CHEMOSTAT, UM SOFTWARE GRATUITO PARA ANÁLISE EXPLORATÓRIA DE DADOS MULTIVARIADOS

The objective of this work was to develop a free access exploratory data analysis software application for academic use that is easy to install and can be handled without user-level programming due to extensive use of chemometrics and its association with applications that require purchased licenses or routines. The developed software, called Chemostat, employs Hierarchical Cluster Analysis (HCA), Principal Component Analysis (PCA), intervals Principal Component Analysis (iPCA), as well as correction methods, data transformation and outlier detection. The data can be imported from the clipboard, text files, ASCII or FT-IR Perkin-Elmer “.sp” files. It generates a variety of charts and tables that allow the analysis of results that can be exported in several formats. The main features of the software were tested using midinfrared and near-infrared spectra in vegetable oils and digital images obtained from different types of commercial diesel. In order to validate the software results, the same sets of data were analyzed using Matlab© and the results in both applications matched in various combinations. In addition to the desktop version, the reuse of algorithms allowed an online version to be provided that offers a unique experience on the web. Both applications are available in English.

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.

ANÁLISE EXPLORATÓRIA DAS CONCENTRAÇÕES DOS METAIS NA, CA, MG, SR E FE EM EXTRATO AQUOSO DE PETRÓLEO, DETERMINADOS POR ICP OES, APÓS OTIMIZAÇÃO EMPREGANDO PLANEJAMENTO DE EXPERIMENTOS

AbstractThe purpose of this study was to evaluate the best operating conditions of ICP OES for the determination of Na, Ca, Mg, Sr and Fe in aqueous extract of crude oil obtained after hot extraction with organic solvents (ASTM D 6470-99 modified). Thus, the full factorial design and central composite design were used to optimize the best conditions for the flow of nebulization gas, the flow of auxiliary gas, and radio frequency power. After optimization of variables, a study to obtain correct classification of the 18 samples of aqueous extract of crude oils (E1 to E18) from three production and refining fields was carried out. Exploratory analysis of these extracts was performed by principal component analysis (PCA), hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA), using the original variables as the concentration of the metals Na, Ca, Mg, Sr and Fe determined by ICP OES.

APPLICATION OF PARAFAC AND OPLS-DA ANALYSES ON HPLC FINGERPRINTS FOR THE CHARACTERIZATION OF Hibiscus sabdariffaCALYXES

The calyxes of Hibiscus sabdariffa are used in traditional medicine around the world. However, quality assurance protocols and chemical variability have not been previously analyzed. In the present study, chemical characterization of a set of samples of H. sabdariffa calyxes commercialized in Colombia was accomplished with the aim to explore the chemical variability among them. Chemometrics-based analyses on the data obtained from the HPLC-UV-DAD-derived profiles were then performed. Thus, the pre-processed single-wavelength data were subjected to principal component analysis (PCA). The PCA-derived results evidenced different groups which were well-correlated to the corresponding total phenolic and total anthocyanin contents. Multi-wavelength chromatographic (HPLC-UV-DAD surfaces) data were additionally examined via parallel factor analysis (PARAFAC) as data reduction method and the obtained loadings were subsequently submitted to PCA and orthogonal partial least squares discriminant analysis (OPLS-DA). Results were thus consistent with those from single-wavelength data. PCA loadings were employed to determine those chemical components responsible for the data variance and OPLS-DA model, constructed from PARAFAC loadings, and indicated differentiation according total anthocyanin contents among samples. The present chemometric analysis therefore demonstrated to be an excellent tool for differentiation of H. sabdariffacalyxes according to their chemical composition.

PROPOSTA EXPERIMENTAL DIDÁTICA PARA O ENSINO DE ANÁLISE DE COMPONENTES PRINCIPAIS

Principal component analysis (PCA) is a chemometric method that allows for the extraction of chemical information that would otherwise be impossible to determine. Teaching chemometrics to undergraduates can contribute to the overall professional development and training of new teachers, whose profiles have been gaining attention due to the current demand for data interpretation. In this study, a didactic experiment involving PCA is proposed. Spectrophotometry was used in the ultraviolet-visible (UV-Vis) region to assess the behavior of anthocyanins extracted from red cabbage at different pH values. The results suggest the possible separation of anthocyanin structures into three distinct groups, according to their chemical characteristics displayed in acid, neutral, and basic media. The objective is to develop educational materials targeted to undergraduate courses, which encompass a larger number of concepts and introduce instrumental techniques currently being employed in both academic research and the industrial sector. Specifically, the proposed experiment introduces concepts related to spectrophotometry in the UV-Vis range and the PCA chemometric method. The materials used are easily accessible, and UV-Vis spectroscopy equipment is less expensive in comparison with other spectroscopy methods.

COMPARAÇÃO ENTRE FUNCIONAIS DE DENSIDADE NO ESTUDO DE PROPRIEDADES ELETRÔNICAS DE DERIVADOS DA ARTEMISININA

The present paper demonstrates the application of functional GGA hybrids, with long-range corrections, for the calculation of the electronic properties of artemisinin and two of its derivatives - artemether e artesunate. Due to the relatively large amount of data obtained, the statistical method of Principal Component Analysis was employed. The functionals of the WB97 family are observed to be the most appropriate for the determining of reactivity indexes, which are the principal descriptors that, probably, are associated with the antimalarial and anticancer properties of this group of molecules. In addition, it was also observed that all the functionals obtained satisfactorily describe the geometric properties of the studied.

Chlorophyll fluorescence of tropical tree species in a semi-deciduous forest gap

The characterization of different ecological groups in a forest formation/succession is unclear. To better define the different successional classes, we have to consider ecophysiological aspects, such as the capacity to use or dissipate the light energy available. The main objective of this work was to assess the chlorophyll fluorescence emission of tropical tree species growing in a gap of a semi-deciduous forest. Three species of different ecological groups were selected: Croton floribundus Spreng. (pioneer, P), Astronium graveolens Jacq. (early secondary, Si), and Esenbeckia febrifuga A. Juss. (late secondary, St). The potential (Fv/Fm) and effective (deltaF/Fm') quantum efficiency of photosystem II, apparent electron transport rate (ETR), non-photochemical (qN) and photochemical (qP) quenching of fluorescence were evaluated, using a modulated fluorometer, between 7:30 and 11:00 h. Values of Fv/Fm remained constant in St, decreasing in P and Si after 9:30 h, indicating the occurrence of photoinhibition. Concerning the measurements taken under light conditions (deltaF/Fm', ETR, qP and qN), P and Si showed better photochemical performance, i.e., values of deltaF/Fm', ETR and qP were higher than St when light intensity was increased. Values of qN indicated that P and Si had an increasing tendency of dissipating the excess of energy absorbed by the leaf, whereas the opposite was found for St. The principal component analysis (PCA), considering all evaluated parameters, showed a clear distinction between St, P and Si, with P and Si being closer. The PCA results suggest that chlorophyll fluorescence may be a potential tool to differentiate tree species from distinct successional groups.

Photosynthetic responses of tropical tree species from different successional groups under contrasting irradiance conditions

This study evaluated the photosynthetic responses of seven tropical trees of different successional groups under contrasting irradiance conditions, taking into account changes in gas exchange and chlorophyll a fluorescence. Although early successional species have shown higher values of CO2 assimilation (A) and transpiration (E), there was not a defined pattern of the daily gas exchange responses to high irradiance (FSL) among evaluated species. Cariniana legalis (Mart.) Kuntze (late secondary) and Astronium graveolens Jacq. (early secondary) exhibited larger reductions in daily-integrated CO2 assimilation (DIA) when transferred from medium light (ML) to FSL. On the other hand, the pioneer species Guazuma ulmifolia Lam. had significant DIA increase when exposed to FSL. The pioneers Croton spp. trended to show a DIA decrease around 19%, while Cytharexyllum myrianthum Cham. (pioneer) and Rhamnidium elaeocarpum Reiss. (early secondary) trended to increase DIA when transferred to FSL. Under this condition, all species showed dynamic photoinhibition, except for C. legalis that presented chronic photoinhibition of photosynthesis. Considering daily photosynthetic processes, our results supported the hypothesis of more flexible responses of early successional species (pioneer and early secondary species). The principal component analysis indicated that the photochemical parameters effective quantum efficiency of photosystem II and apparent electron transport rate were more suitable to separate the successional groups under ML condition, whereas A and E play a major role to this task under FSL condition.

Influence of soil properties on the abundance of plant species in ferruginous rocky soils vegetation, southeastern Brazil

Ferruginous "campos rupestres" are a particular type of vegetation growing on iron-rich primary soils. We investigated the influence of soil properties on plant species abundance at two sites of ferruginous "campos rupestres" and one site of quartzitic "campo rupestre", all of them in "Quadrilátero Ferrífero", in Minas Gerais State, southeastern Brazil. In each site, 30 quadrats were sampled to assess plant species composition and abundance, and soil samples were taken to perform chemical and physical analyses. The analyzed soils are strongly acidic and presented low fertility and high levels of metallic cations; a principal component analysis of soil data showed a clear segregation among sites due mainly to fertility and heavy metals content, especially Cu, Zn, and Pb. The canonical correspondence analysis indicated a strong correlation between plant species abundance and soil properties, also segregating the sites.

Validation of the Beck Depression Inventory for a Portuguese-speaking Chinese community in Brazil

The objective of the present study was to investigate the psychometric properties and cross-cultural validity of the Beck Depression Inventory (BDI) among ethnic Chinese living in the city of São Paulo, Brazil. The study was conducted on 208 community individuals. Reliability and discriminant analysis were used to test the psychometric properties and validity of the BDI. Principal component analysis was performed to assess the BDI's factor structure for the total sample and by gender. The mean BDI score was lower (6.74, SD = 5.98) than observed in Western counterparts and showed no gender difference, good internal consistency (Cronbach's alpha 0.82), and high discrimination of depressive symptoms (75-100%). Factor analysis extracted two factors for the total sample and each gender: cognitive-affective dimension and somatic dimension. We conclude that depressive symptoms can be reliably assessed by the BDI in the Brazilian Chinese population, with a validity comparable to that for international studies. Indeed, cultural and measurement biases might have influenced the response of Chinese subjects.

Discrimination of Brazilian red wines according to the viticultural region, varietal, and winery origin

This work evaluated the physicochemical composition of 171 red Brazilian wines from the 2006 vintage, which were represented by 21 varietals. These wines were produced by 58 Brazilian wineries in different regions of the country, with latitudes varying from 9º to 31º South. Physicochemical wine analysis was performed in the same year and discrimination in the viticultural regions, varietal wines, and wineries was performed by means of the principal component analysis (PCA). The main results show that wines from São Joaquim had higher values of A420, A520, A620, color intensity, total phenolic compounds, anthocyanins, and dry extracts, while those from Toledo had lower values of these variables; those from Vale do São Francisco had higher values of potassium, pH, density, and volatile acidity; from Serra do Nordeste A, they had higher titratable acidity; and from Planalto Superior B, higher hue. Regarding the varietal wines, PCA mainly discriminated the wines produced from the varieties Ancellotta, Teroldego, Egiodola, Refosco, Marselan, Cabernet Sauvignon, Pinotage, Pinot Noir, Malbec, Arinarnoa, Barbera, and Alfrocheiro. In relation to wineries, twenty two of them were discriminated by their higher values of some variables, i.e., three were characterized by color intensity; three by hue; eight by alcohol content; six by potassium, dry extract, density, and pH; and two by titratablel acidity.

Sensory profile of Italian salami with coriander (Coriandrum sativum L.) essential oil

The descriptive terminology and sensory prolife of four samples of Italian salami were determined using a methodology based on the Quantitative Descriptive Analysis (QDA). A sensory panel consensually defined sensory descriptors, their respective reference materials, and the descriptive evaluation ballot. Twelve individuals were selected as judges and properly trained. They used the following criteria: discriminating power, reproducibility, and individual consensus. Twelve descriptors were determined showing similarities and differences among the Italian salami samples. Each descriptor was evaluated using a 10 cm non-structured scale. The data were analyzed by ANOVA, Tukey test, and the Principal Component Analysis (PCA). The salami with coriander essential oil (T3) had lower rancid taste and rancid odor, whereas the control (T1) showed high values of these sensory attributes. Regarding brightness, T4 showed the best result. For the other attributes, T1, T2, T3, and T4 were similar.

Sensory profile of 'Douradão' peaches cold stored under controlled atmosphere

The sensory quality of 'Douradão' peaches cold stored in three different conditions of controlled atmosphere (CA1, CA2, CA3 and Control) was studied. After 14, 21 and 28 days of cold storage, samples were withdrawn from CA and kept for 4 days in ambient air for ripening. The sensory profile of the peaches and the descriptive terminology were developed by methodology based on the Quantitative Descriptive Analysis (QDA). The panelists consensually defined the sensory descriptors, their respective reference materials and the descriptive evaluation ballot. Fourteen panelists were selected based on their discrimination capacity and reproducibility. Seven descriptors were generated showing similarities and differences between samples. The data were analyzed by ANOVA, Tukey test and Principal Component Analysis (PCA). Results showed significant differences in the sensory profiles of the peaches. The PCA showed that CA2 and CA3 treatments were more characterized by the fresh peach flavor, fresh peach appearance, juiciness and flesh firmness, and were effective in keeping the good quality of the 'Douradão' peaches during the 28 days of cold storage. The Control and CA1 treatments were characterized by the mealiness and were ineffective for quality maintenance of the fruits during cold storage.

Monitoring of wine aging process by electrospray ionization mass spectrometry

The characterization of wine samples by direct insertion electrospray ionization mass spectrometry (ESI-MS), without pre-treatment or chromatographic separation, in a process denominated fingerprinting, has been applied to several samples of wine produced with grapes of the Pinot noir, Merlot and Cabernet Sauvignon varieties from the state o Rio Grande do Sul, in Brazil. The ESI-MS fingerprints of the samples detected changes which occurred during the aging process in the three grape varieties. Principal Component Analysis (PCA) of the negative ion mode fingerprints was used to group the samples, pinpoint the main changes in their composition, and indicate marker ions for each group of samples.

Characterization of Brazilian wheat cultivars for specific technological applications

Functional and technological properties of wheat depend on its chemical composition, which together with structural and microscopic characteristics, define flour quality. The aim of the present study was to characterize four Brazilian wheat cultivars (BRS Louro, BRS Timbauva, BRS Guamirim and BRS Pardela) and their respective flours in order to indicate specific technological applications. Kernels were analyzed for test weight, thousand kernel weight, hardness, moisture, and water activity. Flours were analyzed for water activity, color, centesimal composition, total dietary fiber, amylose content and identification of high molecular weight glutenins. The rheological properties of the flours were estimated by farinography, extensography, falling number, rapid visco amylography, and glutomatic and glutork equipment. Baking tests and scanning electron microscopy were also performed. The data were subjected to analysis of variance and principal component analysis. BRS Timbauva and BRS Guamirim presented results that did not allow for specific technological application. On the other hand, BRS Louro presented suitable characteristics for the elaboration of products with low dough strength such as cakes, pies and biscuits, while BRS Pardela seemed suitable for bread and pasta products.