Authenticity study of Phyllanthus species by NMR and FT-IR Techniques coupled with chemometric methods

The importance of medicinal plants and their use in industrial applications is increasing worldwide, especially in Brazil. Phyllanthus species, popularly known as "quebra-pedras" in Brazil, are used in folk medicine for treating urinary infections and renal calculus. This paper reports an authenticity study, based on herbal drugs from Phyllanthus species, involving commercial and authentic samples using spectroscopic techniques: FT-IR, ¹H HR-MAS NMR and ¹H NMR in solution, combined with chemometric analysis. The spectroscopic techniques evaluated, coupled with chemometric methods, have great potential in the investigation of complex matrices. Furthermore, several metabolites were identified by the NMR techniques.

SIMULTANEOUS DETERMINATION OF PROTOCATECHUIC ALDEHYDE AND PROTOCATECHUIC ACID USING THE LOCALIZED SURFACE PLASMON RESONANCE PEAK OF SILVER NANOPARTICLES AND CHEMOMETRIC METHODS

A simple and sensitive spectrophotometric method is proposed for the simultaneous determination of protocatechuic acid and protocatechuic aldehyde. The method is based on the difference in the kinetic rates of the reactions of analytes with [Ag(NH3)2]+ in the presence of polyvinylpyrrolidone to produce silver nanoparticles. The data obtained were processed by chemometric methods using principal component analysis artificial neural network and partial least squares. Excellent linearity was obtained in the concentration ranges of 1.23-58.56 µg mL-1 and 0.08-30.39 µg mL-1 for PAC and PAH, respectively. The limits of detection for PAC and PAH were 0.039 and 0.025 µg mL-1, respectively.

Avaliação quimiométrica da distribuição de metais pesados em composto de lixo urbano domiciliar

The main obstacle to the use of compost from urban waste in agriculture is the presence of heavy metals. Once in the soil, their effect is accumulative and they may contaminate crops and water. The present study reports the evaluation of the chemical distributions of Cu, Pb, Mn and Zn in three different sized fractions (unsieved, < 1,18mm and > 1,18mm) of compost, by means of a sequencial extraction procedure and a chemometric analysis of the total content of all metals in each fraction. The pattern recognition methods showed significant differences in total heavy metal contents for the different fractions. The finest one was the most contaminated. Meanwhile, this fraction presented lower amounts of metals in avaliable forms. This behavior can be attributed to the presence of metal particles in their elemental states in this fraction.

Avaliação do uso de métodos quimiométricos em análise de solos

One of the major interests in soil analysis is the evaluation of its chemical, physical and biological parameters, which are indicators of soil quality (the most important is the organic matter). Besides there is a great interest in the study of humic substances and on the assessment of pollutants, such as pesticides and heavy metals, in soils. Chemometrics is a powerful tool to deal with these problems and can help soil researchers to extract much more information from their data. In spite of this, the presence of these kinds of strategies in the literature has obtained projection only recently. The utilization of chemometric methods in soil analysis is evaluated in this article. The applications will be divided in four parts (with emphasis in the first two): (i) descriptive and exploratory methods based on Principal Component Analysis (PCA); (ii) multivariate calibration methods (MLR, PCR and PLS); (iii) methods such as Evolving Factor Analysis and SIMPLISMA; and (iv) artificial intelligence methods, such as Artificial Neural Networks.

Seleção de variáveis em QSAR

The process of building mathematical models in quantitative structure-activity relationship (QSAR) studies is generally limited by the size of the dataset used to select variables from. For huge datasets, the task of selecting a given number of variables that produces the best linear model can be enormous, if not unfeasible. In this case, some methods can be used to separate good parameter combinations from the bad ones. In this paper three methodologies are analyzed: systematic search, genetic algorithm and chemometric methods. These methods have been exposed and discussed through practical examples.

PARAFAC: uma ferramenta quimiométrica para tratamento de dados multidimensionais. Aplicações na determinação direta de fármacos em plasma humano por espectrofluorimetria

Since the last decade, the combined use of chemometrics and molecular spectroscopic techniques has become a new alternative for direct drug determination, without the need of physical separation. Among the new methodologies developed, the application of PARAFAC in the decomposition of spectrofluorimetric data should be highlighted. The first objective of this article is to describe the theoretical basis of PARAFAC. For this purpose, a discussion about the order of chemometric methods used in multivariate calibration and the development of multi-dimensional methods is presented first. The other objective of this article is to divulge for the Brazilian chemical community the potential of the combination PARAFAC/spectrofluorimetry for the determination of drugs in complex biological matrices. For this purpose, two applications aiming at determining, respectively, doxorrubicine and salicylate in human plasma are presented.

Cafeína: revisão sobre métodos de análise

Gravimetric and Bailey-Andrew methods are tedious and provide inflated results. Spectrofotometry is adequate for caffeine analysis but is lengthy. Gas chromatography also is applied to the caffeine analysis but derivatization is needed. High performance liquid chromatography with ultraviolet detection (HPLC-UV) and reversed phase is simple and rapid for xanthine multianalysis. In HPLC-UV-gel permeation, organic solvents are not used. HPLC-mass spectrometry provides an unequivocal structural identification of xanthines. Capillary electrophoresis is fast and the solvent consumption is smaller than in HPLC. Chemometric methods offer an effective means for chemical data handling in multivariate analysis. Infrared spectroscopy alone or associated with chemometries could predict the caffeine content in a very accurate form. Electroanalytical methods are considered of low cost and easy application in caffeine analysis.

Oxidação de glicerol sobre nanopartículas de ouro suportadas em carvão ativado: monitoramento quimiométrico da reação por ESI-MS e MIR

A study on the monitoring of glycerol oxidation catalyzed by gold nanoparticles supported on activated carbon under mild conditions by chemometric methods is presented. The reaction was monitored by mass spectrometry-electrospray ionization (ESI-MS) and comparatively by mid infrared spectroscopy (MIR). Concentration profiles of reagent and products were determined by chemometric tools such as Principal Component Analysis (PCA), Evolving Factor Analysis (EFA) and Multivariate Curve Resolution (MCR). The gold nanoparticle catalyst was relatively active in glycerol oxidation, favoring formation of high added value products. It was found that the reaction stabilization was reached at four hours, with approximately 70% glycerol conversion and high selectivity for glycerate.

Simultaneous spectrophotometric determination of ezetimibe and simvastatin in pharmaceutical preparations using chemometric techniques

Two spectrophotometric methods are described for the simultaneous determination of ezetimibe (EZE) and simvastatin (SIM) in pharmaceutical preparations. The obtained data was evaluated by using two different chemometric techniques, Principal Component Regression (PCR) and Partial Least-Squares (PLS-1). In these techniques, the concentration data matrix was prepared by using the mixtures containing these drugs in methanol. The absorbance data matrix corresponding to the concentration data matrix was obtained by the measurements of absorbances in the range of 240 - 300 nm in the intervals with Δλ = 1 nm at 61 wavelengths in their zero order spectra, then, calibration or regression was obtained by using the absorbance data matrix and concentration data matrix for the prediction of the unknown concentrations of EZE and SIM in their mixture. The procedure did not require any separation step. The linear range was found to be 5 - 20 µg mL-1 for EZE and SIM in both methods. The accuracy and precision of the methods were assessed. These methods were successfully applied to a pharmaceutical preparation, tablet; and the results were compared with each other.

Chemical pattern of brazilian apples: a chemometric approach based on the Fuji and Gala varieties

The chemical composition of apple juices may be used to discriminate between the varieties for consumption and those for raw material. Fuji and Gala have a chemical pattern that can be used for this classification. Multivariate methods correlate independent continuous chemical descriptors with the categorical apple variety. Three main descriptors of apple juice were selected: malic acid, total reducing sugar and total phenolic compounds. A chemometric approach, employing PCA and SIMCA, was used to classify apple juice samples. PCA was performed with 24 juices from Fuji and Gala, and SIMCA, with 15 juices. The exploratory and predictive models recognized 88% and 64%, respectively, as belonging to a mixed domain. The apple juice from commercial fruits shows a pattern related to cv. Fuji and Gala with boundaries from 0.18 to 0.389 g.100 mL-1 (malic acid), from 8.65 to 15.18 g.100 mL-1 (total reducing sugar) and from 100 to 400 mg.L-1 (total phenolic compounds), but such boundaries were slightly shorter in the remaining set of commercial apple juices, specifically from 0.16 to 0.36 g.100 mL-1, from 9.25 to 15.5 g.100 mL-1 and from 180 to 606 mg.L-1 for acidity, reducing sugar and phenolic compounds, respectively, representing the acid, sweet and bitter tastes.

Methods to classify maize cultivars in use efficiency and response to nitrogen

n plant breeding programs that aim to obtain cultivars with nitrogen (N) use efficiency, the focus is on methods of selection and experimental procedures that present low cost, fast response, high repeatability, and can be applied to a large number of cultivars. Thus, the objectives of this study were to classify maize cultivars regarding their use efficiency and response to N in a breeding program, and to validate the methodology with contrasting doses of the nutrient. The experimental design was a randomized block with the treatments arranged in a split-plot scheme with three replicates and five N doses (0, 30, 60, 120 and 200 kg ha-1) in the plots, and six cultivars in subplots. We compared a method examining the efficiency and response (ER) with two contrasting doses of N. After that, the analysis of variance, mean comparison and regression analysis were performed. In conclusion, the method of the use efficiency and response based on two N levels classifies the cultivars in the same way as the regression analysis, and it is appropriate in plant breeding routine. Thus, it is necessary to identify the levels of N required to discriminate maize cultivars in conditions of low and high N availability in plant breeding programs that aim to obtain efficient and responsive cultivars. Moreover, the analysis of the interaction genotype x environment at experiments with contrasting doses is always required, even when the interaction is not significant.

Comparison of different methods for the determination of total organic carbon and humic substances in Brazilian soils

ABSTRACTAiming to compare three different methods for the determination of organic carbon (OC) in the soil and fractions of humic substances, seventeen Brazilian soil samples of different classes and textures were evaluated. Amounts of OC in the soil samples and the humic fractions were measured by the dichromate-oxidation method, with and without external heating in a digestion block at 130 °C for 30 min; by the loss-on-ignition method at 450 °C during 5 h and at 600 °C during 6 h; and by the dry combustion method. Dry combustion was used as reference in order to measure the efficiency of the other methods. Soil OC measured by the dichromate-oxidation method with external heating had the highest efficiency and the best results comparing to the reference method. When external heating was not used, the mean recovery efficiency dropped to 71%. The amount of OC was overestimated by the loss-on-ignition methods. Regression equations obtained between total OC contents of the reference method and those of the other methods showed relatively good adjustment, but all intercepts were different from zero (p < 0.01), which suggests that more accuracy can be obtained using not one single correction factor, but considering also the intercept. The Walkley-Black method underestimated the OC contents of the humic fractions, which was associated with the partial oxidation of the humin fraction. Better results were obtained when external heating was used. For the organic matter fractions, the OC in the humic and fulvic acid fractions can be determined without external heating if the reference method is not available, but the humin fraction requires the external heating.

Impacts of vinasse and methods of sugarcane harvesting on the availability of K and carbon stock of an Argisol

ABSTRACT Soils of tropical regions are more weathered and in need of conservation managements to maintain and improve the quality of its components. The objective of this study was to evaluate the availability of K, the organic matter content and the stock of total carbon of an Argisol after vinasse application and manual and mechanized harvesting of burnt and raw sugarcane, in western São Paulo.The data collection was done in the 2012/2013 harvest, in a bioenergy company in Presidente Prudente/SP. The research was arranged out following a split-plot scheme in a 5x5 factorial design, characterized by four management systems: without vinasse application and harvest without burning; with vinasse application and harvest without burning; with vinasse application and harvest after burning; without vinasse application and harvest after burning; plus native forest, and five soil sampling depths (0-10 10-20, 20-30, 30-40, 40-50 cm), with four replications. In each treatment, the K content in the soil and accumulated in the remaining dry biomass in the area, the levels of organic matter, organic carbon and soil carbon stock were determined. The mean values were compared by Tukey test. The vinasse application associated with the harvest without burning increased the K content in soil layers up to 40 cm deep. The managements without vinasse application and manual harvest after burning, and without vinasse application with mechanical harvesting without burning did not increase the levels of organic matter, organic carbon and stock of total soil organic carbon, while the vinasse application and harvest after burning and without burning increased the levels of these attributes in the depth of 0-10 cm.

Comparison of methods for classification of the coefficient of variation in papaya

ABSTRACT The objective of this work was to study the distribution of values of the coefficient of variation (CV) in the experiments of papaya crop (Carica papaya L.) by proposing ranges to guide researchers in their evaluation for different characters in the field. The data used in this study were obtained by bibliographical review in Brazilian journals, dissertations and thesis. This study considered the following characters: diameter of the stalk, insertion height of the first fruit, plant height, number of fruits per plant, fruit biomass, fruit length, equatorial diameter of the fruit, pulp thickness, fruit firmness, soluble solids and internal cavity diameter, from which, value ranges were obtained for the CV values for each character, based on the methodology proposed by Garcia, Costa and by the standard classification of Pimentel-Gomes. The results obtained in this study indicated that ranges of CV values were different among various characters, presenting a large variation, which justifies the necessity of using specific evaluation range for each character. In addition, the use of classification ranges obtained from methodology of Costa is recommended.