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.

VIS-NIR SPECTROMETRY, SOIL PHOSPHATE EXTRACTION METHODS AND INTERACTIONS OF SOIL ATTRIBUTES

The objective of this study was to evaluate the relationships between the spectra in the Vis-NIR range and the soil P concentrations obtained from the PM and Prem extraction methods as well as the effects of these relationships on the construction of models predicting P concentration in Oxisols. Soil samples' spectra and their PM and Prem extraction solutions were determined for the Vis-NIR region between 400 and 2500 nm. Mineralogy and/or organic matter content act as primary attributes allowing correlation of these soil phosphorus fractions with the spectra, mainly at wavelengths between 450-550, 900-1100 nm, near 1400 nm and between 2200-2300 nm. However, the regression models generated were not suitable for quantitative phosphate analysis. Solubilization of organic matter and reactions during the PM extraction process hindered correlations between the spectra and these P soil fractions. For Prem,, the presence of Ca in the extractant and preferential adsorption by gibbsite and iron oxides, particularly goethite, obscured correlations with the spectra.

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.

DISCRIMINAÇÃO DE MADEIRAS SIMILARES POR FLUORESCÊNCIA MOLECULAR E MÍNIMOS QUADRADOS PARCIAIS

Wood is an extremely complex biological material, which can show macroscopic similarities that make it difficult to discriminate between species. Discrimination between similar wood species can be achieved by either anatomic or instrumental methods, such as near infrared spectroscopy (NIR). Although different spectroscopy methods are currently available, few studies have applied them to discriminate between wood species. In this study, we applied a partial least squares-discriminant analysis (PLS-DA) model to evaluate the viability of using direct fluorescence measurements for discriminating between Eucalyptus grandis, Eucalyptus urograndis, and Cedrela odorata. The results show that molecular fluorescence is an efficient technique for discriminating between these visually similar wood species. With respect to calibration and the validation samples, we observed no misclassifications or outliers.

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.

Characteristics of pyridine adsorption on Au(111) and Au(210) by EIS parameters fitting procedure

Some aspects of the application of electrochemical impedance spectroscopy to studies of solid electrode / solution interface, in the absence of faradaic processes, are analysed. In order to perform this analysis, gold electrodes with (111) and (210) crystallographic orientations in an aqueous solution containing 10 mmol dm-3 KF, as supporting electrolyte, and a pyridine concentration varying from 0.01 to 4.6 mmol dm-3, were used. The experimental data was analysed by using EQUIVCRT software, which utilises non-linear least squares routines, attributing to the solid electrode / solution interface behaviour described by an equivalent circuit with a resistance in series with a constant phase element. The results of this fitting procedure were analysed by the dependence on the electrode potential on two parameters: the pre-exponential factor, Y0, and the exponent n f, related with the phase angle shift. By this analysis it was possible to observe that the pyridine adsorption is strongly affected by the crystallographic orientation of the electrode surface and that the extent of deviation from ideal capacitive behaviour is mainly of interfacial origin.

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.

Motivational Influences on Transfer: Dimensions and Boundary Conditions

The focus of this dissertation is the motivational influences on transfer in higher education and professional training contexts. To estimate these motivational influences, the dissertation includes seven individual studies that are structured in two parts. Part I, Dimensions, aims at identifying the dimensionality of motivation to transfer and its structural relations with training-related antecedents and outcomes. Part II, Boundary Conditions, aims at testing the predictive validity of motivation theories used in contemporary training research under different study conditions. Data in this dissertation was gathered from multi-item questionnaires, which were analyzed differently in Part I and Part II. Studies in Part I employed exploratory and confirmatory factor analysis, structural equation modeling, partial least squares (PLS) path modeling, and mediation analysis. Studies in Part II used artifact distribution meta-analysis, (nested) subgroup analysis, and weighted least squares (WLS) multiple regression. Results demonstrate that motivation to transfer can be conceptualized as a three-dimensional construct, including autonomous motivation to transfer, controlled motivation to transfer, and intention to transfer, given a theoretical framework informed by expectancy theory, self-determination theory, and the theory of planned behavior. Results also demonstrate that a range of boundary conditions moderates motivational influences on transfer. To test the predictive validity of expectancy theory, social cognitive theory, and the theory of goal orientations under different study settings, a total of 17 boundary conditions were meta-analyzed, including age; assessment criterion; assessment source; attendance policy; collaboration among trainees; computer support; instruction; instrument used to measure motivation; level of education; publication type; social training context; SS/SMC bias; study setting; survey modality; type of knowledge being trained; use of a control group; and work context. Together, the findings cumulated in this thesis support the basic premise that motivation is centrally important for transfer, but that motivational influences need to be understood from a more differentiated perspective than commonly found in the literature, in order to account for several dimensions and boundary conditions. The results of this dissertation across the seven individual studies are reflected in terms of their implications for theory development and their significance for training evaluation and the design of training environments. Limitations and directions to take in future research are discussed.

Alternative methodology for calculating the modulus of elasticity of wooden beams of structural dimensions

This study aims to present an alternative calculation methodology based on the Least Squares Method for determining the modulus of elasticity in bending wooden beams of structural dimensions. The equations developed require knowledge of three or five points measured in displacements along the piece, allowing greater reliability on the response variable, using the statistical bending test at three points and non-destructively, resulting from imposition of measures from small displacements L/300 and L/200, the largest being stipulated by the Brazilian norm NBR 7190:1997. The woods tested were Angico, Cumaru, Garapa and Jatoba. Besides obtaining the modulus of elasticity through the alternative methodology proposed, these were also obtained employing the Brazilian norm NBR 7190:1997, adapted to the condition of non-destructive testing (small displacements) and for pieces of structural dimensions. The results of the modulus of elasticity of the four species of wood according to both calculation approaches used proved to be equivalent, implying the good approximation provided by the methodology of calculation adapted from the Brazilian norm.

Novel Regression Methods For Spectral Data

Singular Value Decomposition (SVD), Principal Component Analysis (PCA) and Multiple Linear Regression (MLR) are some of the mathematical pre- liminaries that are discussed prior to explaining PLS and PCR models. Both PLS and PCR are applied to real spectral data and their di erences and similarities are discussed in this thesis. The challenge lies in establishing the optimum number of components to be included in either of the models but this has been overcome by using various diagnostic tools suggested in this thesis. Correspondence analysis (CA) and PLS were applied to ecological data. The idea of CA was to correlate the macrophytes species and lakes. The di erences between PLS model for ecological data and PLS for spectral data are noted and explained in this thesis. i

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.

Private Equity Fund Performance Determinants: Evidence From Fund Characteristics

The purpose of this thesis is to investigate whether different private equity fund characteristics have any influence on the fund performance. Fund characteristics include fund type (venture capital or buyouts), fund size (sizes of funds are divided into six ranges), fund investment industry, fund sequence (first fund or follow-on fund) and investment market (US or EMEA). Fund performance is measured by internal rate of return, and tested by cross-sectional regression analysis with the method of Ordinary Least Squares. The data employs performance and characteristics of 997 private equity funds between 1985 and 2008. Our findings are that fund type has effect on fund performance. The average IRR of venture capital funds is 2.7% less than average IRR of buyout funds. However, We did not find any relationship between fund size and performance, and between fund sequence and performance. Funds based on US market perform better than funds based on EMEA market. The fund performance differs across different industries. The average IRRs of industrial/energy industry, consumer related industry, communications and media industry and medical/health industry are higher than the average IRR of other industries.

Store experiences and their influence on store performance and brand strength: Case Samsung Experience Store

Experiential marketing is increasingly seen as a new magical key to consumers’ hearts. Brands are turning brick-and-mortar stores into state of the art retail spaces where memorable experiences and strong brand relationships are hoped to be born. Around the globe, several brands have opened up a special format of stores – the experience store. Although many speculations on the positive effects of experiences have been presented, few studies have provided empirical, quantified evidence for the link between store experiences and brand success. In consequence, research was needed to find out whether experience stores truly are so special. The purpose of this thesis was to investigate whether store experiences are capable of building brands and influencing store performance. For this purpose, empirical research was conducted in the Samsung Experience Store Helsinki. As main constructs of the study, store experience, brand equity, store performance, and product class involvement were measured, along with relevant background variables. Data was collected with an electronic survey from actual customers of the store, resulting in a sample of 131 respondents. Partial least squares structural equations modeling (PLS) was used for the analysis of the research model. Also, regression analysis was conducted to account for mediation and moderation effects. The results showed that store experiences do positively influence first, store performance, and second, separate dimensions of brand equity (that is, brand awareness, brand personality, and brand loyalty). Also, the effect of store experiences on store performance was found to be mediated by brand equity. Interestingly, customers’ product class involvement was detected to moderate the effect of store experience on store performance. That is, those who were highly involved with electronics had greater store experiences, and also displayed a stronger linkage between store experience and store performance. The results encourage marketers to continue with efforts to create great experiences for their customers. Experience stores can – and should be seen – as both powerful brand building tools and profitable sales channels. The creation of exceptional experiences can act as an important function of physical stores in the face of severe online competition.

Treadmill exercise testing of asymptomatic men and women without evidence of heart disease

The aim of this study was to test the hypothesis of differences in performance including differences in ST-T wave changes between healthy men and women submitted to an exercise stress test. Two hundred (45.4%) men and 241 (54.6%) women (mean age: 38.7 ± 11.0 years) were submitted to an exercise stress test. Physiologic and electrocardiographic variables were compared by the Student t-test and the chi-square test. To test the hypothesis of differences in ST-segment changes, data were ranked with functional models based on weighted least squares. To evaluate the influence of gender and age on the diagnosis of ST-segment abnormality, a logistic model was adjusted; P < 0.05 was considered to be significant. Rate-pressure product, duration of exercise and estimated functional capacity were higher in men (P < 0.05). Sixteen (6.7%) women and 9 (4.5%) men demonstrated ST-segment upslope ≥0.15 mV or downslope ≥0.10 mV; the difference was not statistically significant. Age increase of one year added 4% to the chance of upsloping of segment ST ≥0.15 mV or downsloping of segment ST ≥0.1 mV (P = 0.03; risk ratio = 1.040, 95% confidence interval (CI) = 1.002-1.080). Heart rate recovery was higher in women (P < 0.05). The chance of women showing an increase of systolic blood pressure ≤30 mmHg was 85% higher (P = 0.01; risk ratio = 1.85, 95%CI = 1.1-3.05). No significant difference in the frequency of ST-T wave changes was observed between men and women. Other differences may be related to different physical conditioning.