Search

Multiple response simultaneous optimisation was used to develop a micellar electrokinetic chromatography method for caffeine determination in decaffeinated coffees. Buffer composition and voltage were optimised using a central composite design. Six responses were evaluated and each set of response values was regressed on the factor levels of the experimental design using linear and quadratic models. The regression models, correlation coefficients and a principal component analysis (PCA) were used to determine the optimum conditions. Successful results were obtained using a buffer containing 10 mmol L −1 sodium carbonate and 50 mmol L −1 sodium dodecylsulfate, 15 kV voltage, 25 °C temperature, 48 cm × 50 μm fused-silica capillary, hydrodynamic injection of 50 mBar during 7 s and detection at 206 nm. This optimised method was applied for caffeine analysis in 45 samples of commercial decaffeinated coffee.

The exhaust emission of the polycyclic aromatic hydrocarbons (PAHs) considered toxic to human health were investigated on two spark ignition light duty vehicles, one being gasohol (Gasohol, in Brazil, is the generic denomination for mixtures of pure gasoline plus 20–25% of anhydrous ethyl alcohol fuel (AEAF).)-fuelled and the other a flexible-fuel vehicle fuelled with hydrated ethanol. The influence of fuel type and quality, aged lubricant oil type and use of fuel additives on the formation of these compounds was tested using standardized tests identical to US FTP-75 cycle. PAH sampling and chemical analysis followed the basic recommendations of method TO-13 (United States. Environmental Protection Agency, 1999. Compendium Method TO-13A – Determination of polycyclic Aromatic hydrocarbons (PAH) in Ambient Air Using Gas Chromatography/Mass Spectrometry (CG/MS). Center for environmental research information, Cincinnati, p. 78), with the necessary modification for this particular application. Results showed that the total PAH emission factor varied from 41.9 μg km−1 to 612 μg km−1 in the gasohol vehicle, and from 11.7 μg km−1 to 27.4 μg km−1 in the ethanol-fuelled vehicle, a significant difference in favor of the ethanol vehicle. Generally, emission of light molecular weight PAHs was predominant, while high molecular weights PAHs were not detected. In terms of benzo(a)pyrene toxicity equivalence, emission factors varied from 0.00984 μg TEQ km−1 to 4.61 μg TEQ km−1 for the gasohol vehicle and from 0.0117 μg TEQ km−1 to 0.0218 μg TEQ km−1 in the ethanol vehicle. For the gasohol vehicle, results showed that the use of fuel additive causes a significant increase in the emission of naphthalene and phenanthrene at a confidence level of 90% or higher; the use of rubber solvent on gasohol showed a reduction in the emission of naphthalene and phenanthrene at the same confidence level; the use of synthetic oil instead of mineral oil also contributed significantly to a decrease in the emission of naphthalene and fluorene. In relation to the ethanol vehicle, the same factors were tested and showed no statistically significant influence on PAH emission.

A 2(3) factorial design was employed to evaluate the quantitative removal of the indigo carmine (IC) dye from aqueous solutions on glutaraldehyde cross-linked chitosan. The variables were chitosan masses of 100 and 300 mg, IC concentrations of 2.0 and 5.0 x 10(-5) mol L(-1) and temperatures of 25 and 35 degrees C. The quantitative and energetic adsorption parameters were analyzed statistically using modeling with bilinear equations. The results indicated that increasing the chitosan mass from 100 to 300 mg decreases the IC adsorption/mass ratio (mol g(-1)) whereas a temperature increase of 25-35 degrees C increases it. The principal effect of the IC concentration did not show statistical significance. The factorial experiments demonstrate the existence of a significant antagonistic interaction effect between the chitosan mass and temperature. The adsorption thermodynamic parameters, namely Delta(ads)H, Delta(ads)G, and Delta(ads)S, were determined for all the factorial design results. Endothermic values were found in relation to the Delta(ads)H. The positive Delta(ads)S values indicate that entropy is a driving force for adsorption. The Delta(ads)G values are also significantly affected by important antagonistic and synergistic effects involving all principal and interactive factors. It is concluded that the thermodynamical spontaneity of the IC adsorption parameters are greatly influenced by the interactive factors and not by the temperature changes alone.

Para a determinação dos teores de umidade de mel, a legislação brasileira adota o método refratométrico proposto pela AOAC. No entanto, em outro trabalho, os autores observaram que a cristalização interferia na medida do índice de refração quando a amostra de mel se encontrava cristalizada e, portanto, eram obtidos teores de umidade superestimados. A Comissão Européia de Mel (EHC) adota outro método refratométrico, que usa um pré-tratamento da amostra quando esta estiver cristalizada. Assim, o objetivo deste trabalho foi comparar a precisão destes métodos refratométricos por diferentes técnicas estatísticas e estabelecer então o procedimento mais adequado para a análise de umidade em mel. Os resultados da análise dos teste t no nível de 95,0% de confiança para os teores médios de umidade das amostras de méis sugeriram que existiam diferenças significativas entre os dois métodos refratométricos (AOAC e EHC) somente para as amostras cristalizadas. A análise dos desvios padrão pela aplicação do teste F e construção de intervalos de confiança mostrou que o método da EHC foi mais preciso que o da AOAC para amostras de méis cristalizados. Desta forma, pode-se sugerir a adoção pela legislação brasileira do método refratométrico da EHC, como método oficial por este não apresentar erros sistemáticos.For the determination of the moisture contents of honey, the Brazilian legislation adopts the refractometric method proposed by AOAC. However, in other work, the authors observed that the crystallization interferes in the refractive index measurement when the honey sample if encountered crystallized and, therefore, moisture contents overestimated were obtained. The European Honey Commission (EHC), adopt other refractometric method that use a pre-treatment of sample when this one was crystallized. So, the objective of this work was to compare the precision of these refractometric methods by different statistical techniques and it establish thus the more adequate procedure for moisture analysis in honey. The results of t-tests analysis in the 95% confidence level for the average moisture contents of the honey samples suggested that there were significant differences between the two-refractometric methods (AOAC e EHC) only for the crystallized samples. The analysis of standard deviations by application of F-test and building of confidence intervals shown that the EHC method was more precise than the AOAC methodology for the crystallized honey samples. In this way, it may be suggested the adoption by Brazilian legislation of refractometric method of EHC, as official method, by this one not present systematic errors.

A procedure has been developed for the simultaneous determination of traces amounts of Cd, Cr, Cu, Mn, Ni and Pb from saline oil-refinery effluents and digested vegetable samples using inductively coupled plasma optical emission spectrometry (ICP OES). The procedure is based on cloud point extraction (CPE) of these metals as 2-(bromo-2-pyridylazo)-5-diethyl-amino-phenol (Br-PADAP) complexes into a micellar phase of octylphenoxypolyethoxyethanol (Triton X-114). Optimization of the procedure was performed by response surface methodology (RSM) using a Doehlert design. Principal components (PC) were used to simplify the multiple response analysis. A response surface for the first PC score is useful in determining the optimum conditions for the Cd, Cr, Cu, Mn and Pb determinations whereas the second PC is highly correlated with the Ni response. Improvement factors of 22, 36, 46, 25, 65 and 39, along with limits of detection (3 σ B ) of 0.081, 0.79, 0.38, 0.83, 0.28 and 0.69 μg L −1 , and precision expressed as relative standard deviation (%R.S.D., n = 8, 20.0 μg L −1 ) of 1.5, 2.2, 3.5, 2.6, 2.5 and 2.5 were achieved for Cd, Cr, Cu, Mn, Ni and Pb, respectively. The accuracy was evaluated by spike tests in oil-refinery effluent samples and analysis of a vegetable certified reference material (NIST 1571, orchard leaves). Results found were in agreement with certified values.

An approximate procedure based on normal probability graphs for selecting significant parameters of models calculated from the results of split-plot designs is proposed. Its application can result in a substantial reduction in the number of experiments that need to be performed. The method is applied to three split-plot design results for real data reported in the literature: (1) three plasticizer mixture components with different extrusion rates and drying temperatures, (2) three fish pattie ingredients at different cooking and frying temperature and times and (3) Cr(VI) catalytic determinations employing three reagents of varying concentrations and three solvent components of varying proportions. Approximate models determined from the proposed procedure are compared with those determined using complete split-plot ANOVA analyses. The robustness of the procedure is tested for one of the split-plot design results using replication, main-plot error and sub-plot error variance estimates that change according to a 2 3 factorial design.

O objetivo deste trabalho foi investigar os parâmetros tecnológicos relevantes no processo de estruturação de polpa concentrada de mamão (16ºBrix), utilizando um delineamento experimental associado a Metodologia de Superfície de Respostas. Os resultados do planejamento composto central utilizado mostraram que as variáveis pectina (x1) e alginato (x2) foram estatisticamente significativas para aumentar a firmeza de fruta estrutura de mamão. Foram realizados experimentos para confirmar as previsões do modelo matemático proposto para firmeza. As frutas estruturadas obtidas com os menores níveis de pectina (7g/kg) e alginato (7g/kg) apresentaram firmeza elevada, em torno de 3,2kg, cerca de 2,4 vezes maior que o valor previsto pelo modelo, provavelmente devido a variações no pH da polpa de mamão. Os resultados mostraram ser possível produzir fruta estruturada com teor elevado de polpa de mamão concentrada (672g/kg) e quantidade mínima de sacarose (364g/kg). O glicerol (x3) na concentração de 100g/kg suprimiu a atividade de água dos géis de polpa concentrada de mamão para 0,922. A secagem (60ºC/6h) sob vácuo (0,8kgf/kg) das frutas estruturadas minimizou o problema de adesividade superficial das frutas estruturadas e, concomitantemente, promoveu redução na atividade de água, para níveis de umidade intermediária, em torno de 0,860.The objective of this study was to investigate the relevant technological parameters of the manufacturing process of restructured fruit made from concentrated papaya pulp (16ºBrix) using an experimental delineation method associated with the Surface Response Methodology. The results of the Central Composed Design utilized show that the effect of the variables pectin (x1) and alginate (x2) on the increase in firmness of the papaya fruit restructured is statistically significant. A series of experiments was conducted to confirm the values predicted by the mathematical model proposed for firmness. The restructured fruits produced with the lowest addition levels of pectin (7g/kg) and alginate (7g/kg) exhibited high firmness values of about 3.2kg. These values were approximately 2.4 times greater than the values for firmness predicted by the model, probably due to variations in the pH of the papaya pulps used in the experiments. The results showed that it is possible to manufacture restructured fruit using high levels of concentrated papaya pulp (672g/kg) and minimum amounts of sucrose (364g/kg). Glycerol (x3) used at the concentration of 100g/kg reduced the level of water activity of the concentrated papaya pulp gels to 0.922. Vacuum drying (60ºC/6h; 0.8kgf/kg) of the restructured fruits minimized the problem of surface adhesion and, at the same time, lowered water activity to intermediate levels of about 0.860.

A 32 factorial design investigation to optimize N-carboxybutylchitosan was carried out varying the levulinic acid/chitosan molar ratio between 1.00 and 3.00 and the sodium borohydride/chitosan molar ratio from 0.50 to 1.00. 1H NMR spectra signals at 1.0 and 2.5 ppm were used to monitor the reaction system. A quadratic model having significant terms for both molar ratios was found for N-carboxybutylchitosan substitution degree whereas a linear model best describes the substitution degree of 5-methylpyrrolidinone chitosan. Maximum N-carboxybutylchitosan and minimum 5-methylpyrrolidinone chitosan substitution degrees occur for levulinic acid/chitosan molar ratios between 2.00 and 3.00 and a 0.50 for sodium borohydride/chitosan molar ratio.

A factorial design to evaluate ash content in honey by thermogravimetry as well as to establish the optimum analysis conditions that produce ash values in agreement with those obtained by the official method (gravimetry) was executed. Heating rate and use of fiber glass paper effects were significant as was the interaction effect between them. Lower heating rates and the use of fiber glass fiber paper are recommended to provide the complete incineration of honey samples by thermogravimetry. To confirm these results and to establish the optimized conditions a completely randomized two block design was executed investigating three procedures: thermogravimetry with fiber glass paper at heating rates of 5 and 10 oC min-1 and standard gravimetry. Only the thermogravimetric method carried out at 5 °C min-1 presented ash content averages in agreement with those obtained by the official method. In this way, TG/DTG can be indicated as an alternative method to gravimetry for this determination in honey samples.

The infrared vibrational intensities of HFCO and DFCO have been calculated at the B3LYP/cc-pVTZ, MP2(FC)/6-311++G(3d,3p) and QCISD(FU)/aug-cc-pVTZ levels. All calculations predict the isotopomers to have identical intensity sums, within about 1 km mol(-1). This is in contrast with experimental intensity sum results reported in the literature. Dipole moment derivative directions calculated by the three methods are in excellent agreement for all in-plane normal coordinates. All the theoretical polar tensor elements are also in good agreement with each other having standard deviations varying between 0.003 and 0.043 e. The oxygen and fluorine atoms have negative mean derivatives (approximately -0.6 e), whereas the carbon mean derivative is very positive (approximately +1.1e) and the hydrogen one is almost zero (approximately +0.03 e). The HFCO theoretical intensity sums calculated by all three methods as well as their carbon and oxygen mean dipole moment derivatives are in good agreement with those estimated from the experimental intensities and atomic mean derivatives of H2CO and F2CO.

Atomic anisotropies determined from gas-phase infrared fundamental intensity data for 30 molecules are compared with anisotropies calculated from wave functions obtained with 6-31+G(d,p) and 6-311++G(3d,3p) basis sets at the Hartree−Fock, B3LYP density functional and MP2 electron correlation levels. The discrepancies between the experimental and theoretical anisotropy values are up to 30 times larger than those found for the mean dipole moment derivatives. Although a change in the basis set from 6-31+G(d,p) to 6-311++G(3d,3p) has small effects on the anisotropy values, they are quite sensitive to the inclusion of post-Hartree−Fock electron correlation treatment. Although the calculated results for anisotropies with values

Dois procedimentos para a reducao de experimentos para o metodo split-plot foram investigados usando um conjunto de dados contendo 160 experimentos, consistindo de 80 duplicatas provenientes da otimizacao de um sistema contendo a mistura de agua-acetona-N,N-dimetilformamida e os reagentes HCl, o-dianisidina e H2O2 para a determinacao de Cr(VI). A estabilidade dos coeficientes do modelo e as medias quadraticas da ANOVA sao usadas como criterio para julgar a eficiencia dos procedimentos. Somente o procedimento que evita a possibilidade de se eliminar completamente uma replicata para um dado conjunto de condicoes das variaveis de processo parece ser praticavel, uma vez que nao resulta em perda de informacao fundamental da modelagem. Seus valores das medias quadraticas da ANOVA permaneceram estaveis para reducoes de ate 30% das replicatas enquanto seus coeficientes dos modelos foram relativamente constantes para ate 70% de reducao das replicatas. Tendo em vista que um planejamento split-plot completo envolvendo variaveis de processo e de mistura requer um grande numero de experimentos, a economia introduzida por planejamentos split-plot incompletos faz seu uso ser muito atraente.

A split-plot design has been used to simultaneously optimize reagent conditions and solvent medium for Pb2+ determination by anodic stripping voltammetry (ASV). Three mixture components, N,N-dimethylformamide (DMF), ethanol and water, and two process variable levels, ammonium acetate (supporting electrolyte) and hydrochloric acid concentrations, were varied. The calculations of main-plot, subplot and main-subplot interaction ANOVA sums of squares for regression and lack of fit are illustrated. These values are shown to be useful for model development. Six different models were evaluated. The bilinear-special cubic model has only a very slight lack of fit and is preferred. Standard error estimates were calculated using a method described in the literature by Cornell, and approximate critical values for t-tests on the model coefficients were investigated. Normal probability graphs seem appropriate for this analysis. The significant terms in this model are capable of describing how the mixture response surfaces change as process level conditions are varied. Optimized mixture proportions for each factorial design level are determined. Optimum conditions in the (− −) main-plot quadrant for the determination of lead by ASV in the homogeneous ternary solvent system were achieved with a solvent composition of 8.0 g of N,N-dimethylformamide (DMF), 7.0 g of ethanol and 5.0 g of water, corresponding to 40% m/m of DMF, 35% n/m of ethanol and 25% m/m of water. Water is essential since the sample and the buffer (0.1 mol kg−1 ammonium acetate containing 0.00880 mol kg−1 HCl) are added to the system as aqueous solutions. The other three main-plot quadrants presented optimum analytical signals for 95% aqueous solutions. The split-plot design seems to be especially appropriate for simultaneously optimizing process and mixture variables of this chemical system facilitating operational procedures by means of block randomization.

This work presents a way to predict the biochemical oxygen demand (BOD) of the output stream of the biological wastewater treatment plant at RIPASA S/A Celulose e Papel, one of the major pulp and paper plants in Brazil. The best prediction performance is achieved when the data are preprocessed using principal components analysis (PCA) before they are fed to a backpropagated neural network. The influence of input variables is analyzed and satisfactory prediction results are obtained for an optimized situation.

The electrochemical properties of methylene blue immobilized on cellulose surfaces modified with titanium dioxide and titanium phosphate were investigated by cyclic voltammetry. The materials synthesized were incorporated into carbon paste electrodes. The electron mediator property of the methylene blue was optimized using a factorial design, consisting of two levels and three factors. The factorial analysis was carried out by searching for better reversibility of the redox process, i.e. the lowest separation between positive and negative peak potentials and a current ratio near unity. The pH does not appear to influence the reversibility of electron transfer but electrolyte concentration and type of modified cellulose surface are important for this chemically modified electrode system. The experimental observations and data analyses indicate that a 0.5 mol l−1 NaCl solution and the cellulose surface modified with titanium phosphate at either a pH of 4.0 or 7.0 are optimal conditions for this system.

Simple potential models relating experimental 1s electron ionization energies for B, N (sp and sp3 hybrids), O, and F atoms; 1s and 2p ionization energies for P atoms; and 2s and 2p ionization energies for Cl atoms as a function of their atomic mean dipole moment derivatives determined from experimental gas phase infrared fundamental band intensities are reported. Potential models using theoretical Koopmans' energies and generalized atomic polar tensor (GAPT) charges are found to form even more precise models than those using experimental data. This is expected because the potential models depend only on the electronic structures of molecules before ionization takes place and do not take into account relaxation effects. If the experimental ionization energies are adjusted by their relaxation energies, models similar to those obtained using Koopmans' energies are determined. The models permit a simple understanding of substituent effects on core ionization energies in terms of atomic charges in molecules. ...

Initially an eleven variable, sixteen assay 215−11 fractional factorial design, was used to determine the key factors in the production of violacein produced by Chromobacterium violaceum, CCT 3496. Subsequently five and three factor central composite designs were executed to determine response surfaces with the aim of optimizing cellular mass and crude violacein production. The 7.5 g l−1 dry cell mass and 0.17 g l−1 crude violacein productions obtained with our initial culture medium were increased to 21 g l−1 and 0.43 g l−1, respectively, for a medium investigated in the three factor design.

Eucalyptus grandis wood was biodegraded by eight basidiomycetes and two ascomycetes. Four groups of decayed wood samples were recognized based on the principal component analysis (PCA) of weight and component loss data. Among the 10 fungal species studied, no selective lignin biodegradation was achieved. PCA was very efficient in recognizing wood decay patterns and seems to be a useful tool to analyse large group of weight- and component-loss data.

Carbon 1s electron binding energies determined by X-ray photoelectron spectroscopy and mean dipole moment derivatives obtained from experimental infrared intensities are shown to be related through the simple potential model proposed by Siegbahn and collaborators. The sp3 carbon atoms in 13 halomethanes, 2 ethanes, 3 methylacetylenes, cyclopropane, and ethylene oxide have 1s energies, which, after correction for electrostatic potentials from neighboring atoms, are linearly related to the carbon mean dipole moment derivatives, presenting a slope of 15.50 ± 0.29 eV/e. The sp2 carbons of ethylene, three haloethylenes, and three carbonyl compounds also exhibit a linear relationship having a significantly different slope of 17.37 ± 0.87 eV/e. The sp carbon atoms in acetylenes, cyanides, CO, CS2, CO2, and OCS show a third linear relationship, with a slope of 18.90 ± 0.75 eV/e. These slopes are proportional to the inverse atomic radii of sp3, sp2, and sp carbon atoms and according to the simple potential equatio...

The present paper describes fundamentals, advantages and limitations of the Box-Behnken design (BBD) for the optimization of analytical methods. It establishes also a comparison between this design and composite central, three-level full factorial and Doehlert designs. A detailed study on factors and responses involved during the optimization of analytical systems is also presented. Functions developed for calculation of multiple responses are discussed, including the desirability function, which was proposed by Derringer and Suich in 1980. Concept and evaluation of robustness of analytical methods are also discussed. Finally, descriptions of applications of this technique for optimization of analytical methods are presented.

This paper describes fundamentals and applications of multivariate statistical techniques for the optimization of chromatographic systems. The surface response methodologies: central composite design, Doehlert matrix and Box-Behnken design are discussed and applications of these techniques for optimization of sample preparation steps (extractions) and determination of experimental conditions for chromatographic separations are presented. The use of mixture design for optimization of mobile phases is also related. An optimization example involving a real separation process is exhaustively described. A discussion about model validation is presented. Some applications of other multivariate techniques for optimization of chromatographic methods are also summarized.

The molecular dipole moment and its derivatives are determined from atomic charges, atomic dipoles, and their fluxes obtained from AIM formalism and calculated at the MP2(FC)/6-311++G(3d,3p) level for 16 molecules: 6 diatomic hydrides, CO, HCN, OCS, CO2, CS2, C2H2, C2N2, H2O, H2CO, and CH4. Root-mean-square (rms) errors of 0.052 D and 0.019 e are found for the dipole moments and their derivatives calculated using AIM parameters when compared with those obtained directly from the MP2(FC)/6-311++G(3d,3p) calculations and 0.097 D and 0.049 e when compared to the experimental values. The major deviations occur for the NaH, HF, and H2O molecules. Parallel polar tensor elements for the diatomic and linear polyatomic molecules, except H2, HF, LiH, and NaH, have values resulting from cancellations of substantial contributions from atomic charge fluxes and atomic dipole fluxes. These fluxes have a large negative correlation coefficient, -0.97. IR fundamental intensity sums for CO, HCN, OCS, CO2, CS2, C2H2, C2N2, H2CO, and CH4 calculated using AIM charges, charge fluxes, and atomic dipole fluxes have rms errors of 14.9 km mol(-1) when compared with sums calculated directly from the molecular wave function and 36.2 km mol(-1) relative to experimental values. The classical model proposed here to calculate dipole-moment derivatives is compared with the charge-charge flux-overlap model long used by spectroscopists for interpreting IR vibrational intensities. The utility of the AIM atomic charges and dipoles was illustrated by calculating the forces exerted on molecules by a charged particle. AIM quantities were able to reproduce forces due to a +0.1 e particle over a 3-8-A separation range for the CO and HF molecules in collinear and perpendicular arrangements. These results show that IR intensities do contain information relevant to the study of intermolecular interactions.

A 2(3) factorial design was employed to evaluate the quantitative removal of Cu(II) and Co(II) on glutaraldehyde-cross-linked chitosan from kinetic isotherms, using chitosan masses of 100 and 300mg and temperatures of 25 and 35 degrees C. The adsorption parameters were analyzed statistically using modeling polynomial equations and a cumulative normal probability plot. The results indicated the higher quantitative preference of the chitosan for Cu(II) in relation to Co(II). Increasing the chitosan mass decreases the adsorption/mass ratio (mol g(-1)) for both metals. The principal effect of the temperature did not show statistical importance. The adsorption thermodynamic parameters, namely Delta(ads)H, Delta(ads)G and Delta(ads)S, were determined. Exothermic and endothermic results were found in relation to a specific factorial design experiment. A comparison of Delta(ads)H values was made in relation to some metal-adsorbent interactions in literature. It is suggested that the adsorption thermodynamic parameters are determined by the influence of the principal and interactive experimental parameters and not by the temperature changes alone.

The results suggest that the two variables studied are significant and that they may be independently optimized. The material of the sample holder interferes with the incineration process only due to the amount of heat transfered. The sample holder volume aids diffusion of the atmosphere to the honey sample, minimizing the foaming effect. According to the results, for the thermogravimetric analysis of ash content in honey, sample holders of platinum or alumina of 150 µL are indicated.

Air samples were collected simultaneously at three urban sites in Sao Paulo City, Brazil, in winter, spring, summer and fall (in 2000 and 2001). Andersen PUF samplers were used for gas and particles sequential sampling. Samples were analyzed using HRGC/HRMS according to US EPA Method 8290. The greater metropolitan area of Sao Paulo is the largest industrialized region of Latin America and has a highly polluted atmosphere. Concentrations of dioxins and furans, which are well-known toxic chemicals, ranged from 1.14 pg m 3 to 13.8 pg m 3 (0.047 pg I-TEQ m 3 to 0.751 pg I-TEQ m 3 ). Principal component analysis showed that all the variables are highly correlated with one another except the 2,3,7,8-TCDD one. This is consistent with the similar concentration profiles observed for the tetra, penta, hexa, hepta and octa-homologous groups of the three sampling sites studied. At all sites, the most abundant compounds were the hepta and octa congeners. The 2,3,4,7,8-PeCDF accounted for 37-46% of the total toxicity and the 2,3,7,8- TCDD accounted for 7-16%. Highest mass concentrations of PCDD/Fs were found in the site where there is influence of industrial activities and heavy vehicular traffic fueled by gasohol, diesel, and ethanol. � 2004 Published by Elsevier Ltd.

Biogenic hydrocarbon emission rates from individual plant species have been estimated experimentally placing small plants or branches in enclosures and measuring the emission rates of the compounds. All-Teflon chambers (cuvettes) where air samples are drawn through tubes packed with adsorbents, have been commonly used for plant enclosure. Sampling of carbonyl compounds emitted from plants has been done using 2,4-dinitrophenylhydrazine coated particles and the derivative carbonyl compounds have been analyzed by HPLC-UV. In this work, the enclosure technique using a cuvette for measurements of carbonyl compound emissions from plants was evaluated. Blank measurements in an empty cuvette have revealed quite different results for experiments performed under laboratory and field conditions. Rigorous univariate statistical analysis of the data obtained indicate that the analytical procedure to determine carbonyl compounds at trace levels in emission samples using the cuvette may lead to positive artifacts during field sampling. This analysis applied to laboratory measurements showed no difference in the results for the cuvette and external lines. Multivariate statistical calculations point out that solar light intensity accounts for the high carbonyl compound levels, especially for acetaldehyde, in the empty cuvette.

The aim of this study was to develop an empirical model that provides accurate predictions of the biochemical oxygen demand of the output stream from the aerated lagoon at International Paper of Brazil, one of the major pulp and paper plants in Brazil. Predictive models were calculated from functional link neural networks (FLNNs), multiple linear regression, principal components regression, and partial least-squares regression (PLSR). Improvement in FLNN modeling capability was observed when the data were preprocessed using the PLSR technique. PLSR also proved to be a powerful linear regression technique for this problem, which presents operational data limitations.

The dipole moments of HCN and N2O are computed for different geometric configurations of these molecules, using the best available wavefunctions from the “near‐Hartree–Fock” calculations of McLean and Yoshimine. From these calculated dipole‐moment functions the derivatives with respect to the two stretching coordinates of each molecule are computed and compared with the experimental values obtained from infrared intensity measurements. The absolute magnitudes of the calculated derivatives for both HCN and N2O agree reasonably well with the experimental values. The relative signs of the calculated derivatives, ∂μ / ∂rNN and ∂μ / ∂rNO, appear to be in agreement with experiment for NNO, whereas the relative signs calculated for ∂μ / ∂rNH and ∂μ / ∂rCN are not consistent with the experimental results for HCN. Possible reasons are suggested for this discrepancy, which appears to be more serious than the recent controversy regarding the sign of the CO dipole moment.

G sum rule graphical solutions for the atomic effective charges, ξα, of the hydrocarbons, acetylene, ethylene, ethane, propane, and cyclopropane, are reported and compared with the numerical solutions. The importance of experimental error uncertainties in the effective charge values is emphasized. Polar tensor and effective charge values have been calculated for all the possible sign combinations of the ∂p/∂Qi’s of ethylene and ethane. ξα values calculated from the G sum rule and the polar tensors show excellent agreement indicating that normal coordinate and band separation approximations introduce little error into the effective charge values. Although ξH is relatively constant for all the hydrocarbons, save acetylene, ξC shows large variations with changes in molecular environment. The empirical relation nCξC = nHξH holds surprisingly well for most hydrocarbons, although the effective charges for methane provide a striking exception to this rule.

O modelo Carga - Fluxo de Carga - Fluxo de Dipolo (CCFDF), em termos dos multipolos da Teoria Quântica de Átomos em Moléculas (QTAIM), foi empregado para investigar as variações das intensidades de infravermelho durante a dimerização de ácidos carboxílicos, na coordenação de carbonilas e grupos cianeto a centros metálicos diversos e durante a excitação eletrônica de moléculas diatômicas simples (AlH, AlF, AlCl, AlBr, BF, BCl, BBr e CS). A intensificação das bandas de estiramento OH durante o processo de dimerização e as variações de intensidade das bandas de estiramento dos ligantes complexados a centros metálicos podem ser justificadas, principalmente, pelo termo cruzado entre carga e fluxo de carga. Por sua vez, a interpretação da variação da intensidade de infravermelho durante a excitação eletrônica requer a consideração de três contribuições, carga e seus termos cruzados com fluxo de carga e fluxo de dipolo. Além disto, a dimerização de ácidos carboxílicos é acompanhada por uma diminuição da densidade eletrônica nos BCPs das ligações O-H, resultando no enfraquecimento e redução do caráter covalente destas ligações. No que se refere à coordenação do ligante carbonil a metais de transição, observa-se também, na maioria dos casos, o enfraquecimento da ligação CO. Certos dados topológicos analisados, advindos da QTAIM, estão em grande concordância com as expectativas em termos da capacidade de retrodoação dos centros metálicos investigados. Por sua vez, as excitações verticais geralmente ocasionam reduções na densidade eletrônica dos pontos críticos de ligação nas moléculas diatômicas estudadas quando comparadas com os respectivos estados fundamentais. A transição eletrônica σ → π* provoca ainda uma inversão no sentido do vetor de momento de dipolo para o estado tripleto das moléculas BF, BCl, BBr e CS. Estas mudanças de sentido deste vetor são causadas pela diminuição expressiva das contribuições de polarização atômica do boro e do carbono durante a excitação. Por fim, baseando-se apenas nas propriedades dos substratos iniciais, as curvaturas da densidade eletrônica nos pontos críticos dos anéis aromáticos (RCP) e dos núcleos de carbono, as densidades de energia cinética e potencial no RCP, juntamente com a energia intra-atômica dos carbonos, são apresentadas como descritores promissores para predizer a reatividade e a regiosseletividade em reações de substituição eletrofílica aromática. The Charge - Charge flux - Dipole flux (CCFDF) model, in terms of multipoles from the Quantum Atom Theory of Molecules (QTAIM), was employed to investigate the variations in infrared intensities during the dimerization of carboxylic acids, in the coordination of carbonyls and cyanide groups to different metallic centers and during the electronic excitation of simple diatomic molecules (AlH, AlF, AlCl, AlBr, BF, BCl, BBr, and CS). The intensification of OH stretching bands during the dimerization process and the variations in the intensity of the stretching bands of ligands complexed to metal centers can be justified, mainly, by the cross term between charge and charge flux. On the other hand, the interpretation of infrared intensity variations during electronic excitation requires the consideration of three contributions, charge and its cross - terms with charge flux and dipole flux. In addition, the dimerization of carboxylic acids is accompanied by a decrease in the electron density at the BCPs of O-H bonds, resulting in the weakening and covalent character decrements of these bonds. Regarding the coordination of carbonyl to transition metals, the CO bond weakening is also observed in most cases. Certain topological data analyzed, obtained from QTAIM, are in great agreement with the expectations regarding the backbonding capacity of the investigated metal centers. On the other hand, vertical excitations usually provoke electron density decrements at the critical points of the studied diatomic molecules when compared with the respective fundamental states. The σ → π* electronic transition also causes dipole moment inversions for the triplet state of BF, BCl, BBr, and CS molecules. The direction changes of this vector can be justified by the significant decrease observed in the atomic polarization contributions of boron and carbon during excitation. Finally, based only on the properties of initial substrates, the electron density curvatures at the critical points of aromatic rings (RCP) and of carbon nuclei, the densities of kinetic and potential energy at the RCP, along with the intra-atomic energy of carbons, are presented as promising descriptors to predict the reactivity and regioselectivity in aromatic electrophilic substitution reactions.

A estrutura da DPC (Difenilciclopropenona) e espectro Raman simulado foram obtidos usando os métodos HF (Hartree - Fock) e DFT (Density Functional Theory). Os espectros Raman e IR foram obtidos, e suas medidas experimentais em acetonitrila mostram vibrações em ca. 1630 e 1850 cm-1 na região do est. (C=O). Estes modos apresentam uma mistura entre o est. (C=O) e movimentos do anel de três membros. O modo em ca. 1630 cm-1 apresenta uma intensidade atípica no IR. Em fase gasosa molécula DPC possui um mínimo global com os anéis fenila dispostos simetricamente fora do plano, o sistema possui uma simetria C2. A comparação entre a molécula DPC e seus precursores, CP (CicloPropenona) e DMC (DiMetilCiclopropenona), destaca a semelhança estrutural e vibracional entre o sistema DPC e DMC. O estudo do efeito de solvente é executado, utilizando-se o sistema DMC para mimetizar os resultados observados para o DPC nos solventes, CCl4, n-hexano, clorofórmio, metanol e a mistura CCl4 com metanol. Os resultados teóricos (HF e DFT) apresentam uma boa correlação com os resultados experimentais. The structure of DPC (DiphenylCycloPropenone), and its simulated Raman spectrum, are obtained using the HF (Hartree-Fock) and DFT (Density Functional Theory). The Raman and IR spectra are obtained, the experimental measurent in acetonitrile shows vibrations at ca. 1630 and 1850 cm-1 in the carbonylic stretching region. These modes show a mixture between the stretching C=O and the three member ring motions. The mode at ca. 1630 cm-1 shows an anomalous intensity in the IR spectrum. The DPC molecule has a global minimum in the gas phase, with the phenyl rings symmetrically out of plane, the system having a C2 symmetry. The comparison betwen DPC and its analogs, CP (Cyclopropenone) and DMC (DiMethylCyclopropenone), highlights the vibrational and structural similarity between DPC and DMC. The study of the solvent effect is carried out using the DMC system to simulate the results observed for DPC in the solvents, CCl4, n-hexane, CCl3H, CH3OH and the CH3OH and CCl4 mixture. The calculations (HF e DFT) show good correlation with the experimental results.

Neste trabalho foram estudadas as moléculas conhecidas corno cetonas-gaiola de Cookson e seus derivados pelo uso de técnicas computacionais de modelagem molecular. Estas moléculas participam de cicloadições [2+2], urna classe de reações cujo mecanismo ainda é estudado. As técnicas usadas foram as do Conjunto Completo de Funções de Base (CBS-4), Hartree-Fock, métodos de Teoria do Funcional de Densidade pBP e B3LYP e semi-empírico PM3. As técnicas foram usadas com diferentes conjuntos de base para analisar as conformações das moléculas e avaliar a exatidão do método em reproduzir resultados experimentais de termodinâmica e ressonância magnética nuclear. Com base na concordância dos resultados e com as caraterísticas do método, procura-se inferir quais as características estruturais e interações atômicas que explicam os resultados experimentais e os calculados. Foi estudada também a solvatação das espécies. Os programas empregados foram o Gaussian 94, Spartan 5.0, MOPAC e Amsol 6.6. Os resultados mostraram as interações interatômicas mais relevantes para a determinação das estabilidades relativas das moléculas. Foi considerado o efeito da estrutura no resultado de cálculos de energias e avaliado o método de reações isodésmicas para moléculas de estrutura complexa. In this work the molecules known as Cookson\'s cage ketones and similar adducts were studied with the use of computational molecular modelling techniques. These molecules participate in cycloadditions [2+2], a class of reactions whose mechanism is still being studied. Toe techniques used were the Complete Basis Set (CBS-4), Hartree-Fock, Density Functional Theory methods pBP and B3LYP and semi-emprical PM3. The techniques were used with some basis sets to analise the molecular conformations and evaluate the agreement of the calculated with the experimental results of thermodynamics and NMR spectroscopy. Based on the agreement between the results and on the characteristics of the methods, it is sought to determine the structural characteristics and atomic interactions that explain the results. The solvation of the species was also studied. The programs used were the Gaussian 94, Spartan 5.0, MOPAC and Amsol 6.6. The results show the more important interactions that determine the relative stabilities of the molecules. The effect of the molecular structure on the energy calculation was studied and the method of isodesmic reactions was evaluated for complex molecules.

A presente tese trata da análise conformacional e estudo das interações eletrônicas de algumas 2-(fenilselanil)-2-(metoxi)-4\'-substituídas-acetofenonas (série I) e das 2-(4-substituídasfenilsulfanil)-2-(metoxi)-4\'-substituídas-acetofenonas (série II) contendo grupos doadores, hidrogênio e atraentes de elétrons na posição para dos anéis fenacílico [4\'-Y-PhC(O)] e fenilsulfanílico (S-Ph-4-X). Através da resolução das bandas de νCO, foi constatada a ocorrência de isomerismo conformacional nos solventes de constante dielétrica crescente (n-C6H14, CCl4, CHCl3, CH2Cl2, CH3CN) em ambas as séries. Cinco compostos da série II apresentaram ressonância de Fermi (RF) no infravermelho e precisaram ser deuterados. Os dados espectroscópicos são concordantes tanto com os resultados dos cálculos de otimização e frequência em fase gasosa quanto com a simulação do efeito do solvente (PCM), no nível de teoria B3LYP/6-31+G(d,p). Em ambas as séries, foram encontradas três conformações estáveis c1, c2 e c3, sendo que c2 é significativamente mais estável que c1 e c3. O confôrmero c1 possui o oxigênio metoxílico e o carbonílico em sinperiplanar enquanto os grupos -SePh/- SPh estão em anticlinal. Os confôrmeros c2 e c3 possuem o hidrogênio metínico em sinperiplanar com a carbonila enquanto os grupos -OMe e -SePh/-SPh estão na anticlinal. O confôrmero c1 pode ser atribuído ao componente de banda (IR) de maior frequência νCO. Da mesma forma, c2 e c3 são o componente de frequência intermediária e de menor frequência, respectivamente, na série I enquanto que na série II eles coalescem em apenas um componente de menor frequência. Os cálculos de PCM mimetizam os dados espectroscópicos, i.e. é possível constatar a inversão populacional entre c1 e c2, conforme a polaridade do solvente aumenta. Através do cálculo de frequências anarmônicas e construção da PED, foram encontrados dois modos vibracionais que combinados interagem com νCO originando a RF (série II). Um modo é de alta frequência e envolve uma porcentagem considerável de &#948C-H(metínico), o outro modo é esqueletal. A análise das interações orbitalares (NBO) mostrou que os confôrmeros c1 e c2 são estabilizados pela transferência de cargas entre LpO5→σ*CS/Se (ca. 18 kcal mol-1) enquanto c3 é estabilizado pela interação menos intensa LpO5→σ*C-C (ca. 9,5 kcal mol-1). As interações eletrônicas foram investigadas a partir dos contatos interatômicoscurtos com apoio das cargas atômicas parciais. Apesar de c1 e c2 apresentarem praticamente a mesma estabilidade em termos de interações orbitalares, o primeiro é fortemente desestabilizado pela repulsão eletrostática entre os átomos O&#948-CO...O&#948-OMe negativamente carregados separados por uma distância menor que a soma dos raios de van der Waals. Este contato curto entre os dipolos C&#948+=O&#948- e C&#948+−O&#948- é responsável pela maior frequência de νCO de c1 frente c2 e c3. A maior estabilidade de c1 nos solventes mais polares, porém, deve-se à melhor solvatação local destes dipolos. As análises dos monocristais (raios-X) indicou que os compostos assumem, no estado sólido, a conformação menos estável c1, obtida em fase gasosa. Não foram encontradas diferenças significativas no que se refere aos substituintes Y e X. Conclui-se que a estabilidade global das conformações é determinada pelo balanço energético entre as interações orbitalares e eletrostáticas, nas duas séries estudadas. This thesis reports the conformational analysis and the electronic interactions study of some 2-(phenylselanyl)-2-(methoxy)-4\'-substituted-acetophenones (series I) and 2-(4-substitutedphenylsulphanyl)-2-(methoxy)-4\'-substituted-acetophenones (series II) bearing electron donating, hydrogen and electron attracting substituents in the para position of the phenacyl [4\'-Y-PhC(O)] and phenylsulphanyl (S-Ph-4-X). The occurrence of conformational isomerism in crescent dielectric constant solvents (n-C6H14, CCl4, CHCl3, CH2Cl2, CH3CN) in the two series was studied through the νCO infrared band decomposition. From the series II compounds, five presented Fermi resonance (FR) and had to be deuterated. The spectroscopic data are in line with theoretical calculations results for optimization and frequency in gas phase as well as for solvent effect simulation (PCM), both in B3LYP/6-31+G(d,p) level. Three stable conformers (c1, c2 and c3) were found for both series being the c2 significantly more stable than c1 and c3. Particularly in the c1 conformer, the methoxyl and the carbonyl oxygens are in sinperiplanar orientation while the -SePh/-SPh groups are in anticlinal. In the c2 and c3 conformers the methyne hydrogen assume a sinperiplanar geometry with respect to the carbonyl whereas both -OMe and -SePh/-SPh are in anticlinal. The c1 conformer can be ascribed to the highest frequency νCO band component (IR). So, c2 and c3 ones can be ascribed to the medium and the lowest frequency νCO component, respectively, in the series I whereas in the series II they come together (coalescence) in one single band component. The PCM calculations are in good agreement with spectroscopic data i.e. it is possible to observe a populational inversion between c1 and c2 conformers as the solvent polarity increases. The anharmonic frequencies and PED theoretical treatment revealed that the combination of two vibrational modes interact with the νCO giving rise to the FR (series II): the high frequency one involves a considerable δC-H(methyne) percentage; whilst the other is skeletal. The orbital interactions analysis (NBO) showed that the c1 and c2 conformers are mainly stabilized by charge transfer LpO5→σ*CS/Se (ca. 18 kcal mol-1) while c3 is stabilized by the less intense interaction LpO5→σ*C-C (ca. 9,5 kcal mol-1). The electronic interactions were investigated by means of interatomic short contacts supported by partial atomic charges calculations. In contrast with the almost similar orbital interactions stability of c1 and c2, the former is strongly destabilized by the electrostatic repulsion between Oδ-CO...Oδ-OMe atoms which are negatively charged separated by a distance shorter than the van der Waals radius sum. This short contact between Cδ+=Oδ- and Cδ+−Oδ- dipoles is responsible for the highest νCO frequency of c1 compared to c2 and c3. In the other hand, the greater stabilization of c1 in the more polar solvents is due to the better solvation of those local dipoles. Last, but not least, the X-ray analysis showed that the compounds in the solid state assume the less stable conformation c1, obtained in gas phase. No significative differences were found in terms of the Y and X substituents. It is suggestive that an energetic balance between orbital and electrostatic interactions determines the global stability of conformations in both studied series.

Leishmaniose e doença de Chagas são parasitoses endêmicas causadas, respectivamente, pelos protozoários Leishmania spp. e Trypanosoma cruzi. Ante à escassez de quimioterápicos, à elevada toxicidade dos fármacos disponíveis e à baixa eficácia destes no combate às formas intracelulares, replicantes, dos parasitos há necessidade de buscar novas alternativas quimioterápicas. A atividade tripanomicida do hidroximetilnitrofural, base de Mannich do nitrofural, já era conhecida. O presente trabalho mostra que este derivado também apresenta atividade leishmanicida, quando ensaiado em formas promastigotas de L. amazonensis, L. chagasi e L. baziliensis. Com o objetivo de obter pró-fármacos potencialmente ativos em doença de Chagas e leishmanioses visceral e mucocutânea, planejaram-se e foram sintetizados derivados hidrossolúveis de hidroximetilnitrofural e quitosana, polissacarídeo que apresenta, também, atividade imunomoduladora. Para a aplicação tópica em leishmaniose cutânea sintetizaram-se membranas de quitosana ligada ao hidroximetilnitrofural. Membranas de quitosana copolimerizadas com enxertos de ácido acrílico e metacrilato de hidroxietila foram sintetizadas e avaliadas quanto à biocompatibilidade - trombogenicidade, citotoxicidade e potencial hemolítico. Aquelas com maior teor em metacrilato de hidroxietila não se mostraram citotóxicas, tampouco hemolíticas; aquelas com maior proporção em ácido acrílico, por sua vez, apresentaram excelentes características de intumescimento, mas certo grau de citotoxicidade e hemólise, possivelmente devido à presença de monômeros que não reagiram no material. A ligação do hidroximetilnitrofural à quitosana, por meio de espaçante succínico, produziu prófármaco com propriedades filmogênicas para a aplicação tópica. Os derivados obtidos pró-fármacos e transportadores (quitosanas modificadas) - foram analisados no infravermelho, por ressonância magnética nuclear (RMN 1H e RMN 13C) e por análise térmica - OMTA, TG, OSC. Ensaios de atividade tripanomicida e leishmanicida dos pró-fármacos poliméricos e membranas serão posteriormente efetuados. Leishmaniasis and Chagas\' disease are endemic parasitosis provoked by the protozoa Leishmania spp and Trypanosoma cruzi, respectively. Due to the scarce chemotherapy, to the high toxicity of the available drugs and to their low effectiveness, mainly in the treatment of intracellular replicant forms of those parasites, the search for new chemotherapeutic alternatives is extremely important. Hydroxymethylnitrofurazone, a nitrofurazone Mannich basis, has proven to be active against trypanomicide before and its activity in cultures of L. amazonensis, L. chagasi and L. braziliensis promastigotes was determined in this work. With the purpose of obtaining prodrugs potentially active in Chagas\' disease and visceral and mucocutaneous leishmaniases, hydrosoluble hydroxymethylnitrofurazone prodrugs have been designed and synthesized using chitosan, a polysaccharide showing immunomudulatory activity, as the carrier. Membranes from chitosan linked with hydroxymethylnitrofurazone have been synthesized for topical administration in cutaneous leishmaniasis. Membranes were obtained by graft copolymerization of hydroxyethy/methacrylate and acrylic acid onto chitosan and their biocompatibility - trombogenicity, citotoxicity and hemolysis potential - was evaluated. Those membranes with higher content of hydroxyethylmethacrylate showed to be neither cytotoxic nor hemolytic; those with higher content of acrylic acid showed good swelling properties, although a certain level of cytotoxicity and haemolysis has been detected, due to the presence of non-reacted monomers. The linkage of hydroxymethylnitrofurazone to chitosan by a succinyl spacer group led to a prodrug with filmogenic properties for topic administration. The derivatives obtained - prodrugs and carriers (modified chitosans) - were analyzed by infrared, nuclear magnetic resonance (1H NMR and 13C NMR) and by thermal analysis - DMTA, TG and DSC. Tests of trypanomicide and leishmanicide activity with polymer prodrugs and membranes will be further developed.

Introdução: Dioxinas, furanos e bifenilas policloradas são poluentes tóxicos para a saúde humana incluindo riscos de incidência de cânceres, efeitos de neurodesenvolvimento, lesões dérmicas, cloroacne. Estes compostos são poluentes orgânicos persistentes (POPs) que podem ser transportados de longas distâncias da fonte de emissão e se bioacumular em ecossistemas. A atmosfera poluída foi recentemente classificada como carcinogênica para os seres humanos pela Organização Mundial da Saúde, mostrando a importância de sua caracterização, principalmente para compostos tóxicos. Entretanto, técnica de coleta ativa tem custo elevado para POPs, e existem poucos estudos de calibração que validem a substituição. Objetivos: Avaliar a toxicidade equivalente da atmosfera por dioxinas, furanos e bifenilas cloradas, utilizando técnicas de coleta ativa e passiva, e verificar gradiente de concentração nos ambientes urbano, urbano/industrial e de background. Método: Amostras de ar foram coletadas, utilizando coletores ativos e passivos, durante dois períodos consecutivos de quatro meses: de setembro a dezembro de 2014 (período 1) e de maio a agosto de 2015 (período 2) em três cidades de São Paulo, SP, em ambientes urbano, urbano/industrial e de background. Todas as amostras foram extraídas com solução de tolueno:acetona (9:1) em Soxhlet por 24 h e padrões marcados (13C12-PCDD/Fs e 13C12-PCBs) foram adicionados em cada amostra antes do processo de extração. Os extratos foram purificados em coluna de sílica mista (40 por cento H2SO4 e 10 por cento AgNO3) seguida por coluna de alumina. O procedimento analítico foi realizado utilizando HRGC/HRMS (High Resolution Gas Chromatograph/High Resolution Mass Spectrometer) operando em ionização de impacto de elétrons com energia de 35 eV no modo SIM (Select Ion Monitoring) e resolução de 10.000. Resultados mostraram que: (1) existe variação sazonal para concentrações de PCDD/Fs no ar entre os períodos 1 e 2 (p=0,03), enquanto as concentrações de dl-PCBs não foram estatisticamente diferentes nestes períodos (p=0,52); (2) existe gradiente de concentração de PCDD/Fs e dl- PCBs que aumenta na seguinte ordem: background < urbano < urbano/industrial, porém não foi encontrada diferença significante entre as concentrações dos locais urbano e urbano/industrial para as amostras da coleta ativa; (3) as concentrações de PCDD/Fs e dl-PCBs das amostras do coletor ativo variaram de 9,34 a 221 fg TEQ/m³ no período 1, e entre 7,76 a 453 fg TEQ/m³ no período 2; nas amostras dos coletores passivos estas concentrações variaram de 6,11 a 32,2 fg TEQ/m³ no período 1, e entre 48,6 e 298 fg TEQ/m³ no período 2; (4) a estimativa da taxa de coleta utilizando duas abordagens diferentes mostrou discrepâncias. Conclusões: o coletor passivo empregado neste estudo pode substituir o coletor ativo para verificação da toxicidade equivalente aos PCDD/Fs e dl-PCBs em diferentes locais, pois as duas técnicas estão em concordância em relação ao perfil dos grupos homólogos e ao gradiente de concentração nos locais urbano, urbano/industrial e background. A toxicidade da atmosfera em relação aos PCDD/Fs no ambiente urbano central da cidade de São Paulo em 2014-2015 não apresentou tendência de diminuição em relação aos anos 2000-2001 e 2006. Introduction: Dioxins, furans and polychlorinated biphenyls are toxic pollutants for human health including risks of cancer incidence, neurodevelopmental effects, dermal lesions, chloracne. These compounds are persistent organic pollutants (POPs) that can be transported to long distances from the emission source and they are bioaccumulated in ecosystems. Recently, the outdoor air pollution were classified as carcinogenic to humans by the World Health Organization, showing the importance of its characterization for toxic compounds. However, active air monitoring has a high cost for POPs, and there is a few calibration studies which support that substitution. Objective: To assess the equivalent toxicity of the atmosphere regarding the measurement of dioxins, furans and polychlorinated biphenyls, using active and passive air samplers, and to evatuate the contrasting concentrations at urban, urban/industrial and background sites. Method: Air samples were collected, using active and passive samplers, over two consecutive periods of four months: from September to December 2014 (period 1) and from May to August 2015 (period 2) at three cities in São Paulo, SP, covering urban, urban/industrial and background sites. All samples were extracted with toluene:acetone (9:1) in a Soxhlet apparatus for 24 hours and surrogate standards (13C12-PCDD/F and 13C12-PCBs) were spiked on each sample media prior to extraction procedure. The extracts were purified on an silica column (40 per cent H2SO4 and 10 per cent AgNO3) followed by an alumina column. The analytical procedure was carried out using HRGC/HRMS (High Resolution Gas Chromatograph/High Resolution Mass Spectrometer) operating in electron impact ionization with an energy of 35 eV in SIM (selected ion monitoring) mode and 10.000 resolution power. Results show that (1) there are seasonal variations for PCDD/F concentrations in air between period 1 and 2 (p=0.03), whereas dl-PCB levels were not statistically different (p=0.52) in those periods. (2) PCDD/F and dl-PCB air levels are in the following order: < urban < urban/industrial for both active and passive samplers; (3) PCDD/F and dl-PCB concentrations in active air samples ranged from 9.34 to 221 fg TEQ/m³ in period 1, and between 7.76 and 453 fg TEQ/m³ in period 2; in the passive air samples, these concentrations ranged from 6.11 to 32.2 fg TEQ/m³ in period 1, and between 48.6 and 298 fg TEQ/m³ in period 2; (4) the estimation of sampling rate using two approachs for PCDD/Fs showed differences. Conclusions: the passive air sampling can replace the active sampling to assess the equivalent toxicity regarding PCDD/Fs and dl-PCBs at different sites, since the two techniques are in agreement with the homologue profile and with the contrasting concentrations at urban, urban/industrial and background sites. The toxicity of the atmosphere regarding the PCDD/Fs at central urban site of city of São Paulo in 2014 and 2015 did not show tendency to decrease compared with the years of 2000, 2001 and 2006. Conclusions: the passive sampling method used in this study can replace the active sampling method to verify the equivalent toxicity to PCDD/Fs and dl-PCBs in different locations, since the two techniques are in agreement with the profile of the homologue groups as well as with the concentration gradient in the urban, urban/industrial and background sites. The toxicity of the atmosphere to the PCDD/Fs in the urban environment of the city of São Paulo in 2014-2015 did not show a tendency to decrease in relation to the years 2000-2001 and 2006.

No intuito de subsidiar e orientar futuras pesquisas astroquímicas pela busca de novas espécies moleculares, foram calculadas diversas propriedades em nível CCSD/cc-pVQZ (como geometrias, cargas atômicas, momentos de dipolo, frequências vibracionais e intensidades fundamentais de infravermelho) de bases de Lewis (B) presentes no meio interestelar (B = CO, CS, SO, HCN, FCN, ClCN, BrCN, HNC, FNC, ClNC, BrNC, OCS, HCNO HOCN, HONC, HNCO, NCCN e CNNC) e de suas espécies protonadas. Além disso, o modelo Carga - Fluxo de Carga - Fluxo de Dipolo (CFCFD), em termos dos multipolos da Teoria Quântica de Átomos em Moléculas (QTAIM), foi empregado para o estudo das variações nas intensidades de infravermelho de modos de estiramento durante a protonação. Os resultados indicam que, dependendo da extremidade da molécula na qual o próton se liga, há fortalecimento ou enfraquecimento das bandas de infravermelho originais. Estes fenômenos parecem estar associados à alteração de carga inicial durante a protonação, com fluxos de carga e de dipolo coordenados com tais mudanças de carga iniciais durante as vibrações. No que concerne ao estiramento da ligação formada após a protonação, [B-H]+, a contribuição de carga é preponderante quando o próton se liga aos átomos mais eletronegativos e menos polarizáveis (O, N e F). Todavia, quando o próton se liga ao par eletrônico isolado do carbono (isonitrilas, CO e CS) ou a outros átomos como cloro, bromo e enxofre, a contribuição de fluxos de carga e de dipolo atômico se tornam mais relevantes. De qualquer maneira, a raiz quadrada da intensidade de infravermelho desta nova banda de absorção correlaciona-se com a carga do próton de forma linear. No que se refere à partição da energia eletrônica por meio da aproximação de Átomos Quânticos Interagentes, verifica-se que: (1) a energia de estabilização do próton é proporcional à carga eletrônica recebida da base; (2) a desestabilização da base aumenta quanto maior a quantidade de carga eletrônica doada para o próton e (3) a energia de interação dos fragmentos é bastante específica de cada sistema, o que origina uma separação em grupos de sistemas semelhantes. In order to support and guide future astrochemical research related to the search for new molecular species, some properties were calculated at the CCSD/cc-pVQZ level (such as geometry, atomic charges, dipole moments, vibrational frequencies and fundamental infrared intensities) for Lewis bases (B) present in the interstellar medium (B = CO, CS, SO, HCN, FCN, ClCN, BrCN, HNC, FNC, ClNC, BRNC, OCS, HCNO, HOCN, HONC, HNCO, NCCN and CNNC) and its protonated species. In addition, the Charge - Charge Flux - Dipole Flux (CCFDF) model in terms of multipoles from the Quantum Theory of Atoms in Molecules (QTAIM) was used to study the variations in the infrared intensities of stretching modes during protonation. The results indicate that there is strengthening or weakening of the original infrared bands depending on the molecule end to which the proton is attached. These phenomena appear to be associated with the initial redistribution of electronic charge during protonation, resulting in charge and dipole fluxes coordinated with such initial rearrangement during the vibrations. Moreover, regarding the stretching intensity of the bond formed after protonation, [BH]+, the charge contribution is predominant when the proton is bound to atoms more electronegative and less polarizable atoms (O, N and F). However, when the proton binds to the lone (electron) pair of carbon (isonitriles, CO and CS) or to other atoms such as chlorine, bromine and sulfur, the charge and dipole fluxes become more significant. Nevertheless, the square root of the intensity for this new infrared absorption band correlates linearly with the charge assumed by the proton. Finally, with respect to the electronic energy partition through the Interaction Quantum Atom proposal, it is seen that (1) the proton stabilization energy is proportional to the electronic charge received from the base; (2) the destabilization of the base increases in line with the amount of electronic charge lost to the proton and (3) the interaction energy between the fragments is very specific of each system, which results in group separations.

Made available in DSpace on 2018-03-16T00:33:18Z (GMT). No. of bitstreams: 1 DaianeSciHorti2017SebroccoliGFAAS.pdf: 1953545 bytes, checksum: 9110fa4794588a8863306f7bfd52b254 (MD5) Previous issue date: 2018-03-15

As cargas, dipolos, quadrupolos e multipolos atômicos de maior ordem, bem como suas derivadas, permitem um maior entendimento de diversas propriedades elétricas em sistemas moleculares, como momentos de dipolo, derivadas do momento dipolar, intensidades de infravermelho e potenciais eletrostáticos, além de forças eletrostáticas. Os multipolos aqui estudados foram aqueles advindos da Teoria Quântica de Átomos em Moléculas (QTAIM) e, em certos casos, foram comparados com resultados do formalismo CHELPG (CHarges from Electrostatic Potentials using a Grid based method). As investigações desse projeto foram divididas em duas etapas distintas, sendo que a primeira focou no desempenho dos multipolos atômicos na descrição dos potenciais eletrostáticos quando da interação de uma carga pontual carregada positivamente com uma molécula. Algumas simples moléculas diatômicas (F2, Cl2, BF, AlF, BeO, MgO, LiH e NaCl) e outras mais complexas (H2O, H2CO, NH3, PH3, BF3 e CO2) foram consideradas nesta etapa, sendo que os cálculos foram feitos com B3LYP/6-311G(3d,3p). Já, na segunda etapa, estudou-se o modelo carga - fluxo de carga - fluxo de dipolo (CCFDF, do inglês \"charge - charge flux - dipole flux\") na investigação e interpretação das intensidades fundamentais de infravermelho em modos de vibração molecular. Nessa etapa optou-se pelo estudo de sistemas que apresentavam ligações de hidrogênio, como homodímeros (H2O-H2O, HF-HF, HCl-HCl, HCN-HCN, HNC-HNC e NH3-NH3) e heterodímeros (HF-HCN, HCl-HF e HF-H2O). Os cálculos destes sistemas foram realizados com CCSD/cc-pVQZ-mod. Os resultados sugerem que os multipolos QTAIM são melhores que as cargas CHELPG, na maioria dos casos, para descrição dos potenciais eletrostáticos em sistemas próton - molécula. Por sua vez, o modelo CCFDF/QTAIM consegue reproduzir as intensidades de infravermelho em dímeros que apresentam ligações de hidrogênio. Finalmente, o aumento de intensidade do estiramento X-H do monômero doador, em dímeros lineares, é explicado pela variação da contribuição de fluxo de carga durante a dimerização. The charges, dipoles, quadrupoles and high order terms, along with their derivatives, allow a better understanding of electric properties. We can cite dipole moments, dipole moment derivatives, infrared intensities, electrostatic potentials and electrostatic forces. The multipoles treated here are obtained from the Quantum Theory of Atoms in molecules (QTAIM) and they are compared with CHELPG (CHarges from Electrostatic Potentials using a Grid based method) results. The investigations of this project can be divided in two distinct parts and the first one focuses in the performance of atomic multipoles in the description of electrostatic potentials when one positive particle interacts with molecules. Some simple diatomic (F2 , Cl2 , BF, AlF, BeO, MgO, LiH and NaCl) and polyatomic molecules (H2O, H2CO, NH3 ,PH3 ,BF3 and CO2) were considered in this investigation and the calculations were carried out at the B3LYP/6-311G(3d,3p) level. The second part of this dissertation was a study of infrared intensities in vibrational modes by means of the charge-charge flux -dipole flux model. The systems treated now are dimers with hydrogen bonds such as homodimers (H2O-H2O, HF-HF, HCl-HCl, HCN-HCN, HNC-HNC and NH3-NH3) and heterodimers (HF-HCN, HCl-HF and HF-H2O). The calculations of these systems were carried out at the CCSD/cc-pVQZ-mod level. The results suggest that QTAIM multipoles are better in describing electrostatic potentials in almost all proton-molecule arrangements than CHELPG charges. The charge-charge flux -dipole flux model can reproduce infrared intensities of dimer with hydrogen bonds. Finally, the increase in intensities of X-H stretching modes associated to the donor monomer in linear dimers is explained by changes in charge flux contributions during dimerization.

Nesta tese foi estudado um grupo de 28 compostos não-imidazólicos antagonistas do receptor H3 através de cálculos de orbitais moleculares utilizando os métodos de química quântica Austin Model 1, Hartree-Fock-Roothaan e Teoria do Funcional da Densidade com o objetivo de investigar possíveis relações entre descritores eletrônicos teóricos e as afinidades ligantes experimentais desses compostos (pKi). Observou-se nos resultados obtidos que as energias dos orbitais FERMOs (Frontier Effective-for-Reaction Molecular Orbitals) apresentam melhor correlação com os valores de pKi do que as energias dos orbitais de fronteira HOMO (Highest Occupied Molecular Orbital) e LUMO (Lowest Unoccupied Molecular Orbital). Além disso, verificou-se pelas análises de métodos multivariados PCA (Principal Componente Analysis) e HCA (Hierarchical Cluster Analysis) que um conjunto de quatro descritores foi capaz de separar os compostos em dois grupos distintos, o primeiro que apresenta valores de afinidades ligantes maiores e o segundo com menores valores de pKi. Esta separação foi possível com o uso dos seguintes descritores teóricos: energia do FERMO (εFERMO), carga derivada do potencial eletrostático no átomo de nitrogênio N1, índice de densidade eletrônica no átomo N1 (Σ(FERMO) ci2) e eletrofilicidade (ω\'). Estes descritores foram utilizados, posteriormente, para a construção de três equações de regressão pelo método PLS (Partial Least Squares). O melhor modelo de regressão gerou os seguintes parâmetros estatísticos Q2 = 0,88 e R2 = 0,927, obtidos com um conjunto treino e de validação externa de 23 e 5 moléculas, respectivamente. Logo após a avaliação da equação de regressão, juntamente com os valores dos descritores selecionados e outros não selecionados, foi sugerido que altos valores de energias dos FERMOs e de Σ(FERMO) ci2 em conjunto com baixos valores de eletrofilicidades e cargas extremamente negativas no átomo N1 são parâmetros relevantes para potencializar as afinidades ligantes de outros compostos a serem sintetizados, que apresentem estruturas químicas semelhantes às moléculas estudadas neste trabalho. Além disso, esses compostos podem ser considerados como doadores de elétrons e, logo, há uma grande probabilidade que tais moléculas interajam com o receptor histamínico H3 a partir de um processo de transferência de carga. In this thesis, molecular orbital calculations were carried out on a set of 28 non-imidazole H3 antihistamine compounds using Austin Moldel 1, Hartree-Fock-Roothaan, and Density Functional Theory methods in order to investigate the possible relationships between electronic descriptors and binding affinity for H3 receptors (pKi). It was observed that the frontier effective-for-reaction molecular orbital (FERMO) energies were better correlated with pKi values than HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) energy values. Exploratory data analysis through hierarchical cluster (HCA) and principal component analysis (PCA) showed a separation of the compounds into two sets by using four descriptors, one grouping the molecules with high pKi values, the other gathering low pKi value compounds. This separation was obtained with the use of the following descriptors: FERMO energies (εFERMO), charges derived from the electrostatic potential on the nitrogen atom (N1), electronic density indexes for FERMO on the N1 atom (Σ(FERMO) ci2), and electrophilicity (ω\'). These electronic descriptors were used to construct three quantitative structure-activity relationship (QSAR) models through the Partial Least Squares Method (PLS). The best model generated Q2 = 0.88 and R2 = 0.927 values obtained from a training set and external validation of 23 and 5 molecules, respectively. After the analysis of the PLS regression equation, the values for the selected electronic descriptors and other descriptors, it is suggested that high values of FERMO energies and of Σ(FERMO) ci2, together with low values of electrophilicity and pronounced negative charges on N1 appear as desirable properties for the conception of new molecules which might have high binding affinity. Moreover, these molecules can be classified as electron donating compounds and have a great probability of interacting through a charge transfer process with the biological receptor H3.

Nas últimas décadas, o desenvolvimento das técnicas de ionização à pressão atmosférica impulsionou a espectrometria de massas, na caracterização e elucidação estrutural de compostos de grande massa molecular. O surgimento dessas técnicas foi o responsável pela amplitude nas aplicações e estudos de espectrometria de massas, sendo a ionização por electrospray a mais versátil dentre essas fontes de ionização. O caráter eletrolítico da fonte de ionização por electrospray permite-se obter íons provenientes de três processos químicos: i) ácido-base; ii) redox e iii) complexação. A extensão com que cada um desses processos ocorrerá dependerá de fatores relacionados à operação da fonte de ionização e grandezas termoquímicas do analito. O notável progresso em técnicas experimentais, processamento de dados e integração entre as mais diversas áreas de aplicação da química, tem estimulado e beneficiado a aplicação da química teórica em estudos de reações em fase gasosa. A aplicação da química computacional fornece uma compreensão quantitativa das variações estruturais e energéticas dos possíveis íons formados durante a ionização da amostra, permitindo também a compreensão das possíveis vias de dissociação. É neste sentido, que o sinergismo entre a aplicação de conceitos derivados da química quântica pode auxiliar nas análises de espectrometria de massas. O objetivo desta tese foi o de se aplicar os modelos fundamentados na mecânica quântica para obtenção de grandezas termoquímicas relacionadas aos fenômenos que ocorrem durante as análises de espectrometria de massas por electrospray. Inicialmente, a comparação entre métodos ab initio, modelos compostos e aqueles embasados na teoria do funcional de densidade foram empregados nos cálculos das grandezas termoquímicas para a -butirolactona e 2-pirrolidinona, com a finalidade de se obter parâmetros termoquímicos de alta qualidade. Os modelos compostos G2, G2(MP2), CBS-Q, CBS-QB3 e os métodos B3LYP, B3P86, B98, PW91PW91 e MP2 foram testados. Os valores obtidos para a entalpia de formação, afinidade protônica e basicidade em fase gasosa para essas duas moléculas foram comparados aos dados experimentais disponíveis na literatura. Os melhores resultados para os valores de entalpia de formação foram obtidos ao se empregar o modelo B3LYP/6-31+G(d,p). A afinidade protônica e basicidade em fase gasosa foram mais bem descritas por B3LYP e G2(MP2). Posteriormente, foram estudadas a 1,4-benzoquinona, 1,4-naftoquinona, bem como seus derivados (2-acetilamina-1,4-naftoquinona; 2-propionilamina-1,4-naftoquinona; 2-butirilamina-1,4-naftoquinona, 2-benzoilamina-1,4-naftoquinona, 2-succinilamina-1,4-naftoquinona e lapachol). A escolha do modelo teórico empregado foi realizada por se comparar as geometrias, afinidade protônica, basicidade em fase gasosa, energia de ionização e afinidade eletrônica obtidos para a 1,4-benzoquinona com aqueles disponíveis na literatura. O modelo B3LYP/6-31+G(d,p) foi o mais exato com relação as grandezas termoquímicas supracitadas, assim, este modelo foi empregado no cálculo dessas mesmas grandezas para a 1,4-naftoquinona e seus derivados. A influência do substituinte na estrutura eletrônica dessas moléculas protonadas, desprotonadas, oxidadas, reduzidas e cationizadas foi estudada utilizando-se análises energéticas, geométricas, eletrônicas e topológicas. O desenvolvimento desses estudos compreendeu as análises das grandezas termoquímicas e análises da densidade eletrônica pelos métodos NBO (Natural Bond Orbital), NSA (Natural Steric Analysis), NRT (Natural Resonance Theory) e AIM (Atoms in molecules). A ionização por electrospray e a dissociação induzida por colisão foram realizadas para os derivados da 1,4-naftoquinona, sendo analisados suas moléculas protonadas, desprotonadas, reduzidas, oxidadas e cationizadas com Na+. As vias mecanísticas de dissociação foram embasadas nas análises da superfície de energia obtidas pelo cálculo das energias de Gibbs e entalpias. In recent decades, the development of atmospheric ionization techniques improved mass spectrometry, principally for characterization and structural elucidation of high-molecular weight compounds. The development of spray ionization was responsible for the spread of applications and studies of mass spectrometry, where the electrospray ionization is the most versatile among the ionization sources. The electrolytic character of electrospray source allows obtaining ions by three different chemical processes: i) acid-base; ii) redox and, iii) metal complexation. These processes will occur through several factors which can be related to the ionization source and thermochemical parameters of analyte. The notable progress of experimental analyses, computational data and the integration between several areas of chemical application have stimulated the use of theoretical chemistry at gas-phase studies. Computational chemistry can furnish a quantitative understanding of the structure and energy of possible ions during the ionization process. For this reason, the synergism between the concepts from quantum chemistry and gas-phase chemistry can help mass spectrometry analysis. The main purpose of this thesis was the application of several quantum mechanical models to obtain thermochemical parameters which can be related to mass spectrometry phenomena. Firstly, the comparison between ab initio, composite model and DFT methods were employed to obtain the thermochemical parameters to -butyrolactone e 2-pyrrolidinona, in order to obtain high performance of thermochemical parameters. The composite G2, G2(MP2), CBS-Q and, the B3LYP, B3P86, B98, PW91PW91 and MP2 methods were tested. The calculated values were compared to experimental values reported in the literature. The best results for enthalpies of formation were obtained when B3LYP/6-31+G(d,p) model was employed. The proton affinity and gas-phase basicity were better described by using of B3LYP and G2(MP2). Secondly, the studies with quinones were performed, where the 1,4-benzoquinone, 1,4-naphthoquinone and its derivatives (2-acylamino-1,4-naphthoquinone; 2-propyonilamino-1,4-naphthoquinone; 2-butyrilamino-1,4-naphthoquinone; 2-benzoylamino-1,4-naphthoquinone; 2-succynilamino-1,4-naphtoquinone and, lapachol) were studied. A search for a theoretical model was made to compare the geometries, proton affinity, gas-phase basicity, ionization energy and electron affinity to 1,4-benzoquinone with those reported in the literature. The most accurate results were obtained by using of B3LYP/6-31+G(d,p). Thus, this model was applied in all studies with 1,4-naphthoquinone derivatives. The influence of substituent groups on electronic structure of protonated, deprotonated, reduced, oxidized and cationized molecules were studied by energetic, geometrics, electronics and topological analyses. The development of these studies and the determination of the thermochemical parameters and wave function analysis was achieved by means of Natural Bond Orbitals, Natural Steric Analysis, Natural Resonance Theory and Atoms in Molecules The electrospray ionization and gas-phase collision-induced dissociation were made for the 1,4-naphtoquinone derivatives by analyzing their protonated, deprotonated species, the radicalar and sodiated ones. The main fragmentation pathways were elucidated on the basis of the energy surface by using Gibbs energies and enthalpies.