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.

Determinação do teor de edta remanescente em soluções de limpeza de equipamentos industriais

Cleaning solutions containing EDTA are widely employed to remove incrustation despite of the costs involved. The free content of EDTA in commercial solutions may be determined by mixing an aliquot to ammonium oxalate and using a standard calcium solution as titrant. The end-point is detected by the formation of insoluble calcium oxalate after all EDTA is complexed. A system for turbidimetric detection of the end-point was envisaged to substitute the visual detection, which impaired the analyses of dark samples. The proposed method was tested with real samples and good accuracy and precision was obtained.

químicos das folhas de Qualea grandiflora: atribuição dos dados de RMN de dois flavonóides glicosilados acilados diastereoisoméricos

Phytochemical investigation from leaves of the Qualea grandiflora (Vochysiaceae) resulted in the isolation and identification of kaempferol-3-O-α-L-(4"-E-p-coumaroyl)-rhamnoside, kaempferol-3-O-α-L-(4"-Z-p-coumaroyl)-rhamnoside, squalene, phytol, lupeol, α-amyrin, β-amyrin, sitosterol, sitostenone, sitosterol-3-O-β-D-glucopyranoside, ursolic and oleanolic acids. The structures of the compounds were identified by 1D- and 2D-NMR experiments, mass and UV spectrometry and comparison with literature data.

Validação de método para determinação de resíduos de amoxicilina aplicado à validação de limpeza em indústria farmacêutica de penicilânicos

The aim of this work was the single-laboratory validation of a quantitative method for the determination of amoxicillin residues in support of cleaning control and validation. Linearity was demonstrated between 2.5 and 17.5 μg/mL, without matrix effects. Mean recoveries ranged from 84.00 to 103.74% and the relative standard deviation under repetitivity and within-reproducibility conditions were from 0.58 to 4.20% and from 0.79 to 4.39%, respectively. The theoretical limits of detection and quantification were 0.133 and 0.442 μg/mL, respectively. The studied method was suitable for cleaning control purpose within good manufacturing practices.

Tratamento de dados censurados em estudos ambientais

Due to the inherent limitations of the analytical methods of measurement, environmental exposure data often present observations described as below a certain detection limit, also called left-censored data. Censored data directly interferes in almost all types of statistical analyzes, including descriptive parameters, hypothesis testing, confidence intervals, correlations and regressions. In this work, we investigated the performance of the main classes of methods from major publications available in the literature, considering their advantages and limitations. Some criteria for selecting the best method of dealing with censored data are presented.

APARATO ELETROQUÍMICO PARA SISTEMA DE AQUISIÇÃO DE DADOS MULTICANAL COM RESOLUÇÃO ESPAÇO-TEMPORAL

Spatiotemporal pattern formation in reaction-transport systems takes place spontaneously when the system is kept far from thermodynamic equilibrium. Targets, reaction fronts, waves, spirals, spots and stripes are some typical examples of selforganized structuring. In electrochemical systems, monitoring spatiotemporal patterns of potential in the solid/liquid interface can be done by the use of equally distributed microprobes located close to the working electrode. However, the physical size of each probe can limit the spatial resolution and alter mass transport properties. In contrast, the direct measurement of discrete electrodes does not suffer from this limitation and allows the accurate manipulation of the spatial coupling through changes in resistors connected to the electric circuit. In this paper, the development of an electrochemical setup for multichannel data acquisition with spatiotemporal resolution is described, especially to monitor low levels of currents usually observed in the electro-oxidation of small organic molecules.

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.

BUSCAS DE INFORMAÇÕES TECNOLÓGICAS COM BASE EM DADOS DE PATENTES: ESTUDO DE CASO DOS LÍQUIDOS IÔNICOS NO BRASIL

This study describes the application of the Art of Scientific and Technological Search to strategically analyze areas of technological and industrial development. Application of scientific search strategies such as the creation of Patent Landscape has been shown to be useful for writing research projects, earning grants, publishing papers, drafting patent applications, and analyzing the market and economic potentials of a previous determined subject. The Patent Landscape regards a simplified analysis of technologies concerning ionic liquids patents applied in Brazil and published by Instituto Nacional da Propriedade Industrial(INPI). A total of 93 patent applications using the keywords "ionic liquids" were found in the INPI database. Among these, 75% were nonresident applications and 25% were Brazilian resident applications. Interestingly, BASF, Chevron Industries, and the Universidade Federal do Rio Grande do Sul (UFRGS) were discovered as higher patent applicant assignees. Differences in the patent application areas were also observed between these applicants, with new solvents and petrochemical applications as the areas of focus for the industrial applications (BASF and Chevron Industries), and energy production, catalysis, and chemical reaction media as the focus for the university applications.

COMPARAÇÃO DE PROCESSAMENTOS MATEMÁTICOS DE DADOS VOLTAMÉTRICOS: APLICAÇÃO NA DETERMINAÇÃO SIMULTÂNEA DE FLUOROQUINOLONAS

This paper describes a comparative study between the procedures of deconvolution and the second-order derivative of square wave voltammograms to achieve separation of the voltammetric peaks of levofloxacin (LEVO) and norfloxacin (NOR), for their simultaneous quantification in urine samples. The obtained results indicate that the use of second-derivative voltammograms coupled with carbon screen-printed electrodes is the most efficient approach for completely separating the voltammetric peaks of LEVO and NOR. In addition, this approach has produced detection limits lower than 1.0 µmol L-1 and a wide linear range for both drugs. The proposed method was successfully used to simultaneously determine LEVO and NOR in spiked human and bovine urine samples with recovery percentages close to 100% for all analyzed samples.

REDUÇÃO DE VARIÁVEIS DE ENTRADA DE REDES NEURAIS ARTIFICIAIS A PARTIR DE DADOS DE ANÁLISE DE COMPONENTES PRINCIPAIS NA MODELAGEM DE OXIGÊNIO DISSOLVIDO

The objective of this work is to demonstrate the efficient utilization of the Principal Components Analysis (PCA) as a method to pre-process the original multivariate data, that is rewrite in a new matrix with principal components sorted by it's accumulated variance. The Artificial Neural Network (ANN) with backpropagation algorithm is trained, using this pre-processed data set derived from the PCA method, representing 90.02% of accumulated variance of the original data, as input. The training goal is modeling Dissolved Oxygen using information of other physical and chemical parameters. The water samples used in the experiments are gathered from the Paraíba do Sul River in São Paulo State, Brazil. The smallest Mean Square Errors (MSE) is used to compare the results of the different architectures and choose the best. The utilization of this method allowed the reduction of more than 20% of the input data, which contributed directly for the shorting time and computational effort in the ANN training.

Detecção do Sugarcane mosaic virus no Paraná e limpeza somaclonal por cultura de tecidos

Um isolado do Sugarcane mosaic virus (SCMV) causando sintomas de mosaico em plantas de cana-de-açúcar do clone RB925268 foi identificado no estado do Paraná. Gemas axilares extraídas de colmos infectados, medindo de 4 a 8 mm, foram utilizadas como explantes e regeneradas em plântulas em meio de cultura MS, suplementado ou não com o antiviral ribavirina, nas concentrações variando de 10-60 mg/L. O efeito fitotóxico da ribavirina foi constatado, resultando na morte dos explantes em concentrações iguais ou superiores a 30 mg/L. Após seis meses de aclimatação das plantas em estufa plástica, o vírus não foi detectado nas plantas provenientes do meio MS contendo ribavirina na concentração de 25 mg/L, confirmado através dos ensaios de inoculação mecânica em sorgo 'Rio' e de RT-PCR.

Estudo da adsorção/dessorção de 2,4-D em solos usando técnica cromatográfica

Este trabalho estudou a adsorção e a desorção do herbicida ácido 2,4-Diclorofenoxiacético (2,4-D) em solo da região de Urbano Santos - MA. A região possui campos de cultivo de eucaliptos para obtenção de celulose. Para a limpeza dos campos, antes da plantação e nos primeiros 12 meses de plantio, são aplicados herbicidas, dentre os quais destacamos o 2,4-D. A isoterma de Freundlich foi utilizado como modelo para este estudo e a concentração de 2,4-D foi determinada por cromatografia líquida de alta eficiência (CLAE), acompanhada de ensaios de recuperação para garantir a confiabilidade dos dados obtidos na investigação de adsorção/dessorção. Os resultados indicaram que o 2,4-D apresenta maior adsorção à matéria orgânica do solo estudado, quando comparado a outros tipos de solo, o que pode resultar em pequena diminuição em sua tendência de lixiviação e de degradação microbiológica. Entretanto, este herbicida apresenta elevado potencial de lixiviação quando comparado a outros pesticidas.

Uso da análise exploratória de dados na avaliação de modificadores químicos para determinação direta e simultânea de metais em álcool combustível por GFAAS

O objetivo deste trabalho foi empregar a análise exploratória de dados, no caso, a técnica de análise de componentes principais (PCA) como ferramenta na avaliação de modificadores químicos na determinação direta e simultânea de Al, As, Cu, Fe, Mn e Ni em álcool etílico combustível por espectrometria de absorção atômica em forno de grafite (GFAAS). Os modificadores químicos avaliados foram: Pd(NO3)2 + Mg(NO3)2; W/Rh; W+ co-injeção de Pd(NO3)2 + Mg(NO3)2 e para cada modificador foram utilizadas trintas amostras de álcool etílico combustível. Como dados experimentais foram utilizados os resultados dos testes de adição e recuperação dos analitos frente aos diferentes modificadores químicos estudados. O emprego da técnica de PCA possibilitou a separação dos tipos de modificadores em função do intervalo de recuperação do analito. Dentre os modificadores avaliados, W+ co-injeção de Pd(NO3)2 + Mg(NO3)2 apresentou-se como a espécie de maior correlação positiva, pois apresenta os maiores teores de recuperação, e sendo assim, foi o escolhido para o desenvolvimento de metodologia para determinação direta e simultânea de Al, As, Cu, Fe, Mn e Ni em álcool etílico combustível por GFAAS.