Biodegradação de uma mistura de corantes têxteis usando o fungo Ganoderma sp: um estudo cinético

The kinetics of biodegradation by the fungus Ganoderma sp of textile dyes Yellow, Blue and Red Procion were studied in effluents using UV-Vis spectroscopy, Partial Least Squares Regression (PLS) and univariate analysis. The kinetic of the reactions were founded intermediate between first and second orders and the rate constants were calculated. The biodegradation after 72 h at 28 ºC were 33.6, 43.5 and 57.7% for the dyes Yellow, Blue and Red Procion, respectively. The quantitative analysis of the effluent by HPLC method can not be used without previous separation.

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.

Implementação de um método robusto para o controle fiscal de umidade em queijo minas artesanal. Abordagem metrológica multivariada

This study developed and validated a method for moisture determination in artisanal Minas cheese, using near-infrared spectroscopy and partial-least-squares. The model robustness was assured by broad sample diversity, real conditions of routine analysis, variable selection, outlier detection and analytical validation. The model was built from 28.5-55.5% w/w, with a root-mean-square-error-of-prediction of 1.6%. After its adoption, the method stability was confirmed over a period of two years through the development of a control chart. Besides this specific method, the present study sought to provide an example multivariate metrological methodology with potential for application in several areas, including new aspects, such as more stringent evaluation of the linearity of multivariate methods.

Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy and chemometric techniques for the determination of adulteration in petrodiesel/biodiesel blends

We propose an analytical method based on fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy to detect the adulteration of petrodiesel and petrodiesel/palm biodiesel blends with African crude palm oil. The infrared spectral fingerprints from the sample analysis were used to perform principal components analysis (PCA) and to construct a prediction model using partial least squares (PLS) regression. The PCA results separated the samples into three groups, allowing identification of those subjected to adulteration with palm oil. The obtained model shows a good predictive capacity for determining the concentration of palm oil in petrodiesel/biodiesel blends. Advantages of the proposed method include cost-effectiveness and speed; it is also environmentally friendly.

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.

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.

MCR-ALS APLICADO NO MONITORAMENTO QUANTITATIVO DO PROCESSO DE ELETRODEGRADAÇÃO DA ATRAZINA USANDO ESPECTROS UV: RESULTADOS COMPARATIVOS COM HPLC-DAD COMO UM MÉTODO DE REFERÊNCIA

Electrodegradation of atrazine in water was performed using homemade (PA and PB) and purchased (PC) boron-doped diamond anodes. The degradation was monitored off-line by analyzing total organic carbon and high performance liquid chromatography with diode array detector (HPLC-DAD) and at-line by UV spectroscopy. The spectra were recorded every 2 min. The rank deficiency problem was resolved by assembling an augmented column-wise matrix. HPLC was employed to separate the original and byproducts degradation components. Aiming the same goal, multivariate curve resolution - alternating least squares (MCR-ALS) was applied to resolve the UV spectroscopic data. Comparison between HPLC and MCR-ALS separations is presented. By using MCR-ALS the spectra of atrazine and two byproducts were successfully resolved and the resulted concentration profiles properly represented the system studied. The ALS explained variance (R2) for PA, PB and PC was equal to 99.99% for all of them and the lack of fit for PA, PB and PC were 0.39, 0.34 and 0.54 respectively. The correlation (R) between the recovered and pure spectra were calculate for each electrodegradation, validating the MCR-ALS results. The average R was equal to 0.997. The spectral and concentration profiles described with this new approach are in agreement with HPLC-DAD results. The proposed method is an alternative to classical analyses for monitoring of the degradation process, mainly due to the simplicity, fast results and economy.

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.

Determination of sulfur in diesel using ATR/FTIR and multivariate calibration

The aim of this present work was to provide a more fast, simple and less expensive to analyze sulfur content in diesel samples than by the standard methods currently used. Thus, samples of diesel fuel with sulfur concentrations varying from 400 and 2500 mgkg-1 were analyzed by two methodologies: X-ray fluorescence, according to ASTM D4294 and by Fourier transform infrared spectrometry (FTIR). The spectral data obtained from FTIR were used to build multivariate calibration models by partial least squares (PLS). Four models were built in three different ways: 1) a model using the full spectra (665 to 4000 cm-1), 2) two models using some specific spectrum regions and 3) a model with variable selected by classic method of variable selection stepwise. The model obtained by variable selection stepwise and the model built with region spectra between 665 and 856 cm-1 and 1145 and 2717 cm-1 showed better results in the determination of sulfur content.

A temperature predicting model for manufacturing processes requiring coiling

A model for predicting temperature evolution for automatic controling systems in manufacturing processes requiring the coiling of bars in the transfer table is presented. Although the method is of a general nature, the presentation in this work refers to the manufacturing of steel plates in hot rolling mills. The predicting strategy is based on a mathematical model of the evolution of temperature in a coiling and uncoiling bar and is presented in the form of a parabolic partial differential equation for a shape changing domain. The mathematical model is solved numerically by a space discretization via geometrically adaptive finite elements which accomodate the change in shape of the domain, using a computationally novel treatment of the resulting thermal contact problem due to coiling. Time is discretized according to a Crank-Nicolson scheme. Since the actual physical process takes less time than the time required by the process controlling computer to solve the full mathematical model, a special predictive device was developed, in the form of a set of least squares polynomials, based on the off-line numerical solution of the mathematical model.

Inovatividade, envolvimento, atitude e experiência na adoção da compra on-line

Este trabalho procura analisar as inter-relações entre a inovatividade, o envolvimento, a atitude dentro do modelo Theory of Planned Behavior (TPB) decomposto desenvolvido na psicologia social, e a experiência com a Internet com o processo de adoção da compra pela internet. Foi elaborado um modelo integrativo que possibilitasse explicar a relação entre esses fatores e a compra pela internet, e foi desenvolvida uma pesquisa de campo considerando uma amostra não probabilística de estudantes. Foi utilizado o método multivariado de modelagem de equações estruturais, aplicado por meio da técnica Partial Least Squares (PLS) para a verificação, explicação e comparação das relações entre os construtos. Os resultados mostram que a intenção da compra pela internet é diretamente influenciada pela atitude e pela inovatividade, e a atitude é influenciada pelo envolvimento. Não foi encontrada relação entre a experiência com a internet e a compra pela internet.

Cross-cultural validity of the demand-control questionnaire: Swedish and Brazilian workers

OBJECTIVE To evaluate the cross-cultural validity of the Demand-Control Questionnaire, comparing the original Swedish questionnaire with the Brazilian version. METHODS We compared data from 362 Swedish and 399 Brazilian health workers. Confirmatory and exploratory factor analyses were performed to test structural validity, using the robust weighted least squares mean and variance-adjusted (WLSMV) estimator. Construct validity, using hypotheses testing, was evaluated through the inspection of the mean score distribution of the scale dimensions according to sociodemographic and social support at work variables. RESULTS The confirmatory and exploratory factor analyses supported the instrument in three dimensions (for Swedish and Brazilians): psychological demands, skill discretion and decision authority. The best-fit model was achieved by including an error correlation between work fast and work intensely (psychological demands) and removing the item repetitive work (skill discretion). Hypotheses testing showed that workers with university degree had higher scores on skill discretion and decision authority and those with high levels of Social Support at Work had lower scores on psychological demands and higher scores on decision authority. CONCLUSIONS The results supported the equivalent dimensional structures across the two culturally different work contexts. Skill discretion and decision authority formed two distinct dimensions and the item repetitive work should be removed.

Evaluation of geostatistical techniques to estimate the spatial distribution of aboveground biomass in the Amazon rainforest using high-resolution remote sensing data

ABSTRACT The spatial distribution of forest biomass in the Amazon is heterogeneous with a temporal and spatial variation, especially in relation to the different vegetation types of this biome. Biomass estimated in this region varies significantly depending on the applied approach and the data set used for modeling it. In this context, this study aimed to evaluate three different geostatistical techniques to estimate the spatial distribution of aboveground biomass (AGB). The selected techniques were: 1) ordinary least-squares regression (OLS), 2) geographically weighted regression (GWR) and, 3) geographically weighted regression - kriging (GWR-K). These techniques were applied to the same field dataset, using the same environmental variables derived from cartographic information and high-resolution remote sensing data (RapidEye). This study was developed in the Amazon rainforest from Sucumbíos - Ecuador. The results of this study showed that the GWR-K, a hybrid technique, provided statistically satisfactory estimates with the lowest prediction error compared to the other two techniques. Furthermore, we observed that 75% of the AGB was explained by the combination of remote sensing data and environmental variables, where the forest types are the most important variable for estimating AGB. It should be noted that while the use of high-resolution images significantly improves the estimation of the spatial distribution of AGB, the processing of this information requires high computational demand.

Detection of cytomegalovirus in urine of HIV-infected patients by DNA-DNA hybridization comparison with virus isolation, immunofluorescence and immunoperoxidase

Immunofluorescence and immunoperoxidase test directed against early viral antigens, and DNA-DNA hybridization were compared with viral isolation for their abilities to detect Cytomegalovirus (CVM) in the urine of 89 HIV infected patients. From the 100 urine samples collected, 70 were found positive by at least one method. Considering viral isolation as the "gold standard" technique, immunofluorescence and immunoperoxidase had a sensitivity of 92.3% and88% respectively, with a specificity in both cases of 95%. DNA-DNA hybridization showed a sensitivity of 90% but with lower (60%) specificity. All of the three assays were effective in detecting CVM from urine and the technical advantage of each is discussed.

Antecedentes da intenção de uso de sistemas de home broker sob a ótica dos investidores do mercado acionário

Na pesquisa aqui relatada, visa-se investigar os antecedentes da intenção de uso de sistemas de home broker sob a ótica dos investidores do mercado acionário. Para atingir esse objetivo, por meio de referencial teórico baseado em teorias de aceitação de sistemas de informação, difusão da inovação, confiança em ambientes virtuais e satisfação do usuário, foi elaborado um modelo teórico e foram propostas hipóteses de pesquisa. Por meio de técnicas de equações estruturais baseadas em Partial Least Squares (PLS), a partir de 152 questionários válidos, coletados via web survey junto a investidores do mercado acionário brasileiro, foram testados o modelo proposto e as hipóteses de pesquisa. Identificaram-se, assim, os fatores compatibilidade, utilidade percebida e facilidade de uso percebida como antecedentes estatisticamente significantes do fator satisfação do usuário com o sistema de home broker, o qual, por sua vez, teve efeito estatisticamente significante na intenção de uso do sistema. São apresentadas, ainda, as implicações acadêmicas e gerenciais do trabalho, assim como suas limitações e uma agenda de pesquisa para essa importante área do conhecimento.