The effects of water-deficit stress on irrigated and unirrigated field plants of Coffea arabica L. genotype IAPAR 59 were investigated. Plant extracts were obtained following an ethanol-dichloromethane-hexane statistical mixture design. Proton nuclear magnetic resonance (1H NMR) fingerprints of the extracts were discriminated using factor analysis (FA) and hierarchical clustering techniques. Extracts from the 1:1:1 ternary mixture presented the largest discriminations compared with those from the pure solvents or their 1:1 binary mixtures. Metabolites resulting from fermentation processes and nutritional deficiencies as well as senescence and abscission precursors such as lactate, arginine and methionine were prevalent in unirrigated plants that can provoke expressive decreases in bean productivity as well as premature plant aging. Amino acids that control regulatory, physiological processes and soil salinization have higher concentrations in the irrigated plants. The NMR assignments of eighteen substances observed here were confirmed by electrospray ionization mass spectrometry.

Rollinia mucosa fruit has generated great interest due to the presence of bioactive compounds, which exhibit promising biological activities. Fingerprinting analytical techniques, chromatographic-diode array detection (DAD), infrared, mass spectrometric, 1H and 13C nuclear magnetic resonance (NMR) spectra, associated with chemometric analysis and mixture design, were used to determine chemical discriminations of sun-exposed and self-shaded leaves of Rollinia mucosa in each of the four seasons. Sunlit leaves in winter presented higher metabolite signals related to the acetogenins, whereas shaded leaves have higher abundances of carbohydrates and terpenes. Sunlit leaves harvested in the summer had the smallest metabolite abundances. Fingerprints confirmed the presence of two acetogenins, annonacin A and annonastatin. Ternary and quaternary mixtures of the statistical mixture design were most effective for revealing important discriminations.

Coffee bean chemical compositions has been extensively studied. However, there is a small amount of research on other parts of the coffee plant, including leaves. Fourier transform infrared (FTIR) spectral profiles of Coffea arabica L. cv. IAPAR 59 leaf extracts from a simplex-centroid design were studied by principal component analysis (PCA) to evaluate the effect of solvent extractor on its metabolites. PCA indicated that the extractor solvents containing ethanol were the most suitable for this study. FTIR spectra in conjunction with orthogonal signal correction and partial least squares-discrimination analysis (OSC-PLS-DA) were used to classify and discriminate the leaves of irrigated and non-irrigated plants by bands related to carbohydrates, amino acids and lipids. Leaves receiving different intensities of solar radiation were also discriminated by bands corresponding to caffeine, carbohydrates and lipids. FTIR spectral profile analyzed with chemometric tools showed to be a useful, powerful and simple procedure to discriminate coffee leaves collected from different microclimate conditions.

This review contains experimental values of polar tensors and generalized atomic polar tensor (GAPT) charges determined since the publication of the polar tensor formulism for infrared intensity interpretation in 1961. GAPT charges, also called mean dipole moment derivatives, for 167 atoms of 67 molecules are discussed and compared with infrared charges also determined completely from experimental intensities. The importance of the charge transfer and polarization dynamic contributions to the GAPT charge are emphasized as they differentiate this charge from most theoretically calculated charges. The inclusion of these dynamic contributions is shown to be necessary to provide adequate numerical descriptions of core electron ionization energy processes. These contributions are expected to be important in studies of chemical reactivity.

Ultraviolet characteristic profiles and infrared spectroscopic (FTIR) fingerprints of green bean extracts of Coffea arabica L., cv. IAPAR 59, cultivated in two planting patterns, rectangular and square, and at two different densities, 10,000 and 6,000 plants ha-1, identified as R10, R6, S10, and S6 were analyzed with principal component and hierarchical cluster analyses. A simplex centroid design for four solvents (ethanol, acetone, dichloromethane, hexane) was used for sample extraction. The largest chlorogenic acid (CGA) contents were found at the lower planting density. The dichloromethane extracts of the S10 treatment showed the highest levels of unsaponifiable lipids (cafestol and kahweol). The R6 treatment showed a slightly higher content of cafestol and kahweol. Cluster analysis of FTIR fingerprints confirmed that the CGA and caffeine levels differentiate the spatial arrangements. The FTIR fingerprints suggest that green beans from S6 and R10 were richer in lipids and the other two treatments had more sugars and proteins.

Um método computacional interativo foi desenvolvido para a separação eletroforética de 13 compostos fenólicos de azeite de oliva extravirgem, usando valores individuais de resposta para cada pico. Um planejamento composto central foi executado para a otimização da concentração de tetraborato de sódio, pH e voltagem aplicada. Foram determinados modelos estatísticos para oito respostas de resolução e treze de mobilidades efetivas. Seis modelos de resolução apresentaram significativa falta de ajuste após ANOVA, o que limitou sua acurácia para uso nas funções de desejabilidade de Derringer-Suich na busca pelas condições ótimas de separação. Nenhum dos 13 modelos de mobilidade efetiva apresentou falta de ajuste significativa. Visto que não foi possível definir valores alvos para as funções de desejabilidade, um programa de computador interativo, desenvolvido em nossos laboratórios, foi aplicado aos modelos individuais de cada pico. Movimentos do mouse ou do cursor foram executados para definir as condições experimentais nas simulações dos eletroferogramas. Essas simulações resultaram em uma melhor separação dos picos, especialmente para os picos de apigenina e luteolina, em 35 min, comparado aos obtidos para cerca de 50 min com os modelos de resolução. Experimentos de verificação executados 2 e 3 anos depois confirmaram a robustez dos modelos.

An interactive computer method is proposed for the electrophoretic separation of 13 phenolic compounds from extra-virgin olive oil using single peak response values. A central composite design was executed for optimization of the sodium tetraborate concentration, pH and applied voltage. Statistical models were determined for eight resolution responses and thirteen effective mobilities. Six of the resolution models had highly significant ANOVA lack of fit values, limiting their accuracies for use in Derringer´s desirability function search for optimal separation conditions. None of the 13 effective mobility models suffered from significant lack of fit. Since it is not possible to define effective mobility target values for the desirability function, an interactive computer program developed in our laboratories was applied to the single peak models. Mouse or cursor movements were executed to define experimental conditions in model simulations of the electropherogram. These simulations resulted in superior peak separations, especially for the apigenin and luteolin peaks, in 35 min, compared with those obtained in close to 50 min with the resolution models. Verification experiments performed 2 and 3 years later confirmed the robustness of the models.

O presente trabalho descreve a otimização e validação de um método para determinação direta de cádmio em amostras de vinho por espectrometria de absorção atômica com atomização eletrotérmica (ET AAS). A otimização foi realizada empregando um planejamento fatorial completo de 2 níveis, incluindo os fatores: tempo (10 s) e temperatura de pirólise (600 ºC), temperatura de atomização (1300 ºC) e massa de modificador (15 µg). Sob as condições otimizadas, foi encontrada uma massa característica de 0,7 pg, limite de detecção e quantificação de 0,030 e 0,100 µg L-1, respectivamente, para um volume de amostra de 20 µL. A precisão foi de 0,30, 0,37 e 0,49% (RSD) para amostras de vinho com concentrações de 1,286, 0,266 e 0.356 µg L-1, respectivamente. A exatidão da metodologia de determinação direta empregando ET AAS foi avaliada por comparação usando um método de digestão ácida e determinação também por ET AAS para cinco amostras de vinho. O método foi aplicado para determinação de cádmio em 30 amostras de vinhos brasileiros. A concentração de cádmio variou de 0,146 a 1,563 µg L-1, cujos valores estão abaixo do nível máximo permitido pela Organização Internacional de Vinha e Vinho (OIV) e pela legislação brasileira, 10 µg L-1.

This work describes the optimization and validation of a direct method employing electrothermal atomic absorption spectrometry (ET AAS) for the determination of cadmium in wine. The optimization step was carried out using a two-level full factorial design, involving the followings factors: pyrolysis time (10 s) and temperature (600 ºC), atomization temperature (1300 ºC) and modifier mass (15 µg). Under the optimized conditions, a characteristic mass of 0.7 pg and limits of detection and quantification of 0.030 and 0.100 µg L-1, respectively, were obtained using a sample volume of 20 µL. The precision expressed as relative standard deviation (RSD %) was 0.30, 0.37 and 0.49% for wines with cadmium concentrations of 1.286, 0.266 and 0.356 µg L-1, respectively. The accuracy of the new direct determination methodology applying ET AAS was assessed by comparison with an acid digestion methodology, also with determination by ET AAS, using five wine samples. The proposed method was applied for the determination of cadmium in 30 Brazilian wine samples. The cadmium content varied from 0.146 to 1.563 µg L-1; all these values are lower than the permissible maximum level stipulated by the International Organization of Vine and Wine (OIV) and also by Brazilian legislation, which is 10 µg L-1.

Neste trabalho, foi avaliada a composição mineral da farinha de trigo consumida no Brasil. Na etapa de amostragem foram coletadas 54 amostras em 15 cidades, incluindo as principais cidades brasileiras como: São Paulo, Rio de Janeiro, Salvador, Porto Alegre, Recife e outras. Os elementos determinados foram: cálcio, cobre, magnésio, manganês, ferro, fósforo, potássio e zinco. As amostras foram digeridas usando acido nítrico e peróxido de hidrogênio em sistema aberto. A técnica analítica empregada foi a espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES). A validação do método (incluindo digestão e determinação) foi confirmada usando um material de referência certificado de farinha de trigo fornecido pelo National Institute of Standards & Technology (NIST). Considerando as 54 amostras analisadas, os resultados demonstraram que os macronutrientes: cálcio, magnésio, potássio e fósforo encontram-se em média de 0,27; 0,35; 1,71 e 1,92 mg g-1, com variação da concentração de 0,11-1,96; 0,19-0,51; 0,76-3,16 e 0,81-7,15 mg g-1, respectivamente. Os micronutrientes: cobre, ferro, manganês e zinco encontram-se em média de 1,84; 37,82; 8,25 e 9,41 µg g-1, com a variação de concentração de 1,00-2,80; 10,46-146,58; 3,89-14,74 e 5,07-13,93 µg g-1, respectivamente. Os resultados foram também avaliados usando as técnicas de análise multivariadas: análise de componente principal (PCA) e análise de agrupamento hierárquico (HCA).

In the present paper, the mineral composition of wheat flour consumed in Brazil was evaluated. In the sampling step 54 samples were collected in 15 cities, including principal Brazilian cities such as: São Paulo, Rio de Janeiro, Salvador, Porto Alegre, Recife and others. The elements determinate were: calcium, copper, magnesium, manganese, iron, phosphorus, potassium and zinc. The samples were digested using nitric acid and hydrogen peroxide in open system. The analytical technique employed was Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES). The method validation (including digestion and determination) was performed using a certified reference material of wheat flour furnished by National Institute of Standards & Technology (NIST). Considering the 54 samples analyzed, the results demonstrated that the macronutrients: calcium, magnesium, potassium and phosphorus have average contents of 0.27, 0.35, 1.71 and 1.92 mg g-1, for concentration ranges of 0.11-1.96, 0.19-0.51, 0.76-3.16 and 0.81-7.15 mg g-1, respectively. The micronutrients: copper, iron, manganese and zinc have average contents of 1.84, 37.8, 8.2 and 9.4 µg g-1, for concentration ranges of 1.00-2.80, 10.5-146.6, 3.9-14.7 and 5.1-13.9 µg g-1, respectively. The results were also evaluated using the multivariate analysis techniques: principal component analysis (PCA) and hierarchical cluster analysis (HCA).

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.

In this study atmospheric particulates of PAHs were measured in Araraquara, Piracicaba and São Paulo in July 2003 (sugarcane harvest season in Araraquara and Piracicaba) and in Araraquara in March of 2003. The results were normalized to the total PAH concentrations. Comparison among the sites and principal component analysis (PCA) were used to investigate possible tracers of emission. Fluoranthene and pyrene concentrations were higher in Piracicaba and Araraquara samples. These PAH were also responsible for the largest negative loadings on the second principal component and account for the negative scores and for the formation of the Araraquara and Piracicaba group.

Chemometric activities in Brazil are described according to three phases: before the existence of microcomputers in the 1970s, through the initial stages of microcomputer use in the 1980s and during the years of extensive microcomputer applications of the ´90s and into this century. Pioneering activities in both the university and industry are emphasized. Active research areas in chemometrics are cited including experimental design, pattern recognition and classification, curve resolution for complex systems and multivariate calibration. New trends in chemometrics, especially higher order methods for treating data, are emphasized.

Um planejamento de misturas foi usado para otimizar a composição da fase móvel para a separação dos carboidratos em mel por Cromatografia Líquida de Alta Eficiência. Nove fases móveis ternárias de acetonitrila, água e acetato de etila, correspondendo a um planejamento centróide simplex com pontos axiais foram testadas para separar os carboidratos mais freqüentemente encontrados em amostras de mel. Os resultados sugerem que um modelo cúbico especial descreve precisamente as mudanças nas proporções destes solventes na fase móvel próxima a região ótima da separação dos picos. A adição de um terceiro solvente, acetato de etila, à fase móvel binária de água e acetonitrila permitiu uma melhora significativa na separação dos carboidratos que pode ser aplicada à análise quantitativa destes compostos em mel.

A mixture design was used to optimize the mobile phase composition for separation of carbohydrates in honey by High Performance Liquid Chromatography. Nine ternary acetronitrile, water and ethyl acetate mobile phases corresponding to a simplex centroid design with axial points were test to separate those carbohydrates most frequently encountered in honey samples. The results suggest that a special cubic model accurately describes changes in the proportions of these solvents in the mobile phase close to the region of optimal peak separation. The addition of a third solvent, ethyl acetate, to binary mobile phase of water and acetonitrile permitted a significant improvement in carbohydrate separation that can be applied to the quantitative analysis of these compounds in honey.

Um planejamento fatorial foi aplicado para avaliar o conteúdo de cinzas em mel pela termogravimetria bem como para estabelecer as condições de análise ótimas que produzem conteúdos de cinzas em concordância com aqueles obtidos pelo método oficial (gravimetria). Os efeitos de taxa de aquecimento e papel de fibra de vidro foram significativos bem como o efeito de interação entre estas variáveis. Taxas de aquecimento e o emprego do papel de fibra de vidro são recomendados para obter a incineração completa de mel pela termogravimetria. Para confirmar estes resultados e estabelecer as condições otimizadas foi executado um planejamento completamente aleatorizado em blocos investigando três procedimentos: termogravimetria com papel de fibra de vidro a 5 e 10 ºC min-1 e gravimetria. Somente o método termogravimétrico realizada à 5 ºC min-1 apresentou conteúdos médios de cinzas em concordância com aqueles obtidos pelo método oficial. Assim, a TG/DTG pode ser indicada como um método alternativo à gravimetria para esta determinação em mel.

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.

Dois procedimentos para a redução de experimentos para o método split-plot foram investigados usando um conjunto de dados contendo 160 experimentos, consistindo de 80 duplicatas provenientes da otimização de um sistema contendo a mistura de água-acetona-N,N-dimetilformamida e os reagentes HCl, o-dianisidina e H2O2 para a determinação de Cr(VI). A estabilidade dos coeficientes do modelo e as médias quadráticas da ANOVA são usadas como critério para julgar a eficiência dos procedimentos. Somente o procedimento que evita a possibilidade de se eliminar completamente uma replicata para um dado conjunto de condições das variáveis de processo parece ser praticável, uma vez que não resulta em perda de informação fundamental da modelagem. Seus valores das médias quadráticas da ANOVA permaneceram estáveis para reduções de até 30% das replicatas enquanto seus coeficientes dos modelos foram relativamente constantes para até 70% de redução das replicatas. Tendo em vista que um planejamento split-plot completo envolvendo variáveis de processo e de mistura requer um grande número de experimentos, a economia introduzida por planejamentos split-plot incompletos faz seu uso ser muito atraente.

Two experiment reduction procedures for split-plot designs are investigated using a data set containing 160 experiments, consisting of 80 duplicate results for the optimization of a water-acetone-N,N-dimethylformamide mixture with HCl, o-dianisidine and H2O2 reagent system for the analytical determination of Cr(VI). Stabilities of the model coefficients and ANOVA mean squares are used as quality criteria to judge the effectiveness of the procedures. Only the procedure that avoids the possibility of eliminating entire replicates for any given set of process variable conditions seems to be feasible, since it does not result in loss of valuable modeling information. Its mean square ANOVA values remain stable for up to a 30% replicate reduction whereas its model coefficients are relatively constant for even 70 % replicate reduction. Since complete split-plot designs involving both process and mixture variables require large numbers of experiments, the economy gained by performing incomplete split-plot designs makes their use more attractive.

Recentemente Galabov and Bobadova-Parvanova mostraram que a energia de formação da ligação de hidrogênio obtida por cálculo no nível HF/6-31G(d,p) está altamente correlacionada com o potencial eletrostático molecular na região aceptora em alguns compostos carbonílicos simples. Neste trabalho mostramos que o potencial eletrostático pode ser substituído pela energia de Koopmans. A correlação entre esta energia e a energia de formação da ligação de hidrogênio é tão alta quanto aquela observada por Galabov e Bobadova-Parvanova. O potencial de Siegabhn relacionando às energias de Koopmans e cargas GAPT mostra que a energia de ligação de hidrogênio não está simplesmente correlacionada com a carga da região aceptora pois as cargas dos átomos vizinhos são também importantes no processo de ligação de hidrogênio.

Recently Galabov and Bobadova-Parvanova have shown that the energy of hydrogen bond formation calculated at the HF/6-31G(d,p) level is highly correlated with the molecular electrostatic potential at the acceptor site for a number of simple carbonyl compounds. Here it is shown that the electrostatic potential can be replaced by Koopmans' energy. The correlation between this energy and the hydrogen bond formation energy is just as high as the one observed by Galabov and Bobadova-Parvanova. The Siegbahn simple potential relating Koopmans' energies and GAPT charges shows that the hydrogen bond energy is not simply correlated with the charge of the acceptor site because the charges on the neighboring atoms are also important in the hydrogen bonding process.