Impressões digitais de folhas de Coffea arabica expostas à luz solar e autossombreadas colhidas na mesma planta, foram usadas para determinar as variações das concentrações dos metabólitos devido a diferentes ambientes de luz e fases fenológicas. Os rendimentos dos extratos nos solventes etanol, acetona, hexano e diclorometano, bem como as suas misturas são apresentados. Os maiores rendimentos para todas as folhas autossombreadas e expostas ao sol são obtidos com misturas binárias etanol-acetona. Análise de componentes principais (PCA) dos espectros de infravermelho com transformada de Fourier (FTIR) dos extratos indicam diferenças espectrais entre 2962-2828, 1759-1543 e inferiores a 1543 cm-1 que podem ser atribuídos a maiores concentrações de ésteres de ácidos graxos ou grupo éster em triglicerídeos, cafeína, ácidos clorogênicos e carboidratos, que são mais predominantes em folhas na fase de floração. Os espectros dos picos de cromatografia líquida de alta eficiência com detector UV de arranjo de diodos (HPLC-UV-DAD) dos extratos mostraram que folhas expostas ao sol apresentam absorções mais fortes para a cafeína, ácido clorogênico e teobromina. Experimentos confirmatórios para determinar a concentração de cafeína realizados com curvas de calibração UV, mostram que a cafeína de folhas expostas ao sol são cerca de duas vezes maior que as folhas autossombreadas na fase de floração. O conhecimento da quantidade de cafeína em folhas de Coffea arabica é de importância ecológica, já que plantas expostas ao sol parecem mais estressadas do que as autossombreadas para esta espécie. As concentrações lipídicas em folhas autossombreadas são quase o dobro daquelas expostas ao sol.

Fingerprints of self-shaded and sunlight-exposed leaves of the same Coffea arabica plant were obtained to determine metabolic concentration changes owing to different light environments and phenological stages. Leaf extract yields of the ethanol, acetone, dichloromethane and hexane solvents, as well as their statistical design mixtures, are reported. Highest yields are obtained with binary 1:1 ethanol-acetone mixtures for all sun-exposed and self-shaded leaves. Principal component analysis (PCA) of Fourier transform infrared (FTIR) spectra of leaf extracts indicate spectral differences between 2962-2828, 1759-1543 and below 1543 cm-1 that can be attributed to higher concentrations of fatty acid esters or the ester group in triglycerides, caffeine, chlorogenic acids and carbohydrates that are more prevalent in leaves of flowering plants. High-performance liquid chromatography with UV diode array detector (HPLC-UV-DAD) spectra of the chromatographic peaks for the extracts showed that sun-exposed samples contain stronger absorptions for caffeine, chlorogenic acid and theobromine. Confirmatory experiments carried out with reference UV calibration curves determined caffeine contents for sun-exposed leaves that are about double those for self-shaded leaves of flowering plants. Knowledge of leaf caffeine content in Coffea arabica is of ecological importance since sun-exposed conditions seem more stressful than self-shading ones for this species. Lipid concentrations in self-shaded leaves are almost double those that were sun-exposed.

An experiment was proposed applying the Chemometric approach of Multivariate Analysis for inclusion in undergraduate Chemistry courses to promote and expand the use of this analytical-statistical tool. The experiment entails the determination of the acid dissociation constant of dyes via UV-Vis electronic spectrophotometry. The dyes used show from simple equilibrium to very complex systems involving up to four protolytic species with high spectral overlap. The Chemometric methodology was more efficient than univariate methods. For use in classes, it is up to the teacher to decide which systems should be utilized given the time constraints and laboratory conditions.

In this research work the effects of four solvents and their mixtures on the extraction of chlorogenic acids, caffeine and trigonelline in crude extracts of four coffee cultivars, traditional red bourbon, IAPAR59, IPR101 and IPR108 cultivars, were investigated by UV spectrophotometry and UV spectra obtained from RP-HPLC-DAD. The experimental results and the principal component analysis of UV spectra showed that the effect of solvent extraction of the metabolites does not depend on cultivars, because the spectral characteristics are similar, but the concentrations are different. The UV and UV-DAD spectra for four simplex centroid design mixtures were also similar but the concentrations of caffeine, trigonelline and the chlorogenic acids are different and depend on the solvent used in the extraction.

Ten common doubts of chemistry students and professionals about their statistical applications are discussed. The use of the N-1 denominator instead of N is described for the standard deviation. The statistical meaning of the denominators of the root mean square error of calibration (RMSEC) and root mean square error of validation (RMSEV) are given for researchers using multivariate calibration methods. The reason why scientists and engineers use the average instead of the median is explained. Several problematic aspects about regression and correlation are treated. The popular use of triplicate experiments in teaching and research laboratories is seen to have its origin in statistical confidence intervals. Nonparametric statistics and bootstrapping methods round out the discussion.

A spectrophotometric method was proposed for Ni(II) determination in alloys using a dopa-semiquinone (L-1) to form [Ni(II)(L1-)3]1-, ε = 9.3 x 10³ L mol-1 cm-1. The optimal conditions for the determination were: wavelength 590 nm, temperature 25 °C, reaction time 45 min and pH 7.5. The Beer's law was obeyed for nickel from 3.33 x 10-5 to 1.78 x 10-4 mol L-1. The method was applied to complex samples, such as inox, nickel-titanium and cobalt-chromium alloys. A study of the potential interferents revealed that Mn was the major interferent. The limit of detection and quantification were 2.88 x 10-5 mol L-1 and 3.06 x 10-5 mol L-1, respectively.

Anthocyanins are among the most important plant pigments. Due to their potential benefits for human health, there is considerable interest in these natural pigments. Nonetheless, there is great difficulty in finding a technique that could provide the identification of structurally similar compounds and estimate the number and concentration of the species present. A lot of techniques have been tried to find the best methodology to extract information from these systems. In this paper, a review of the most important procedures is given, from the extraction to the identification of anthocyanins in natural extracts.

O objetivo deste trabalho foi avaliar os efeitos alimentares estimulantes e arrestantes para Diabrotica speciosa (Ger.), a partir de formulações amiláceas com cucurbitacina, variando-se as fontes de amido e adicionando-se lignato de potássio. Em ensaio com lâmina de vidro, comparou-se a resistência à lavagem das formulações. O lignato de potássio não aumentou a resistência à lavagem. Pó de Lagenaria vulgaris L., cuja concentração de cucurbitacina B foi determinada como sendo de 0,28%, foi adicionado à formulação mais adesiva. O material resultante foi utilizado em ensaios com dupla chance de escolha, nos quais folhas de feijão, Phaseolus vulgaris L., pulverizadas com concentrações de 2,5%, 5%, 10%, 15% e 20% foram oferecidas aos insetos juntamente com folhas não tratadas. Foram observados maior número de insetos e maior quantidade de folhas consumidas nas folhas tratadas com formulações com cucurbitacina (2,5%, 5% - maior resposta -, 10% e 15%) do que nas folhas não tratadas. A formulação cuja concentração teve maior resposta foi pulverizada em lavoura de feijão, nas dosagens de 1.000, 1.900 e 3.000 g ha-1. O maior número de adultos de D. speciosa foi encontrado nas parcelas tratadas com a maior dosagem, aos 3 e 6 dias após a pulverização. Dez dias após a pulverização, não foram encontradas diferenças entre as dosagens, provavelmente por causa da lavagem da isca pelas chuvas.

The objective of this work was to evaluate arrestant and stimulant feeding effects on Diabrotica speciosa (Ger.), using cucurbitacin-content starch-based formulations prepared with varying starch sources, and adding potassium lignate. In a glass slide assay, the wash off resistance of formulations was compared. Potassium lignate did not improve wash off resistance. Lagenaria vulgaris L. powder, in which cucurbitacin B concentration was determined as 0.28%, was added to the most adhesive formulation. The resultant material was used in a two-choice assay in which leaves of common bean, Phaseolus vulgaris L., treated with concentrations of 2.5%, 5%, 10%, 15% and 20% were offered to insects together with untreated control leaves. Greater number of insects and leaves consumed were found on leaves treated with cucurbitacin-content formulation (2.5%, 5% - greatest response -, 10% and 15% concentrations) than on untreated control leaves. The concentration, in which responses were higher, was sprayed in a bean field at 1,000, 1,900 and 3,000 g ha-1. Greater number of beetles was found in plots treated with the highest dosage, 3 and 6 days after spraying. Ten days after spraying, no significant differences were found among dosages, probably due to washoff of the bait.

A multivariate calibration method to determine chemical compositions of systems with severely overlapped bands is proposed. Q mode factors are determined from the spectral data and subsequently rotated using the varimax and oblique transformation of Imbrie. The method is applied to two sets of simulated data to test the sensitivity of analytical results to random experimental error. The chemical concentrations of alanine and threonine mixture are determined from spectral data of the 302,5 - 548,5 nm region.