalyptus LAI from MODIS data, which could be used in an operational way.

Augmented Lagrangian method with nonmonotone penalty parameters for constrained optimization

At each outer iteration of standard Augmented Lagrangian methods one tries to solve a box-constrained optimization problem with some prescribed tolerance. In the continuous world, using exact arithmetic, this subproblem is always solvable. Therefore, the possibility of finishing the subproblem resolution without satisfying the theoretical stopping conditions is not contemplated in usual convergence theories. However, in practice, one might not be able to solve the subproblem up to the required precision. This may be due to different reasons. One of them is that the presence of an excessively large penalty parameter could impair the performance of the box-constraint optimization solver. In this paper a practical strategy for decreasing the penalty parameter in situations like the one mentioned above is proposed. More generally, the different decisions that may be taken when, in practice, one is not able to solve the Augmented Lagrangian subproblem will be discussed. As a result, an improved Augmented Lagrangian method is presented, which takes into account numerical difficulties in a satisfactory way, preserving suitable convergence theory. Numerical experiments are presented involving all the CUTEr collection test problems.

Structural refinement, growth process, photoluminescence and photocatalytic properties of (Ba1-xPr2x/3)WO4 crystals synthesized by the coprecipitation method

Barium praseodymium tungstate (Ba1-xPr2x/3)WO4 crystals with (x = 0, 0.01, and 0.02) were prepared by the coprecipitation method. These crystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinements, Fourier-transform Raman (FT-Raman) and Fourier-transform infrared (FT-IR) spectroscopies. The shape and size of these crystals were observed by field emission scanning electron microcopy (FE-SEM). Their optical properties were investigated by ultraviolet visible (UV-vis) absorption and photoluminescence (PL) measurements. Moreover, we have studied the photocatalytic (PC) activity of crystals for degradation of rhodamine B (RhB) dye. XRD patterns, Rietveld refinements data, FT-Raman and FT-IR spectroscopies indicate that all crystals exhibit a tetragonal structure without deleterious phases. FT-Raman spectra exhibited 13 Raman-active modes in a range from 50 to 1000 cm(-1), while FT-IR spectra have 8 infrared active modes in a range from 200 to 1050 cm(-1). FE-SEM images showed different shapes (bonbon-, spindle-, rice-and flake-like) as well as a reduction in the crystal size with an increase in Pr3+ ions. A possible growth process was proposed for these crystals. UV-vis absorption measurements revealed a decrease in optical band gap values with an increase of Pr3+ into the matrix. An intense green PL emission was noted for (Ba1-xPr2x/3)WO4 crystals (x = 0), while crystals with (x = 0.01 and 0.02) produced a reduction in the wide band PL emission and the narrow band PL emission which is related to f-f transitions from Pr3+ ions. High photocatalytic efficiency was verified for the bonbon-like BaWO4 crystals as a catalyst in the degradation of the RhB dye after 25 min under UV-light. Finally, we discuss possible mechanisms for PL and PC properties of these crystals.

The boundedness of penalty parameters in an augmented Lagrangian method with constrained subproblems

Augmented Lagrangian methods are effective tools for solving large-scale nonlinear programming problems. At each outer iteration, a minimization subproblem with simple constraints, whose objective function depends on updated Lagrange multipliers and penalty parameters, is approximately solved. When the penalty parameter becomes very large, solving the subproblem becomes difficult; therefore, the effectiveness of this approach is associated with the boundedness of the penalty parameters. In this paper, it is proved that under more natural assumptions than the ones employed until now, penalty parameters are bounded. For proving the new boundedness result, the original algorithm has been slightly modified. Numerical consequences of the modifications are discussed and computational experiments are presented.

Processing of high resolution magic angle spinning spectra of breast cancer cells by the filter diagonalization method

Proton nuclear magnetic resonance (H-1 NMR) spectroscopy for detection of biochemical changes in biological samples is a successful technique. However, the achieved NMR resolution is not sufficiently high when the analysis is performed with intact cells. To improve spectral resolution, high resolution magic angle spinning (HR-MAS) is used and the broad signals are separated by a T-2 filter based on the CPMG pulse sequence. Additionally, HR-MAS experiments with a T-2 filter are preceded by a water suppression procedure. The goal of this work is to demonstrate that the experimental procedures of water suppression and T-2 or diffusing filters are unnecessary steps when the filter diagonalization method (FDM) is used to process the time domain HR-MAS signals. Manipulation of the FDM results, represented as a tabular list of peak positions, widths, amplitudes and phases, allows the removal of water signals without the disturbing overlapping or nearby signals. Additionally, the FDM can also be used for phase correction and noise suppression, and to discriminate between sharp and broad lines. Results demonstrate the applicability of the FDM post-acquisition processing to obtain high quality HR-MAS spectra of heterogeneous biological materials.

Gaussian deconvolution: a useful method for a form-free modeling of scattering data from mono- and multilayered planar systems

A new method for analysis of scattering data from lamellar bilayer systems is presented. The method employs a form-free description of the cross-section structure of the bilayer and the fit is performed directly to the scattering data, introducing also a structure factor when required. The cross-section structure (electron density profile in the case of X-ray scattering) is described by a set of Gaussian functions and the technique is termed Gaussian deconvolution. The coefficients of the Gaussians are optimized using a constrained least-squares routine that induces smoothness of the electron density profile. The optimization is coupled with the point-of-inflection method for determining the optimal weight of the smoothness. With the new approach, it is possible to optimize simultaneously the form factor, structure factor and several other parameters in the model. The applicability of this method is demonstrated by using it in a study of a multilamellar system composed of lecithin bilayers, where the form factor and structure factor are obtained simultaneously, and the obtained results provided new insight into this very well known system.

New Improved Version of J 1 ...J 4 Interferometry Method and its Application to Nanometric Vibration Measurements

Piezoelectric ceramics, such as PZT, can generate subnanometric displacements, bu t in order to generate multi- micrometric displacements, they should be either driven by high electric voltages (hundreds of volts ), or operate at a mechanical resonant frequency (in narrow band), or have large dimensions (tens of centimeters). A piezoelectric flextensional actuator (PFA) is a device with small dimensions that can be driven by reduced voltages and can operate in the nano- and micro scales. Interferometric techniques are very adequate for the characterization of these devices, because there is no mechanical contact in the measurement process, and it has high sensitivity, bandwidth and dynamic range. A low cost open-loop homodyne Michelson interferometer is utilized in this work to experimentally detect the nanovi brations of PFAs, based on the spectral analysis of the interfero metric signal. By employing the well known J 1 ...J 4 phase demodulation method, a new and improved version is proposed, which presents the following characteristics: is direct, self-consistent, is immune to fading, and does not present phase ambiguity problems. The proposed method has resolution that is similar to the modified J 1 ...J 4 method (0.18 rad); however, differently from the former, its dynamic range is 20% larger, does not demand Bessel functions algebraic sign correction algorithms and there are no singularities when the static phase shift between the interferometer arms is equal to an integer multiple of  /2 rad. Electronic noise and random phase drifts due to ambient perturbations are taken into account in the analysis of the method. The PFA nanopositioner characterization was based on the analysis of linearity betw een the applied voltage and the resulting displacement, on the displacement frequency response and determination of main resonance frequencies.

Rheology and Fourier-transform rheology on water-based systems

The influence of shear fields on water-based systems was investigated within this thesis. The non-linear rheological behaviour of spherical and rod-like particles was examined with Fourier-Transform rheology under LAOS conditions. As a model system for spherical particles two different kinds of polystyrene dispersions, with a solid content higher than 0.3 each, were synthesised within this work. Due to the differences in polydispersity and Debye-length, differences were also found in the rheology. In the FT-rheology both kinds of dispersions showed a similar rise in the intensities of the magnitudes of the odd higher harmonics, which were predicted by a model. The in some cases additionally appearing second harmonics were not predicted. A novel method to analyse the time domain signal was developed, that splits the time domain signal up in four characteristic functions. Those characteristic functions correspond to rheological phenomena. In some cases the intensities of the Fourier components can interfere negatively. FD-virus particles were used as a rod-like model system, which already shows a highly non-linear behaviour at concentrations below 1. % wt. Predictions for the dependence of the higher harmonics from the strain amplitude described the non-linear behaviour well at large, but no so good at small strain amplitudes. Additionally the trends of the rheological behaviour could be described by a theory for rod-like particles. An existing rheo-optical set-up was enhanced by reducing the background birefringence by a factor of 20 and by increasing the time resolution by a factor of 24. Additionally a combination of FT-rheology and rheo-optics was achieved. The influence of a constant shear field on the crystallisation process of zinc oxide in the presence of a polymer was examined. The crystallites showed a reduction in length by a factor of 2. The directed addition of polymers in combination with a defined shear field can be an easy way for a defined change of the form of crystallites.