Avaliação das variáveis analíticas do método de Folin-Ciocalteu para determinação do teor de taninos totais utilizando como modelo o extrato aquoso de folhas de psidium guajava L.

The main analytical variables of a modified Folin-Ciocalteu method were studied by UV-Vis and gradient HPLC-PDA methods, using purified (PC) and technical grade (TGC) casein. Rutin and an aqueous extract of Psidium guajava L. leaves were used as models. The best results were ascribed to TGC. Certainly PC bonds the polyphenols of the P. guajava extract better than TGC, but TGC afforded better precision. A lack of specificity occurred when rutin was analyzed together with the P guajava extract. Additional analyses performed with the flavonoid fraction of P. guajava extract by HPLC-PDA had confirmed that casein was able to bind catechin, gallic acid and P. guajava flavonoids in a non-specific way.

Desviaciones al modelo logarítmico-lineal en la solubilidad de ibuprofén y naproxén en mezclas cosolventes propilenoglicol-agua

The deviations observed in the solubility of ibuprofen (IBP) and naproxen (NAP) in propylene glycol (PG) + water (W) cosolvent mixtures with respect to the logarithmic-linear model proposed by Yalkowsky have been analyzed at 25.00 ± 0.05 ºC. Negative deviations were obtained in all cosolvent compositions for both drugs; they were greater for IBP. Another treatment, based on Gibbs free energy relationships, was also employed showing an apparent hydrophobicity chameleonic effect, because at low PG proportions NAP is more hydrophobic, whereas at high PG proportions IBP is more hydrophobic. The results are discussed in terms of solute-solvent and solvent-solvent interactions.

Cânfora: um bom modelo para ilustrar técnicas de RMN

The use of Nuclear Magnetic Resonance spectroscopy to establish the three-dimensional structures of molecules is an important component of modern Chemistry courses. The combination of techniques that can be used for this purpose is conveniently illustrated by their application to the camphor molecule. This paper presents applications of several techniques used in NMR spectral interpretation in an increasing order of complexity. The result of individual experiments is illustrated in order to familiarize the user with the way connectivity through bonds and through space is established from 1D/2D-NMR spectra and molecular stereochemistry is determined from different NMR experiments.

Caracterización de la reactividad intrínseca de los halobencenos en el modelo conceptual de la teoría de funcionales de la densidad (TFD)

The aim of this paper is to study the family of halobenzenes for characterizing their intrinsic reactivity and in this way to establish a rational order of the intrinsic reactivity of this family of molecules in the electrophilic aromatic substitution. This study was carried out in the framework of Density Functional Theory which provides a global and local index that can be used in the characterization of the reactivity. This index is related to some concept derivatives of experimental chemistry, being a good approach to the characterization of halobenzenes.

Desarrollo de un modelo SIMCA para la clasificación de kerosinas mediante el empleo de la espectroscopía infrarroja

In the petroleum refining industry, the use of crude from several origins is frequent. This leads to a product of variable chemical composition during refining, hindering quality control. Therefore, it is important to develop classification models that help to better characterize those products. The objective of this study is to develop a SIMCA recognition pattern to classify kerosene using infrared spectroscopy data. The model permits to differentiate two kerosene groups with different chemical compositions, which was corroborated by mass spectrometry.

Predição da demanda química de oxigênio em chorume maduro contendo reagente de Fenton, por meio de modelo matemático empírico gerado com planejamento fatorial completo

COD is an important parameter to estimate the concentration of organic contaminants. The closed system technique with the use of K2Cr2O7 is the most important one, however, it has the inconvenience to suffer positive chemical interferences from inorganic compounds such as Fe2+ and H2O2 (not enough reported in the literature). This paper considers a statistical-experimental set capable to validate a empirical mathematical model generated from a 23 experimental design, in the presence of Fe2+ and H2O2. The t test shows that mathematical model has 99,99999% confidence degree and the experimental validation test indicates absolute mean error of 4,70%.

Implementação computacional do modelo carga-fluxo de carga-fluxo de dipolo para cálculo e interpretação das intensidades do espectro infravermelho

The first computational implementation that automates the procedures involved in the calculation of infrared intensities using the charge-charge flux-dipole flux model is presented. The atomic charges and dipoles from the Quantum Theory of Atoms in Molecules (QTAIM) model was programmed for Morphy98, Gaussian98 and Gaussian03 programs outputs, but for the ChelpG parameters only the Gaussian programs are supported. Results of illustrative but new calculations for the water, ammonia and methane molecules at the MP2/6-311++G(3d,3p) theoretical level, using the ChelpG and QTAIM/Morphy charges and dipoles are presented. These results showed excellent agreement with analytical results obtained directly at the MP2/6-311++G(3d,3p) level of theory.

Micropartículas nanorrevestidas contendo um fármaco modelo hidrofóbico: preparação em etapa única e caracterização biofarmacêutica

The aim of this work was to prepare and characterize spray-dried nanocapsule-coated microparticles obtained in one step, using indomethacin as a hydrophobic drug model and poly(e-caprolactone) or Eudragit® RS100, as polymers. Nanocapsule-coated microparticles showed micrometric mean sizes (10 - 15 µm) and a reduced surface area (75 - 85 m²g-1) compared to the raw material (214 m²g-1). Microparticles coated with Eudragit® RS100-nanocapsules showed a better control of the drug release. The release profiles fit to the monoexponetial model and to the Power Law. The mechanism of the indomethacin release from the microparticles is non-Fickian and depends on the particles desagglomeration.

Cromatografia gasosa bidimensional abrangente (GC × GC)

This paper presents the fundamental principles, instrumentation and selected applications of comprehensive two-dimensional gas chromatography (GC × GC). In this technique, introduced in 1991, two capillary columns are coupled and proper modulating interfaces continuously collect the eluate from the first column, transferring it to the second column. The result is a geometric increment in the chromatographic resolution, ensuring separation of extremely complex mixtures in time periods shorter or comparable to those of analysis using conventional gas chromatography and with better detectabilities and sensitivities.

Desenvolvimento de métodos analíticos para determinação de agrotóxicos em sedimentos por cromatografia gasosa monodimensional e bidimensional abrangente com micro detector de captura de elétrons

The development of analytical methods for determination of eight pesticides of different chemical classes (trichlorfon, propanil, fipronil, propiconazole, trifloxystrobin, permethrin, difenoconazole and azoxystrobin) in sediments with gas chromatography-micro-electron capture detector (GC/µECD) and comprehensive two-dimensional gas chromatography with micro-electron capture detector (GCxGC/µECD) is described. These methods were applied to real sediment samples, and the best results were obtained using a 5% diphenyl-methylpolysiloxane column for 1D-GC. For GCxGC the same column was employed in the first dimension and a 50%-phenyl-methylpolysiloxane stationary phase was placed in the second dimension. Due to the superior peak capacity and selectivity of GCxGC, interfering matrix peaks were separated from analytes, showing a better performance of GCxGC.

Comparação da labilidade de metais empregando voltametria, difusão em filmes finos por gradiente de concentração (DGT) e modelo computacional

Speciation of metals in a synthetic freshwater was comparatively evaluated using Anodic Stripping Voltammetry, Diffusive Gradients in Thin Films and a Chemical Equilibrium Model. The labile fractions of Cu and Zn quantified by DGT were similar to the ones measured by ASV. The labile species of Cd and Pb could not be determined by both experimental methods due to the formation of inert complexes with organic ligands in the sample. Despite the differences among the methods, the speciation results obtained by the use of DGT and ASV agreed well with predictions made by the chemical equilibrium model.

Aplicação do modelo Tucker-3 para a análise da biodegradação de diesel

Tucker-3 model offers several advantages for analysis of environmental data but its interpretation is still challenging. A Tucker-3 model was applied to a biodegradation experiment involving a large number of overlapped chromatographic peaks and a temporal variation. The Tucker-3 model allowed the data to be decomposed in two processes: evaporation and biodegradation. The results suggest that linear hydrocarbons were those biodegraded first and demonstrate that the data analysis can be simplified by interpreting the elements of the core array. The approach discussed in this work can be applied in similar problems involving multi-way data in other areas of chemistry.

Simulação Monte Carlo de mecanismo de transferência de energia de excitação eletrônica: modelo de Perrin para a supressão estática da luminescência

A software based in the Monte Carlo method has been developed aiming the teaching of the Perrin´s model for static luminescence quenching. This software allows the student to easily simulate the luminescence decays of emissive molecules in the presence of quenching ones. The software named PERRIN was written for FreeBASIC compiler and it can be applied for systems where the molecules remain static during its excited state lifetime. The good agreement found between the simulations and the expected theoretical results shows that it can be used for the luminescence and excited states decay kinetic teaching.

Aplicação da cromatografia gasosa bidimensional abrangente com microdetector de captura de elétrons para determinação de agrotóxicos em sedimentos

Analysis of seven pesticides in sediments was successfully achieved using comprehensive two-dimensional gas chromatography with micro-electron capture detection, as it provided higher sensitivity and less matrix interference. Repeatability and intermediate precision of peak areas and heights were less than 4% and the recovery percentage for the analytes ranged from 52 to 115%. Instrumental LOD and LOQ were in the range of 0.60 to 2.31 μg L-1 and 1.83 to 5.62 μg L-1, respectively. Concentrations of 3.34 μg kg-1 (dry basis) for trifloxystrobin and azoxystrobin (below the LOQ) were found in a sediment sample.

Uso da cromatografia gasosa bidimensional abrangente (GC×GC) na caracterização de misturas biodiesel/diesel: aplicação ao biodiesel de sebo bovino

The growth of biodiesel market and the implementation of regulations related to biodiesel production and biodiesel/diesel blending has encouraged the development of appropriate analytical methods to control the composition of this type of mixture. In this study, an evaluation of the potential of GC×GC for the characterization of samples of beef tallow biodiesel and the composition of blends of biodiesel/diesel is presented. The methodology was applied to beef tallow biodiesel and its mixtures with petrodiesel, ranging from B2 to B50. Results allowed not only the identification and quantification of the biodiesel esters, but also the biodiesel percentage in biodiesel/diesel blends.