Uma introdução à análise exploratória de dados multivariados

The modern technological ability to handle large amounts of information confronts the chemist with the necessity to re-evaluate the statistical tools he routinely uses. Multivariate statistics furnishes theoretical bases for analyzing systems involving large numbers of variables. The mathematical calculations required for these systems are no longer an obstacle due to the existence of statistical packages that furnish multivariate analysis options. Here basic concepts of two multivariate statistical techniques, principal component and hierarchical cluster analysis that have received broad acceptance for treating chemical data are discussed.

Calibração multivariada para sistemas com bandas sobrepostas através da análise da fatores do tipo Q

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.

Chemical characterization of tin-lead glazed pottery from the Iberian Peninsula and the Canary Islands: initial steps toward a better understanding of Spanish Colonial pottery in Americas

Majolica pottery was the most characteristic tableware produced in Europe during the Medieval and Renaissance periods. Because of the prestige and importance attributed to this ware, Spanish majolica was imported in vast quantities into the Americas during the Spanish Colonial period. A study of Spanish majolica was conducted on a set of 186 samples from the 10 primary majolica production centres on the Iberian Peninsula and 22 sherds from two early colonial archaeological sites on the Canary Islands. The samples were analysed by neutron activation analysis (NAA), and the resulting data were interpreted using an array of multivariate statistical approaches. Our results show a clear discrimination between different production centres, allowing a reliable provenance attribution of the sherds from the Canary Islands.

Reaction Kinetics and Viscosity Modelling in the Fusion Syntheses of Ca- and Ca/Mg-resinates

Rosin is a natural product from pine forests and it is used as a raw material in resinate syntheses. Resinates are polyvalent metal salts of rosin acids and especially Ca- and Ca/Mg- resinates find wide application in the printing ink industry. In this thesis, analytical methods were applied to increase general knowledge of resinate chemistry and the reaction kinetics was studied in order to model the non linear solution viscosity increase during resinate syntheses by the fusion method. Solution viscosity in toluene is an important quality factor for resinates to be used in printing inks. The concept of critical resinate concentration, c crit, was introduced to define an abrupt change in viscosity dependence on resinate concentration in the solution. The concept was then used to explain the non-inear solution viscosity increase during resinate syntheses. A semi empirical model with two estimated parameters was derived for the viscosity increase on the basis of apparent reaction kinetics. The model was used to control the viscosity and to predict the total reaction time of the resinate process. The kinetic data from the complex reaction media was obtained by acid value titration and by FTIR spectroscopic analyses using a conventional calibration method to measure the resinate concentration and the concentration of free rosin acids. A multivariate calibration method was successfully applied to make partial least square (PLS) models for monitoring acid value and solution viscosity in both mid-infrared (MIR) and near infrared (NIR) regions during the syntheses. The calibration models can be used for on line resinate process monitoring. In kinetic studies, two main reaction steps were observed during the syntheses. First a fast irreversible resination reaction occurs at 235 °C and then a slow thermal decarboxylation of rosin acids starts to take place at 265 °C. Rosin oil is formed during the decarboxylation reaction step causing significant mass loss as the rosin oil evaporates from the system while the viscosity increases to the target level. The mass balance of the syntheses was determined based on the resinate concentration increase during the decarboxylation reaction step. A mechanistic study of the decarboxylation reaction was based on the observation that resinate molecules are partly solvated by rosin acids during the syntheses. Different decarboxylation mechanisms were proposed for the free and solvating rosin acids. The deduced kinetic model supported the analytical data of the syntheses in a wide resinate concentration region, over a wide range of viscosity values and at different reaction temperatures. In addition, the application of the kinetic model to the modified resinate syntheses gave a good fit. A novel synthesis method with the addition of decarboxylated rosin (i.e. rosin oil) to the reaction mixture was introduced. The conversion of rosin acid to resinate was increased to the level necessary to obtain the target viscosity for the product at 235 °C. Due to a lower reaction temperature than in traditional fusion synthesis at 265 °C, thermal decarboxylation is avoided. As a consequence, the mass yield of the resinate syntheses can be increased from ca. 70% to almost 100% by recycling the added rosin oil.

Tratamento estatístico dos parâmetros da qualidade das águas da bacia do alto curso do Rio das Velhas

Water quality was monitored at the upper course of the Rio das Velhas, a major tributary of the São Francisco basin located in the state of Minas Gerais, over an extension of 108 km from its source up to the limits with the Sabara district. Monitoring was done at 37 different sites over a period of 2 years (2003-2004) for 39 parameters. Multivariate statistical techniques were applied to interpret the large water-quality data set and to establish an optimal long-term monitoring network. Cluster analysis separated the sampling sites into groups of similarity, and also indicated the stations investigated for correlation and recommended to be removed from the monitoring network. Principal component analysis identified four components, which are responsible for the data structure explaining 80% of the total variance of the data. The principal parameters are characterized as due to mining activities and domestic sewage. Significant data reduction was achieved.

LS-SVM: uma nova ferramenta quimiométrica para regressão multivariada. Comparação de modelos de regressão LS-SVM e PLS na quantificação de adulterantes em leite em pó empregando NIR

Least-squares support vector machines (LS-SVM) were used as an alternative multivariate calibration method for the simultaneous quantification of some common adulterants found in powdered milk samples, using near-infrared spectroscopy. Excellent models were built using LS-SVM for determining R², RMSECV and RMSEP values. LS-SVMs show superior performance for quantifying starch, whey and sucrose in powdered milk samples in relation to PLSR. This study shows that it is possible to determine precisely the amount of one and two common adulterants simultaneously in powdered milk samples using LS-SVM and NIR spectra.

Avaliação do efeito da piscicultura em sistemas aquáticos em Assis e Cândido Mota, São Paulo, por indicador de qualidade da água e análise estatítica multivariada

In this work, the impact of fish farming activities on the Queixada, Macuco and Pari-Veado Rivers in the Paranapanema watershed was evaluated. Physical, chemical and microbiological parameters were quantified in these aquatic systems followed by application of multivariate statistical analysis (MSA) and water quality index (WQI) tools. Watersheds where fish farming activities are predominant presented WQI > 52 indicating good quality, whereas MSA demonstrated bad quality for these aquatic bodies. The results showed that the degradation in this watershed follows the fish farming activity. The MSA index is more restricted than the "National Foundation Sanitation" (NFS) index routinely used to infer water quality.

Perfil químico de cultivares de feijão (phaseolus vulgaris) pela técnica de high resolution magic angle spinning (HR-MAS)

The application of one-dimensional proton high-resolution magic angle spinning (¹H HR-MAS) NMR combined with a typical advantages of solid and liquid-state NMR techniques was used as input variables for the multivariate statistical analysis. In this paper, different cultivars of beans (Phaseolus vulgaris) developed and in development by Embrapa - Arroz e Feijão were analyzed by ¹H HR-MAS, which have been demonstrated to be a valuable tool in its differentiation according chemical composition and avoid the manipulation of the samples as used in other techniques.

Adsorção de Cr(VI) em esferas reticuladas de quitosana: novas correlações cinéticas e termodinâmicas utilizando microcalorimetria isotérmica contínua

The synthesis and characterization of crosslinked chitosan microbeads and their application in the removal of Cr(VI) are described. New kinetic and thermodynamic parameters of Cr(VI) adsorptions processes were found using continuous isothermal calorimetry. All adsorption processes are exothermic in nature. However, a multivariate statistical analysis have pointed out that adsorption enthalpies were affected by important binary interactions of the initial Cr(VI) in solution and temperature. The adsorption energetic data were well fitted to a kinetic exponential model, which have indicated fractionary adsorption kinetic orders.

Aplicação de métodos quimiométricos na caracterização de charutos utilizando extração por dispersão da matriz em fase sólida e análise por cromatografia gasosa acoplada à espectrometria de massas

In this work, the organic compounds of cigar samples from different brands were analyzed. The compound extraction was made using the matrix solid-phase dispersion (MSPD) technique, followed by gas chromatography and identification by mass spectrometry (GC-MS) and standards, when available. Thirty eight organic compounds were found in seven different brands. Finally, with the objective of characterizing and discriminating the cigar samples, multivariate statistical analyses were applied to data, e.g.; principal component analysis (PCA) and hierarchical cluster analysis (HCA). With such analyses, it was possible to discriminate three main groups of three quality levels.

Determinação simultânea de ácido kójico e hidroquinona por espectrofotometria visível e calibração multivariada

A multivariate spectrophotometric method was developed for analysis of kojic acid/hydroquinone associations in skin whitening cosmetics. The method is based on the reaction between kojic acid and Fe3+ and on the reduction of Fe3+ by hydroquinone and further complexation of Fe2+ with 1,10-phenanthroline. The multivariate model was developed by Partial Least Squares Regression (PLSR), using 25 synthetic mixtures and mean-centered spectral data (350-380 nm). The use of 3 (kojic acid) and 2 (hydroquinone) latent variables permits the observation of mean errors of about 5% in the external validation phase.

Avaliação do perfil de dissolução de medicamentos utilizando-se espectroscopia eletrônica multivariada

In this work the evaluation of the dissolution profile of captopril-hydrochlorothiazide and zidovudine-lamivudine associations were carried out by multivariate spectroscopic method. The models were developed by partial least square regression from 20 synthetic mixtures using mean-centered spectral data. The external validation was accomplished with 5 synthetic mixtures shown mean prevision error of about 1%. Good agreement was observed in the analyses of commercial drugs (content uniformity and dissolution profile), considering the results obtained by the standard chromatographic method, with prevision error lower than 10%.

A formação dos docentes de química: uma perspectiva multivariada aplicada à rede pública de ensino médio de Goiás

This paper presents a multivariate statistical analysis as a valuable tool for educational management applied to public high school chemistry teacher formation. From 2003 to 2007, a decrease of 10% in the number of public high schools was seen, as well as a reduction of 7% in the number of teachers. Contrarily, there was an increase in the number of university graduate teachers. Principal Component Analyses reveal that in 2003, most chemistry teachers were not university graduates. In 2007, eight Regional Offices of Education reported teachers holding academic degrees, qualifying them as chemistry teacher in the school system

Ácidos fenólicos, flavonoides e atividade antioxidante em méis de Melipona fasciculata, M. flavolineata (Apidae, Meliponini) e Apis mellifera (Apidae, Apini) da Amazônia

Honey produced by three stingless bee species (Melipona flavolineata, M. fasciculata and Apis mellifera) from different regions of the Amazon was analyzed by separating phenolic acids and flavonoids using the HPLC technique. Data were subjected to multivariate statistical analysis (PCA, HCA and DA). Results showed the three species of honey samples could be distinguished by phenolic composition. Antioxidant activity of the honeys was determined by studying the capacity of inhibiting radicals using DPPH assay. Honeys with higher phenolic compound contents had greater antioxidant capacity and darker color.

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.