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.

Experimento didático de quimiometria para análise exploratória de óleos vegetais comestíveis por espectroscopia no infravermelho médio e análise de componentes principais: um tutorial, parte I

This manuscript aims to show the basic concepts and practical application of Principal Component Analysis (PCA) as a tutorial, using Matlab or Octave computing environment for beginners, undergraduate and graduate students. As a practical example it is shown the exploratory analysis of edible vegetable oils by mid infrared spectroscopy.

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.

Quimiometria I: calibração multivariada, um tutorial

The aim of this work is to present a tutorial on Multivariate Calibration, a tool which is nowadays necessary in basically most laboratories but very often misused. The basic concepts of preprocessing, principal component analysis (PCA), principal component regression (PCR) and partial least squares (PLS) are given. The two basic steps on any calibration procedure: model building and validation are fully discussed. The concepts of cross validation (to determine the number of factors to be used in the model), leverage and studentized residuals (to detect outliers) for the validation step are given. The whole calibration procedure is illustrated using spectra recorded for ternary mixtures of 2,4,6 trinitrophenolate, 2,4 dinitrophenolate and 2,5 dinitrophenolate followed by the concentration prediction of these three chemical species during a diffusion experiment through a hydrophobic liquid membrane. MATLAB software is used for numerical calculations. Most of the commands for the analysis are provided in order to allow a non-specialist to follow step by step the analysis.

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.

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.

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.

Experimento didático de quimiometria para análise exploratória de óleos vegetais comestíveis por espectroscopia no infravermelho médio e análise de componentes principais: um tutorial, parte I

This manuscript aims to show the basic concepts and practical application of Principal Component Analysis (PCA) as a tutorial, using Matlab or Octave computing environment for beginners, undergraduate and graduate students. As a practical example it is shown the exploratory analysis of edible vegetable oils by mid infrared spectroscopy.

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.

Experimento didático de quimiometria para calibração multivariada na determinação de paracetamol em comprimidos comerciais utilizando espectroscopia no infravermelho próximo: um tutorial, parte II

The aim of this manuscript was to show the basic concepts and practical application of Partial Least Squares (PLS) as a tutorial, using the Matlab computing environment for beginners, undergraduate and graduate students. As a practical example, the determination of the drug paracetamol in commercial tablets using Near-Infrared (NIR) spectroscopy and Partial Least Squares (PLS) regression was shown, an experiment that has been successfully carried out at the Chemical Institute of Campinas State University for chemistry undergraduate course students to introduce the basic concepts of multivariate calibration in a practical way.

Experimento didático de quimiometria para planejamento de experimentos: avaliação das condições experimentais na determinação espectrofotométrica de ferro II com o-fenantrolina. Um tutorial, parte III

The objective of this manuscript is to describe a practical experiment that can be employed for teaching concepts related to design of experiments using Matlab or Octave computing environment to beginners, undergraduate and graduate students. The classical experiment for determination of Fe (II) using o-phenanthroline was selected because it is easy to understand, and all the required materials are readily available in most analytical laboratories. The approach used in this tutorial is divided in two steps: first, the students are introduced to the concept of multivariate effects, how to calculate and interpret them, and the construction and evaluation of a linear model to describe the experimental domain by using a 2³ factorial design. Second, an extension of the factorial design by adding axial points is described, thereby, providing a central composite design. The quadratic model is then introduced and used to build the response surface.

A quimiometria nos cursos de graduação em química: proposta do uso da análise multivariada na determinação de pkª

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.

Quimiometria como ferramenta analitica para definição das condiçoes de ensaio da enzima peroxidase de soja

Enzimas Peroxidases são heme-proteínas encontradas nos diferentes organismos vivos, especialmente vegetais, apresentam importante papel fisiológico/bioquímico como proteção contra microorganismos invasores. A soja, um dos mais importantes produtos para o agronegócio brasileiro apresenta na casca de suas sementes (subproduto) alta atividade de peroxidase, denominada soybean peroxidase,com potencial de utilização em métodos analíticos clínicos. A proposta do trabalho foi aplicar o planejamento fatorial para otimização das condições extração da enzima, definição das condições ótimas de atividade (pH e temperatura), utilizando metodologia de superfície de resposta. Os dados obtidos com clara definição foram: i) extração em pó cetonico, ii) meio reacional: pH 3,3, volume da amostra contendo a enzima 330 µL - 340 µL, peróxido de hidrogênio 4,2 mmol.L-1 150 µL, tempo de reação 20 segundos, temperatura 50º C, substrato guaiacol 30mmol.L-1 300 µL, e 0,1 mol.L-1 de NaCl. O uso da dessa metodologia para definição das condições de extração e estudos cinético-enzimáticos da peroxidase de soja foram eficientes e mais precisos, comparado a metodologia de variações/repetições (tentativa e erro).

Espectrometria de emissão óptica com plasma indutivamente acoplado aliada à quimiometria na determinação de íons metálicos no molusco Mytella falcata para discriminação de estuários potiguares

This work examined the possibility of using mussel Mytella falcata as bioindicator sample to detect metal ions in several estuaries potiguares, since species substances that accumulate in their tissues due to its characteristics filter feeders have been used for environmental monitoring. The chemometrics by principal components analysis was used to reduce the size of the original data in order to establish a pattern of distribution of metal ion. Samples were collected at three different points in the estuaries Curimataú, Guaraíra-Papeba, Potengi, Galinhos-Guamaré and Piranhas-Assu having been marked with the location using GPS (Global Positioning System). The determination of humidity content and digestion of the samples were performed using methods described in the Compendium of analytical standards of the Institute Adofo Lutz (2005) and the determination of metal ions of the elements Al, Ba, Cd, Cr, Cu, Mn, Ni, Pb, Sn and Zn were performed by optical emission spectrometry with inductively coupled plasma as described by USEPA method 6010C. The results show that it is possible to use this molluscum Mytella falcata in the estuaries of Rio Grande do Norte for the determination of metal ions. The data were subjected to principal components analysis (PCA) which enabled us to verify the distribution pattern of the metal ions studied in several estuaries potiguares and group them according to the metal ions in common with and relate them to the activities in each region