Calibração multivariada para sistemas com bandas sobrepostas através da análise da fatores do tipo Q

A multivariate calibration method to determine chemical compositions of systems with severely overlapped bands is proposed. Q mode factors are determined from the spectral data and subsequently rotated using the varimax and oblique transformation of Imbrie. The method is applied to two sets of simulated data to test the sensitivity of analytical results to random experimental error. The chemical concentrations of alanine and threonine mixture are determined from spectral data of the 302,5 - 548,5 nm region.

Avaliação do uso de métodos quimiométricos em análise de solos

One of the major interests in soil analysis is the evaluation of its chemical, physical and biological parameters, which are indicators of soil quality (the most important is the organic matter). Besides there is a great interest in the study of humic substances and on the assessment of pollutants, such as pesticides and heavy metals, in soils. Chemometrics is a powerful tool to deal with these problems and can help soil researchers to extract much more information from their data. In spite of this, the presence of these kinds of strategies in the literature has obtained projection only recently. The utilization of chemometric methods in soil analysis is evaluated in this article. The applications will be divided in four parts (with emphasis in the first two): (i) descriptive and exploratory methods based on Principal Component Analysis (PCA); (ii) multivariate calibration methods (MLR, PCR and PLS); (iii) methods such as Evolving Factor Analysis and SIMPLISMA; and (iv) artificial intelligence methods, such as Artificial Neural Networks.

Idiosyncratic Volatility Puzzle: Influence of Macro-Finance Factors

In this paper, we scrutinize the cross-sectional relation between idiosyncratic volatility and stock returns. As a novelty, the idiosyncratic volatility is obtained by conditioning upon macro-finance factors as well as upon traditional asset pricing factors. The macro-finance factors are constructed from a large pool of macroeconomic and financial variables. Cleaning for macro-finance e§ects reverses the puzzling negative relation between returns and idiosyncratic volatility documented previously. Portfolio analysis shows that the effects from macro-finance factors are economically strong. The relation between idiosyncratic volatility and returns does not vary with the NBER business cycles. The empirical results are highly robust. Keywords: Idiosyncratic volatility puzzle; Macro-finance predictors; Factor analysis; Business cycle. JEL Classifications: G12; G14

Aplicação de métodos quimiométricos na especiação de Cr(VI) em solução aquosa

The equilibria, the spectra and the identities of the species of Cr(VI) that are present in aqueous solution have long been an active subject of discussion in the literature. In this paper, three different chemometric methodologies are applied to sets of UV/Visible spectra of aqueous Cr(VI) solutions, in order to solve a chemical system where there is no available information concerning the composition of the samples nor spectral information about the pure species. Imbrie Q-mode factor analysis, followed by varimax rotation and Imbrie oblique projection, were used to estimate the composition of Cr(VI) equilibrium solutions and, by combining these results with the k-matrix method, to obtain the pure spectra of the species. Evolving factor analysis and self modeling curve resolution were used to confirm the number of the species and the resolution of the system, respectively. Sets of 3.3×10-4 and 3.3×10-5 mol L-1 Cr(VI) solutions, respectively, were analyzed in the pH range from 1 to 12. Two factors were identified, which were related to the chromate ion (CrO4(2-)) and bichromate ion (HCrO4-). The pK of the equilibrium was estimated as 5.8.

La Semiperiferia como necesidad del capitalismo global. Una aproximación a través del análisis factorial

A partir de una definición de la Semiperiferia basada en criterios del sistema productivo más que de la posición comercial, en este trabajo se avanza sobre la teorización de la existencia de tal parte del Sistema, diferenciada tanto del Centro como de la Periferia del mismo, ofreciendo propuestas de medición empírica de tal especificidad. Proponemos esta aproximación a partir de la utilización del análisis factorial.

Composição química da precipitação atmosférica no sul do Brasil: estudo preliminar

The present work is a preliminary study of total and wet precipitation in the Candiota region, RS. The samples were collected from January to June 2001 at four different sites. The following variables were analysed: pH, conductivity, alkalinity, Cl-, NO3-, F-, SO4(2-), Na+, K+, Mg2+, NH4+, Ca2+ and Zn, Cu, Fe, Al, Mn. The results showed slightly acidic precipitation and higher concentrations of NH4+, Na+, Cl- and SO4(2-). Factor analysis applied to the variables studied allowed identifying the major sources. Na+, Cl- and Mg2+ have their origin in sea salts and NH4+, Ca2+, K+, SO4(2-) and NO3- are from local anthropogenic sources.

Self-assessment of individual differences in language switching

Language switching is omnipresent in bilingual individuals. In fact, the ability to switch languages (code switching) is a very fast, efficient, and flexible process that seems to be a fundamental aspect of bilingual language processing. In this study, we aimed to characterize psychometrically self-perceived individual differences in language switching and to create a reliable measure of this behavioral pattern by introducing a bilingual switching questionnaire. As a working hypothesis based on the previous literature about code switching, we decomposed language switching into four constructs: (i) L1 switching tendencies (the tendency to switch to L1; L1-switch); (ii) L2 switching tendencies (L2-switch); (iii) contextual switch, which indexes the frequency of switches usually triggered by a particular situation, topic, or environment; and (iv) unintended switch, which measures the lack of intention and awareness of the language switches. A total of 582 SpanishCatalan bilingual university students were studied. Twelve items were selected (three for each construct). The correlation matrix was factor-analyzed using minimum rank factor analysis followed by oblique direct oblimin rotation. The overall proportion of common variance explained by the four extracted factors was 0.86. Finally, to assess the external validity of the individual differences scored with the new questionnaire, we evaluated the correlations between these measures and several psychometric (language proficiency) and behavioral measures related to cognitive and attentional control. The present study highlights the importance of evaluating individual differences in language switching using self-assessment instruments when studying the interface between cognitive control and bilingualism.

PARAFAC: uma ferramenta quimiométrica para tratamento de dados multidimensionais. Aplicações na determinação direta de fármacos em plasma humano por espectrofluorimetria

Since the last decade, the combined use of chemometrics and molecular spectroscopic techniques has become a new alternative for direct drug determination, without the need of physical separation. Among the new methodologies developed, the application of PARAFAC in the decomposition of spectrofluorimetric data should be highlighted. The first objective of this article is to describe the theoretical basis of PARAFAC. For this purpose, a discussion about the order of chemometric methods used in multivariate calibration and the development of multi-dimensional methods is presented first. The other objective of this article is to divulge for the Brazilian chemical community the potential of the combination PARAFAC/spectrofluorimetry for the determination of drugs in complex biological matrices. For this purpose, two applications aiming at determining, respectively, doxorrubicine and salicylate in human plasma are presented.

Distribution Patterns of Soil Properties in a Rural Mediterranean Area in Northeastern Spain

Soil properties on the Cap de Creus Peninsula, NE Spain depend primarily on scarce agricultural practices and early abandonment. In the study area, 90% of which is mainly covered by Cistus shrubs, 8 environments representing variations in land use/land cover and soil properties at different depths were identified. In each environment variously vegetated areas were selected and sampled. The soils, collected at different depths, were classified as Lithic Xerorthents according to the United States Department of Agriculture system of soil classification (USDA-NRCS 1975). Differences in soil properties were largely found according to the evolution of the plant canopy and the land use history. To identify underlying patterns in soil properties related to environmental evolution, factor analysis was performed and factor scores were used to determine how the factor patterns varied between soil variables, soil depths and selected environments. The three-factor model always accounted for 80% of the total variation in the data at the different soil depths. Organic matter was the more relevant soil property at 0–2 cm depth, whereas active minerals (silt and clay) were found to be the most relevant soil parameters controlling soil dynamics at the other depths investigated. Results showed that vineyards and olive tree soils are poorly developed and present worse conditions for mineral and organic compounds. Analysis of factor scores allowed independent assessment of soils, depth and plant cover and demonstrated that soils present the best physico-chemical characteristics under Erica arborea and meadows. In contrast, soils under Cistus monspeliensis were less nutrient rich and less well structured

Multimorbidity patterns in a national representative sample of the Spanish adult population.

BACKGROUND: In the context of population aging, multimorbidity has emerged as a growing concern in public health. However, little is known about multimorbidity patterns and other issues surrounding chronic diseases. The aim of our study was to examine multimorbidity patterns, the relationship between physical and mental conditions and the distribution of multimorbidity in the Spanish adult population. METHODS: Data from this cross-sectional study was collected from the COURAGE study. A total of 4,583 participants from Spain were included, 3,625 aged over 50. An exploratory factor analysis was conducted to detect multimorbidity patterns in the population over 50 years of age. Crude and adjusted binary logistic regressions were performed to identify individual associations between physical and mental conditions. RESULTS: THREE MULTIMORBIDITY PATTERNS ROSE: 'cardio-respiratory' (angina, asthma, chronic lung disease), 'mental-arthritis' (arthritis, depression, anxiety) and the 'aggregated pattern' (angina, hypertension, stroke, diabetes, cataracts, edentulism, arthritis). After adjusting for covariates, asthma, chronic lung disease, arthritis and the number of physical conditions were associated with depression. Angina and the number of physical conditions were associated with a higher risk of anxiety. With regard to multimorbidity distribution, women over 65 years suffered from the highest rate of multimorbidity (67.3%). CONCLUSION: Multimorbidity prevalence occurs in a high percentage of the Spanish population, especially in the elderly. There are specific multimorbidity patterns and individual associations between physical and mental conditions, which bring new insights into the complexity of chronic patients. There is need to implement patient-centered care which involves these interactions rather than merely paying attention to individual diseases.

Validation of an instrument to evaluate quality of life in the aging population: WHOQOL-AGE.

BACKGROUND: There is a need for short, specific instruments that assess quality of life (QOL) adequately in the older adult population. The aims of the present study were to obtain evidence on the validity of the inferences that could be drawn from an instrument to measure QOL in the aging population (people 50+ years old), and to test its psychometric properties. METHODS: The instrument, WHOQOL-AGE, comprised 13 positive items, assessed on a five-point rating scale, and was administered to nationally representative samples (n = 9987) from Finland, Poland, and Spain. Cronbach's alpha was employed to assess internal consistency reliability, whereas the validity of the questionnaire was assessed by means of factor analysis, graded response model, Pearson's correlation coefficient and unpaired t-test. Normative values were calculated across countries and for different age groups. RESULTS: The satisfactory goodness-of-fit indices confirmed that the factorial structure of WHOQOL-AGE comprises two first-order factors. Cronbach's alpha was 0.88 for factor 1, and 0.84 for factor 2. Evidence supporting a global score was found with a second-order factor model, according to the goodness-of-fit indices: CFI = 0.93, TLI = 0.91, RMSEA = 0.073. Convergent validity was estimated at r = 0.75 and adequate discriminant validity was also found. Significant differences were found between healthy individuals (74.19 ± 13.21) and individuals with at least one chronic condition (64.29 ± 16.29), supporting adequate known-groups validity. CONCLUSIONS: WHOQOL-AGE has shown good psychometric properties in Finland, Poland, and Spain. Therefore, considerable support is provided to using the WHOQOL-AGE to measure QOL in older adults in these countries, and to compare the QOL of older and younger adults.

Adaptación del Índice de Bienestar Personal para adolescentes en lengua española y portuguesa

The psychometric properties of the Personal Wellbeing Index are analyzed on a Spanish and Portuguese adolescent sample. We test the reliability of the scale using Cronbach’s alpha. And complementarily we analyze the item-total correlations in the different wellbeing domains included. We execute an exploratory factor analysis (principal components) and a multigroup Confirmatory Factor Analysis (CFA). The results show that Cronbach’s alpha is 0.79 for the Chilean version and in the Brazilian version is 0.78 confirming adequate levels of reliability found in previous studies. Correlations between fields of well-being shows values ranging between 0.224 and 0.496 for Chile and from 0.24 to 0.46 for Brazil. The results are similar to those obtained in other countries. The monofactorial structure of the scale is cinfirmed, also the adjustment to the scale structure to the data of the two samples and the comparability of means of global indices. The results suggest the existence of other well-being domains that had not been considered in the original proposal of the scale

Psychometric Properties of the Personal Wellbeing Index in Brazilian and Chilean Adolescents Including Spirituality and Religion = Propriedades Psicométricas do Personal Wellbeing Index em Adolescentes Brasileiros e Chilenos Incluindo Espiritualidade e Religião

This study compared the 7-item Personal Wellbeing Index (PWI) with two other versions which include the domains “Spirituality” and “Religion”, separately, in a sample of Brazilian (n = 1.047) and Chilean (n = 1.053) adolescents. A comparison of psychometric properties between the PWI versions was carried out through multigroup confi rmatory factor analysis showing adequate adjustments (CFI > .95, RMSEA < .08), whereas the item spirituality presented better performance. For the analysis of the differential contribution of each domain to the notion of global satisfaction, a regression on the item Overall Life Satisfaction (OLS) was applied using structural equations. It isrecommended the inclusion of the item spirituality in the original scale, considering the importance of such domain in both cultures

The factorial structure of the 41-item version of the Screen for Child Anxiety Related Emotional Disorders (SCARED) in a Spanish population of 8 to 12 years-old

On this instrumental study we intend to analyse the factorial structure of the Screen for Child Anxiety Related Emotional Disorders (SCARED) in a Spanish sample using exploratory and confirmatory factorial analysis. As a second objective we intend to develop a short form of it for rapid screening and, finally, to analyze the reliabilities of both questionnaires. The SCARED was administered to a community sample of 1,508 children aged between 8 and 12 years. The sample was randomly split using half for the exploratory analysis and the other half for the confirmatory study. Furthermore a reduced version of the SCARED was developed using the SchmidLeiman procedure. Exploratory Factor Analysis yielded a four factor structure comprised of Somatic/panic, Generalized anxiety, Separation anxiety and Social phobia factors This structure was confirmed using Confirmatory Factor Analysis. The four factors, the full scale and the short scale showed good reliabilities. The results obtained seem to indicate that the Spanish version of the SCARED has good internal consistency, and along with other recent results, has a structure of four related factors that replicates the dimensions proposed for anxiety disorders by the DSM-IV-TR

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.