Quimiometria II: planilhas eletrônicas para cálculos de planejamentos experimentais, um tutorial

This work describes, through examples, a simple way to carry out experimental design calculations applying an spreadsheets. The aim of this tutorial is to introduce an alternative to sophisticated commercial programs that normally are too complex in data input and output. An overview of the principal methods is also briefly presented. The spreadsheets are suitable to handle different types of computations such as screening procedures applying factorial design and the optimization procedure based on response surface methodology. Furthermore, the spreadsheets are sufficiently versatile to be adapted to specific experimental designs.

Classificação de água de coco processada e natural por meio de HCA, PCA e teores de íons metálicos determinados por ICP OES

Inductively Coupled Plasma Optical Emission Spectrometry was used to determine Ca, Mg, Mn, Fe, Zn and Cu in samples of processed and natural coconut water. The sample preparation consisted in a filtration step followed by a dilution. The analysis was made employing optimized instrumental parameters and the results were evaluated using methods of Pattern Recognition. The data showed common concentration values for the analytes present in processed and natural samples. Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) indicated that the samples of different kinds were statistically different when the concentrations of all the analytes were considered simultaneously.

25 anos de quimiometria no Brasil

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.

Reconhecimento de padrões por métodos não supervisionados: explorando procedimentos quimiométricos para tratamento de dados analíticos

An activity for introducing hierarchical cluster analysis (HCA) and principal component analysis (PCA) during the Instrumental Analytical Chemistry course is presented. The posed problem involves the discrimination of mineral water samples according to their geographical origin. Thirty-seven samples of 9 different brands were considered and the results from the determination of Na, K, Mg, Ca, Sr and Ba were taken into account. Non-supervised methods for pattern recognition were explored to construct a dendrogram, score and loading plots. The devised activity can be adopted for introducing Chemometrics devoted to data handling, stressing its importance in the context of modern Analytical Chemistry.

Estudo da capacidade de complexação e sua relação com algumas variáveis ambientais em cinco represas do Rio Tietê/Brasil

The copper and cadmium complexation properties in natural sediment suspensions of reservoirs of the Tietê River were studied using the solid membrane copper and cadmium ion-selective electrodes. The complexation and the average conditional stability constants were determined under equilibrium conditions at pH=6.00 ± 0.05 in a medium of 1.0 mol L-1 sodium nitrate, using the Scatchard method. The copper and cadmium electrodes presented Nernstian behavior from 1x10-6 to 1x10-3 mol L-1 of total metal concentration. Scatchard graphs suggest two classes of binding sites for both metals. A multivariate study was done to correlate the reservoirs and the variables: complexation properties, size, total organic carbon, volatile acid sulfide, E II and pH.

Análise multivariada de parâmetros físico-químicos em amostras de vinhos tintos comercializados na região metropolitana do Recife

The Brazilian legislation requires analysis of certain parameters to classify a wine and allow its commercialization. Some physico-chemical and some color parameters were determined in this work in samples of different red wines sold in the metropolitan area of Recife. Multivariate analysis comprising principal component analysis and hierarchical cluster analysis was employed to distinguish the analyzed wines. The results for pH, chloride concentration, color parameters and ammonium content were the most important variables for sample classification. It was also possible to classify the wines as soft or dry wines and amongst the soft wines we could determine two out of four winegrowing producers.

Distinção entre cachaças destiladas em alambiques e em colunas usando quimiometria

One hundred fifteen cachaça samples derived from distillation in copper stills (73) or in stainless steels (42) were analyzed for thirty five itens by chromatography and inductively coupled plasma optical emission spectrometry. The analytical data were treated through Factor Analysis (FA), Partial Least Square Discriminant Analysis (PLS-DA) and Quadratic Discriminant Analysis (QDA). The FA explained 66.0% of the database variance. PLS-DA showed that it is possible to distinguish between the two groups of cachaças with 52.8% of the database variance. QDA was used to build up a classification model using acetaldehyde, ethyl carbamate, isobutyl alcohol, benzaldehyde, acetic acid and formaldehyde as chemical descriptors. The model presented 91.7% of accuracy on predicting the apparatus in which unknown samples were distilled.

Análise screening de vinhos empregando um analisador fluxo-batelada, espectroscopia UV-VIS e quimiometria

A simple, robust, versatile, high analytical frequency method was proposed to check if a sample of wine is within the range of standards set by the manufacturer, using the UV-VIS spectroscopy, multivariate analysis and a flow-batch analyzer. Two hundred and fifty-two samples of wines were analyzed. The results from the application of Hierachical Cluster Analysis (HCA) to the matrix of the data involving all samples show the formation of fifteen types of wine. A Soft Independent Modelling of Class Analogy (SIMCA) model was constructed and used to classify the samples of the overall forecast. As a result, it is observed that the prediction was performed with a success rate of 99.2% for a confidence level of 95%. This shows that the proposed methodology can be used as an effective tool for classifying of samples of wines.

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.

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

Espectroscopia no infravermelho médio e análise sensorial aplicada à detecção de adulteração de café torrado por adição de cascas de café

Mid-infrared spectroscopy and chemometrics were used to identify adulteration in roasted and ground coffee by addition of coffee husks. Consumers' sensory perception of the adulteration was evaluated by a triangular test of the coffee beverages. Samples containing above 0.5% of coffee husks from pure coffees were discriminated by principal component analysis of the infrared spectra. A partial least-squares regression estimated the husk content in samples and presented a root-mean-square error for prediction of 2.0%. The triangular test indicated that were than 10% of coffee husks are required to cause alterations in consumer perception about adulterated beverages.

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.

O tempo de pega em gelatinas comerciais: uma experiência da disciplina de quimiometria para estudantes de graduação em Química

The aim of this paper is to describe a chemometrics experiment for undergraduate chemistry students using basic concepts of experimental design to determine setting-time of commercial gelatins.

Grape juice quality control by means of ¹H nmr spectroscopy and chemometric analyses

This work shows the application of ¹H NMR spectroscopy and chemometrics for quality control of grape juice. A wide range of quality assurance parameters were assessed by single ¹H NMR experiments acquired directly from juice. The investigation revealed that conditions and time of storage should be revised and indicated on all labels. The sterilization process of homemade grape juices was efficient, making it possible to store them for long periods without additives. Furthermore, chemometric analysis classified the best commercial grape juices to be similar to homemade grape juices, indicating that this approach can be used to determine the authenticity after adulteration.

Resolução multivariada de curvas com mínimos quadrados alternantes: descrição, funcionamento e aplicações

Multivariate Curve Resolution with Alternating Least Squares (MCR-ALS) is a resolution method that has been efficiently applied in many different fields, such as process analysis, environmental data and, more recently, hyperspectral image analysis. When applied to second order data (or to three-way data) arrays, recovery of the underlying basis vectors in both measurement orders (i.e. signal and concentration orders) from the data matrix can be achieved without ambiguities if the trilinear model constraint is considered during the ALS optimization. This work summarizes different protocols of MCR-ALS application, presenting a case study: near-infrared image spectroscopy.