Preparo de óxido de nióbio suportado em alumina por deposição química em fase vapor: caracterização por espectroscopia vibracional e termogravimetria

Alumina supported niobium oxide was prepared by chemical vapor deposition (CVD) of NbCl5. The alumina was calcined and pretreated at differents temperatures in order to vary the density of OH groups on the surface which was determined by thermogravimetric analysis. A good correlation was found between the amount of anchored niobium and the total number of anionic sites (oxide and hydroxyl groups) on the surface of the alumina. The infrared spectra on the OH stretching region indicate that OH groups coordinated to at least one tetrahedral aluminum were more reactive towards NbCl5.

Nova rota de preparação do 2-cloro-1,3,2-dioxofosfolana e 2-cloro-4,5-benzo-1,3,2-dioxofosfolana e caracterização por espectroscopia de RMN multinuclear

A new method for the preparation of 2-chloro-1,3,2-dioxaphospholane (1) and 2-chloro-4,5-benzo-1,3,2-dioxaphospholane (2), are reported. The modifications introduced in the synthetic route improved the yield and facilitated the control of reaction, but the synthesis require longer reaction time. The compounds were characterized by ¹H, 13C{¹H} and31P{¹H} NMR spectroscopy. Due to the complexity of the spin system AA'BB'X (A, A', B, B' = ¹H; X = 31P) of 2, a simulation of the ¹H NMR spectra was done and it's in agreement with the bibliography.

Espectroscopia óptica de vidros fluoroindatos dopados com íons Er3+ e Yb3+

Optical spectroscopy in the 400-1700nm wavelength range was performed on rare earth doped heavy metal fluoride (HMF) glasses. In the present work In-based fluoride glasses with a fixed 2 mol % YbF3 concentration and an ErF3 content ranging from 0 to 8 mol % were investigated. According to the experimental spectroscopic data a dependence in the absorption coefficient, the photoluminescence intensity and in the radiative lifetime could be verified as a function of the ErF3 content. In addition, at liquid nitrogen temperature, light emission corresponding to indirect transitions in the infrared energy range could be easily observed as a consequence of the low phonon frequency characteristic of this class of fluoride glasses. For all the studied compositions, strong upconversion to the green and red light was observed by pumping these Er3+- and Yb3+-doped HMF glasses with 790 and 980nm photon sources.

Estudo por espectroscopia no infravermelho da interação metal-suporte em Pt/TiO2. A influência da adsorção de hidrogênio

The influence of the presence of hydrogen on Pt/TiO2 catalysts submitted to reduction treatment has been studied by FT-IR at room temperature. After submitting to LTR treatment, the hydrogen spillover has been detected and the presence of hydrogen at the bulk is shown to produce a strong absorption in the infrared spectral region. After HTR treatment, the hydrogen is strongly chemissorbed.

Aplicação de algoritmos genéticos na seleção de variáveis em espectroscopia no infravermelho médio: determinação simultânea de glicose, maltose e frutose

Genetic algorithm was used for variable selection in simultaneous determination of mixtures of glucose, maltose and fructose by mid infrared spectroscopy. Different models, using partial least squares (PLS) and multiple linear regression (MLR) with and without data pre-processing, were used. Based on the results obtained, it was verified that a simpler model (multiple linear regression with variable selection by genetic algorithm) produces results comparable to more complex methods (partial least squares). The relative errors obtained for the best model was around 3% for the sugar determination, which is acceptable for this kind of determination.

Espectroscopia vibracional: sistemática para o cálculo dos estiramentos CO de complexos carbonílicos e determinação da sua atividade IV e Raman

IR bands related to M-C stretchings are not diagnostically significant for the identification of carbonyl groups in the spectra of carbonyl complexes. Otherwise, the frequency, intensity and number of bands for the CO stretchings provide very useful informations about the number of CO ligands and many others structural proprieties, like the presence of bridged CO groups. We report about a relatively simple and useful method for the determination of the CO stretchings of carbonyl complexes, which considers only the bond stretching internal coordinates of the CO groups.

Aplicação de alguns modelos quimiométricos à espectroscopia de fluorescência de raios-X de energia dispersiva

The objective of this work was to accomplish the simultaneous determination of some chemical elements by Energy Dispersive X-ray Fluorescence (EDXRF) Spectroscopy through multivariate calibration in several sample types. The multivariate calibration models were: Back Propagation neural network, Levemberg-Marquardt neural network and Radial Basis Function neural network, fuzzy modeling and Partial Least Squares Regression. The samples were soil standards, plant standards, and mixtures of lead and sulfur salts diluted in silica. The smallest Root Mean Square errors (RMS) were obtained with Back Propagation neural networks, which solved main EDXRF problems in a better way.

Aplicação da espectroscopia de ressonância magnética nuclear para estudos de difusão molecular em líquidos: a técnica DOSY

Diffusion coefficients provide uniquely detailed and easily interpreted information on molecular organization and phase structure. They are quite sensitive to structural changes, and to binding and association phenomena, in particular for liquid colloidal or macromolecular systems. This paper describes the principles of diffusion measurements in liquids by pulsed magnetic field gradient spin-echo (PFG-SE) NMR spectroscopy. The important PFG-SE technique known as DOSY is presented and discussed. This is a noninvasive technique that can provide individual multicomponent translational diffusion coefficients with good precision in a few minutes, without the need for radioactive isotopic labelling.

Modelo de calibração da concentração de metilmetacrilato em solução aquosa utilizando espectroscopia de absorção no ultravioleta

Dilutions of methylmetacrylate ranging between 1 and 50 ppm were obtained from a stock solution of 1 ml of monomer in 100 ml of deionised water, and were analyzed by an absorption spectrophotometer in the UV-visible. Absorbance values were used to develop a calibration model based on the PLS, with the aim to determine new sample concentrations. The number of latent variables used was 6, with the standard errors of calibration and prediction found to be 0,048 ml/100 ml and 0,058 ml/100 ml. The calibration model was successfully used to calculate the concentration of monomer released in water, where complete dentures were kept for one hour after polymerization.

Determinação da concentração micelar crítica de ácidos húmicos por medidas de condutividade e espectroscopia

The aim of this study was the determination of the critical micelle concentration (CMC) of the sodium dodecyl sulfate (SDS) surfactant using spectroscopic and conductimetric determinations and to compare these methodologies in the determination of the CMC of different humic acids (HA). The CMC obtained by conductimetric determination was satisfactory. By spectroscopic determination two values of the CMC were obtained for HA. These values can be to due the intra and intermolecular interactions in the HA structure.

Validação de modelos de calibração multivariada: uma aplicação na determinação de pureza polimórfica de carbamazepina por espectroscopia no infravermelho próximo

The application of analytical procedures based on multivariate calibration models has been limited in several areas due to requirements of validation and certification of the model. Procedures for validation are presented based on the determination of figures of merit, such as precision (mean, repeatability, intermediate), accuracy, sensitivity, analytical sensitivity, selectivity, signal-to-noise ratio and confidence intervals for PLS models. An example is discussed of a model for polymorphic purity control of carbamazepine by NIR diffuse reflectance spectroscopy. The results show that multivariate calibration models can be validated to fulfill the requirements imposed by industry and standardization agencies.

Espectroscopia de correlação bidimensional: fundamentos, aplicações e perspectivas

This paper presents the basic theory of generalized two-dimensional correlation spectroscopy. This method is applicable to various types of spectroscopy, including Infrared, Near Infrared and Raman Spectroscopy and it emphasizes spectral features not readily observable in conventional one-dimensional spectra. Some applications are cited, including work developed in Brazil.

Espectroscopia de fotoelétrons de limiares de átomos e moléculas

A threshold photoelectron spectrometer applied to the study of atomic and molecular threshold photoionization processes is described. The spectrometer has been used in conjunction with a toroidal grating monochromator at the National Synchrotron Radiation Laboratory (LNLS), Brazil. It can be tuned to accept threshold electrons (< 20 meV) and work with a power resolution of 716 (~18 meV at 12 eV) with a high signal/noise ratio. The performance of this apparatus and some characteristics of the TGM (Toroidal Grating Monochromator) beam line of LNLS are described and discussed by means of argon, O2 and N2 threshold photoelectron spectra.

Espectroscopia de impedância eletroquímica aplicada ao estudo das reações heterogêneas em ânodos dimensionalmente estáveis

This paper discusses different aspects related to the application of electrochemical impedance spectroscopy (EIS) in the study of heterogeneous electrochemical reactions occurring on Dimensionally Stable anodes (DSA®). The most relevant aspects of the semiconductor/electrolyte interface, the application of the EIS classical equivalent circuit approach and the ac porous model in DSA are presented. The paper shows that DSA type electrodes can be consistently investigated by using the ac porous model and an analysis is presented showing the advantage of applying this kind of approach to study heterogeneous reactions on DSA electrodes. Furthermore, some preliminary results on Ti/Ru0,3Ti(0,7-x)Sn x O2 based electrodes are presented to exemplify the use of the ac porous model analysis.

Elucidando os estados de oxidação do nitrogênio através da espectroscopia de absorção de raios-X na borda K do nitrogênio

The potentialities of X-ray Absorption Near Edge Spectroscopy (XANES) of the N K edge (N K) obtained with the spherical grating monochromator beam line at the Brazilian National Synchrotron Light Laboratory are explored in the investigation of poly(aniline), nanocomposites and dyes. Through the analysis of N K XANES spectra of conducting polymers and many other dye compounds that are dominated by 1s®p* transitions, it was possible to correlate the band energy value with the nitrogen oxidation states. An extensive N K XANES spectral database was obtained, thus permitting the elucidation of the nature of different nitrogens present in the intercalated conducting polymers.