Estudo do efeito do cloreto em catalisadores de paládio usando a análise no infravermelho e de fotoelétrons excitados por raios x

Chloride poisoning is known as having an inhibitor effect in the activity of metal catalysis. In this work in situ infrared spectroscopy (FTIR) of adsorbed carbon monoxide and x-ray photoelectron spectroscopy (XPS) were used to investigate the effect of chloride presence in the electronic metal density in the d subshell of palladium dispersed on alumina. The chloride poisoning effect was interpreted as an electronic effect since a weak back-bonded Pd-CO was formed due to the decrease in the electronic density of the d subshell of palladium, which could be also detected by the higher Pd 3d5/2 binding energy in the chloride presence. A similar poisoning effect was also observed for chloride free Pd/Al2O3 reduced at 500 ºC, and it was interpreted based on the interaction of metal with the alumina surface. The use of molybdena/alumina binary system as support, yield a contrary effect due to the metal-support interaction.

Sistemas interfaceados de análise por injeção em fluxo e eletroforese capilar (FIA - CE): desafios, aplicações e perspectivas

A review about the state-of-the-art of flow injection analysis (FIA) -- capillary electrophoresis (CE) systems is presented. The basic principles of flow injection and capillary electrophoresis are briefly revised. The main aspects of the FIA-CE hybridization, including advantages and shortcomings, are discussed. Some applications involving all different designs are also presented. This review covers the literature from 1997 up to 2000.

A quimiluminescência como ferramenta analítica: do mecanismo a aplicações da reação do luminol em métodos cinéticos de análise

Relevant aspects of proposed mechanisms of the chemiluminescent reaction of luminol are presented and commented to emphasize its perspectives for kinetic analysis. A careful search for analytical applications of this reaction is discussed in order to point out new trends of the studies. Kinetic analysis using the luminol reaction is proposed to be a very attractive due to the good performance of the reaction in analytical applications and the positive characteristics of kinetic analysis, such as low cost and sensibility. It is pointed out that kinetic analysis using the chemiluminescent reaction of luminol should be encouraged.

Estudo QSPR sobre os coeficientes de partição: descritores mecânico-quânticos e análise multivariada

Quantum chemistry and multivariate analysis were used to estimate the partition coefficients between n-octanol and water for a serie of 188 compounds, with the values of the q 2 until 0.86 for crossvalidation test. The quantum-mechanical descriptors are obtained with ab initio calculation, using the solvation effects of the Polarizable Continuum Method. Two different Hartree-Fock bases were used, and two different ways for simulating solvent cavity formation. The results for each of the cases were analised, and each methodology proposed is indicated for particular case.

Análise de glicocorticosteróides por CG-EM: uma nova abordagem de derivatização para o controle de dopagem no esporte

Glucocorticosteroids (CT) show a powerful anti-inflammatory effect. In view of this, they are extensively used in sports medicine, but their misuse (systemic administration) can lead to severe injuries on athletes and has been restricted by the IOC in recent years. For GC-MS analysis, a derivatization step is necessary in order to convert them to a stable form, thus preventing thermal breakdown with the loss of the ketone side chain. Derivatization of CT is reviewed and a new approach of silylation is presented for screening of CT in urine.

Análise de suspensões de argilas por espectrometria de emissão óptica com plasma induzido com configuração axial

The goal of this study was to evaluate the feasibility of direct introduction of clay slurries in an inductively coupled plasma optical emission spectrometer with axial view configuration. Calibration was performed using a certified reference material with a mean particle size of 13 µm (IPT-42) and the analytical curve was applied for quantification of two others reference materials (IPT-28 and IPT-32) and four samples. It was demonstrated that the analytical curve thus obtained was not completely suitable for IPT-28 and samples due to different mineralogical phases determined by X-ray diffraction. After considering this effect, it was possible for most elements to obtain results in agreement with certified values or with values obtained by a conventional technique at a 95% confidence level. It was demonstrated that the ICP-OES with axial view configuration did not present any incompatibility with the direct introduction of a complex inorganic suspension.

Determinação enzimática de dopamina em formulações farmacêuticas utilizando sistema de análise por injeção em fluxo com extrato bruto de abacate (Persea americana)

In this work, a spectrophotometric flow injection analysis system using a crude extract of avocado (Persea americana) as a source of polyphenol oxidase to dopamine determination was developed. The substrates and enzyme concentrations from 2.4x10-7 to 5.3x10-4 mol L-1 and 28 to 332 units mL-1 were evaluated, respectively. In addition, the FIA parameters such as sample loop (50 to 500 µL), flow rate (1.4 to 4.3 mL min-1) and reactor length (100 to 500 cm) were also evaluated in a 0.1 mol L-1 phosphate buffer solution (pH 7.0). Dopamine solution concentrations were determined using 277 units mL-1 enzyme solution, 400 mL enzyme loop, 375 µL sample loop, 2.2 mL min-1 flow rate and a reactor of 350 cm. The analytical curve showed a linearity from 5.3x10-5 to 5.3x10-4 mol L-1 dopamine with a detection limit of 1.3x10-5 mol L-1. The analytical frequency was 46 h-1 and the RSD lower than 0.5% for 5.3x10-4 mol L-1 dopamine solution (n=10). A paired t-test showed that all results obtained for dopamine in commercial formulations using the proposed flow injection procedure and a spectrophotometric procedure agree at the 95% confidence level.

Emprego de padrão único para a construção de curvas analíticas em sistema de análise por injeção em fluxo associado à espectrofotometria em fase sólida

In this work two procedures were proposed for analytical curves construction using a single standard solution employing a flow injection system with solid phase spectrophotometric detection (FI-SPS). A flow cell contends the chromogenic reagent 1-(2-tiazolylazo)-2-naphtol was positioned on the optical path. The first procedure was based on controlled concentration of analyte on solid phase and the relations between absorbance and the total volume of injected allowed the calculation of analyte concentration. The second procedure was developed employing controlled dispersion/retention in flow system where analyte concentration was obtained by exploiting the relation between transient signals of samples and single standard solution at equivalent reading time. The procedures were successfully applied for zinc determination in synthetic solutions with good precision and accuracy at 95% confidence level.

Análise de ácidos graxos por eletroforese capilar utilizando detecção condutométrica sem contato

This article describes a novel approach to the separation of fatty acids ranging from 8 to 20 carbons using capillary electrophoresis with contactless conductivity detection. Complete separation of nine linear chain fatty acids (from C8:0 to C20:0) was achieved in 15 min under normal polarity operation. Limits of detection ranged from 35 to 319 µmol L-1 for C20:0 to C8:0, respectively. The optimized running electrolyte composition was 5.0 mmol L-1 phosphate buffer at pH 7, 4.0 mmol L-1 dimethyl-b-cyclodextrin, 2.0 mmol L-1 trimethyl-b-cyclodextrin, acetonitrile 50% (v/v), and methanol 20% (v/v). The applicability of the separation system was demonstrated by the analysis of coconut vegetable oil.

O uso de radiação ultravioleta para o pré-tratamento de amostras em análise inorgânica

The basic principles of UV irradiation as sample pre-treatment step and its potential for inorganic analysis are illustrated and discussed through significant examples from the literature. Not only does this overview cover the classical applications of this technique in the decomposition of organic matter in electroanalysis, but it also presents recent trends, including the increasing interest in employing UV irradiation in flow analytical systems, successful attempts to enhance its effectiveness and the coupling with chromatographic and spectroscopic methodologies. Furthermore, a number of relevant cases of UV-driven derivatization reactions involving photo-sensitive inorganic species are presented, showing some convenient options to perform fast and reliable determination of inorganic and organic analytes.

Estabilidade relativa de alcenos: análise dos critérios encontrados nos livros textos de graduação e uma proposta de explicação operacional para alcenos dissubstituídos

Despite of being used as thermodynamic criterion to rank alkene stability in a number of undergraduate textbooks, the heat of hydrogenation does not describe adequately the relative stability of disubstituted alkenes. In this work, both the heat of formation and the heat of combustion were used as thermodynamic criteria to rank correctly the stability of alkenes according to the degree of alkyl substitution and also in the disubstituted series (geminal > trans > cis). An operational model based on molecular orbital and valence bond representations of hyperconjugation is proposed to show how this effect can explain the order of stability of this class of compounds.

Análise teórica da interação de CO, CO2 e NH3 com ZnO

This paper presents a study of the interaction of small molecules with ZnO surfaces by means of theoretical methods. The AM1 semi-empirical method was used for optimizing the geometric parameters of adsorbed molecules. The optimized AM1 structures were used in the calculations of the ab initio RHF method with the 3-21G* basis set. The interaction of CO, CO2 and NH3 molecules were studied with (ZnO)22 and (ZnO)60 cluster models. We have analyzed the interaction energy, SCF orbital energies, Mulliken charges and the density of states (DOS).

Amônia (NH3) atmosférica: fontes, transformação, sorvedouros e métodos de análise

Ammonia is the most common alkaline gas of the atmosphere, being important in the neutralization of various processes that occur in the atmosphere. Its main sources of emission are the decomposition of organic matter and dejections of animals. Ammonia is used by man in diverse activities of production, therefore it is a gas that can contaminate work environments. Measurements of ammonia concentration in some parts of the world have shown great spatial and weather variation. This large variability makes it difficult to estimate the input of reduced nitrogen to different ecosystems from measurements.

A importância da análise de especiação do chumbo em plasma para a avaliação dos riscos à saúde

Lead absorption is influenced by the species that are formed and the physicochemical characteristics of lead, among others. Lead plasma concentration is < 5% of total blood lead and represents the biologically active fraction able to cross the cell membranes. Health risks mainly depend on a specific metal and its species. Speciation analysis is the analytical activity of identifying and determining different metal species. Chromatographic methods are very useful in the identification of species and the techniques most used to determine metals in biological fluids are ICP OES/MS and AAS. Lead speciation analysis in blood plasma is fundamental for understanding and evaluating the interaction mechanisms between that analyte and its biological targets.

Um experimento de análise em fluxo envolvendo reações enzimáticas e quimiluminescência

An experiment is proposed to introduce some fundamentals of flow analysis, chemiluminescence and kinetic monitoring of enzymatic reactions in undergraduate courses. Chemiluminescence detection is performed with a simple spectrophotometer equipped with a lab-made spiral flow cell constructed from a polyethylene tube. The hydrogen peroxide produced by the glucose oxidation in the presence of glucose oxidase is continuously monitored by the reaction with luminol in alkaline media in a flow injection system. The exercise allows also the discussion of important analytical features and the comparison with different optical methods of analysis.