Development of a fast capillary electrophoresis method to determine inorganic cations in biodiesel samples

The aim of this study was to develop a fast capillary electrophoresis method for the determination of inorganic cations (Na(+), K(+), Ca(2+), Mg(2+)) in biodiesel samples, using barium (Ba(2+)) as the internal standard. The running electrolyte was optimized through effective mobility curves in order to select the co-ion and Peakmaster software was used to determine electromigration dispersion and buffer capacity. The optimum background electrolyte was composed of 10 mmol L(-1) imidazole and 40 mmol L(-1) of acetic acid. Separation was conducted in a fused-silica capillary (32 cm total length and 23.5 cm effective length, 50 mu m I.D.), with indirect UV detection at 214 nm. The migration time was only 36 s. In order to obtain the optimized conditions for extraction, a fractional factorial experimental design was used. The variables investigated were biodiesel mass, pH, extractant volume, agitation and sonication time. The optimum conditions were: biodiesel mass of 200 mg, extractant volume of 200 mu L. and agitation of 20 min. The method is characterized by good linearity in the concentration range of 0.5-20 mg kg(-1) (r > 0.999), limit of detection was equal to 0.3 mg kg(-1), inter-day precision was equal to 1.88% and recovery in the range of 88.0-120%. The developed method was successfully applied to the determination of cations in biodiesel samples. (c) 2010 Elsevier B.V. All rights reserved.

Development of a fast capillary electrophoresis method for the determination of propranolol-Total analysis time reduction strategies

The aim of this study was to develop a fast capillary electrophoresis method for the determination of propranolol in pharmaceutical preparations. In the method development the pH and constituents of the background electrolyte were selected using the effective mobility versus pH curves. Benzylamine was used as the internal standard. The background electrolyte was composed of 60 mmol L(-1) tris(hydroxymethyl)aminomethane and 30 mmol L(-1) 2-hydroxyisobutyric acid,at pH 8.1. Separation was conducted in a fused-silica capillary (32 cm total length and 8.5 cm effective length, 50 mu m I.D.) with a short-end injection configuration and direct UV detection at 214 nm. The run time was only 14 s. Three different strategies were studied in order to develop a fast CE method with low total analysis time for propranolol analysis: low flush time (Lflush) 35 runs/h, without flush (Wflush) 52 runs/h, and Invert (switched polarity) 45 runs/h. Since the three strategies developed are statistically equivalent, Mush was selected due to the higher analytical frequency in comparison with the other methods. A few figures of merit of the proposed method include: good linearity (R(2) > 0.9999); limit of detection of 0.5 mg L(-1): inter-day precision better than 1.03% (n = 9) and recovery in the range of 95.1-104.5%. (C) 2009 Elsevier B.V. All rights reserved.

Pendimethalin determination in natural water, baby food and river sediment samples using electroanalytical methods

This work describes the electroanalytical determination of pendimethalin herbicide levels in natural waters, river sediment and baby food samples, based on the electro-reduction of herbicide on the hanging mercury drop electrode using square wave voltammetry (SWV). A number of experimental and voltammetric conditions were evaluated and the best responses were achieved in Britton-Robinson buffer solutions at pH 8.0, using a frequency of 500 s(-1). a scan increment of 10 mV and a square wave amplitude of 50 mV. Under these conditions, the pendimethalin is reduced in an irreversible process, with two reduction peaks at -0.60 V and -0.71 V. using a Ag/AgCl reference system. Analytical curves were constructed and the detection limit values were calculated to be 7.79 mu g L(-1) and 4.88 mu g L(-1), for peak 1 and peak 2, respectively. The precision and accuracy were determinate as a function of experimental repeatability and reproducibility, which showed standard relative deviation values that were lower than 2% for both voltammetric peaks. The applicability of the proposed methodology was evaluated in natural water, river sediments and baby food samples. The calculated recovery efficiencies demonstrate that the proposed methodology is suitable for determining any contamination by pendimethalin in these samples. Additionally, adsorption isotherms were used to evaluate information about the behavior of pendimethalin in river sediment samples. (C) 2010 Elsevier B.V. All rights reserved.

Children's recall of words spoken in their first and second language : Effects of Signal-to-Noise Ratio and Reverberation Time

Speech perception runs smoothly and automatically when there is silence in the background, but when the speech signal is degraded by background noise or by reverberation, effortful cognitive processing is needed to compensate for the signal distortion. Previous research has typically investigated the effects of signal-to-noise ratio (SNR) and reverberation time in isolation, whilst few have looked at their interaction. In this study, we probed how reverberation time and SNR influence recall of words presented in participants' first- (L1) and second-language (L2). A total of 72 children (10 years old) participated in this study. The to-be-recalled wordlists were played back with two different reverberation times (0.3 and 1.2 s) crossed with two different SNRs (+3 dBA and +12 dBA). Children recalled fewer words when the spoken words were presented in L2 in comparison with recall of spoken words presented in L1. Words that were presented with a high SNR (+12 dBA) improved recall compared to a low SNR (+3 dBA). Reverberation time interacted with SNR to the effect that at +12 dB the shorter reverberation time improved recall, but at +3 dB it impaired recall. The effects of the physical sound variables (SNR and reverberation time) did not interact with language. © 2016 Hurtig, Keus van de Poll, Pekkola, Hygge, Ljung and Sörqvist.

Um estudo sobre o valor e a reatância nas reações dos consumidores brasileiros frente ao recall de produtos

Neste projeto busca-se identificar as reações dos consumidores brasileiros ao recall de produtos. No exterior recall é prática mais antiga enquanto que no Brasil é um procedimento recente, mas que vem ganhando crescente importância nos últimos anos. De fato, esse alerta, que um determinado lote da produção não saiu de fábrica como o planejado, feito pelos fabricantes a um grupo de compradores de seus produtos, vem ocorrendo com mais freqüência e particularmente no setor automobilístico. Todavia, é bem possível que muitos consumidores ainda não conheçam esse procedimento e nem saibam que estão sujeitos a imprevistos como o de adquirir um produto que, mesmo tendo passado pelos testes de qualidade do fabricante, possa estar sendo objeto de um chamado desse tipo, pois algo diferente do que era esperado foi encontrado no produto: ele não passou por alguma sabatina posterior de testes do fabricante ou até mesmo de sua matriz no exterior! O objetivo do estudo é o de identificar as reações do consumidor frente ao recall de produtos e os impactos que possa estar criando para ele.

A percepção de valor do consumidor frente ao recall de veículos no Brasil : um estudo exploratório em São Paulo

Este estudo analisa o comportamento do consumidor brasileiro frente ao recall de veículos automotivos. O processo de compra, uso e descarte dos automóveis que sofreram o chamamento é analisado sob a ótica da teoria da reatância psicológica, originária da psicologia e que visa explanar a reação de indivíduos a limitações em sua liberdade. O objetivo do estudo é dimensionar a reatância psicológica individual e verificar a percepção dos consumidores ao recall de veículos automotivos, através dos indicativos de valor percebido e a qualidade no relacionamento percebida pelo indivíduo. A resultante do processo foi o comportamento de compra pós recall. Os maiores beneficiários deste estudo serão os próprios consumidores bem como as montadoras de veículos, os órgãos de defesa dos consumidores e entidades jurídicas interessadas neste tema. A originalidade de avaliar as implicações deste acontecimento sob a ótica do consumidor é uma contribuição deste estudo, pois o recall ainda não foi estudado sob este ponto de vista anteriormente no Brasil, apesar do constante escrutínio do tema na mídia. O estudo tem início com um histórico do recall nos Estados Unidos da América e no Brasil. Em seguida, foi elaborada uma revisão de conhecimento reunindo os principais conceitos apresentados anteriormente e foi proposto um esquema unindo as variáveis. Em seguida, foram elaboradas na cidade de São Paulo duas pesquisas: uma qualitativa, exploratória a fim de examinar o processo de compra e pensamentos sobre o recall e outra quantitativa a fim de traduzir as escalas para o dimensionamento das variáveis: (a) reatância psicológica (o questionário para o dimensionamento da reatância psicológica de Merz (1983), (b) o valor percebido pelo consumidor (dimensionado através da escala PERVAL de Sweeney e Soutar (2001) e (c) a qualidade percebida no relacionamento entre consumidor e organização de Roberts et al (2003) e apresentar as relações existentes entre elas. Os resultados indicam que o consumidor não passa ileso pelo recall. Ele cria uma memória e sabedoria das conseqüências do chamamento. Duas perspectivas do consumidor frente ao recall foram identificadas: uma visão negativa, mais reatante, que aparentemente fica mais preocupada com o incômodo que o processo todo causa do que com uma potencial ameaça a sua segurança e mais propensa a mudar de fornecedor; e outra visão positiva, pouco reatante e que considera o processo como uma atitude responsável, que transmite credibilidade e confiança do fabricante, esta por sua vez mais propensa a permanecer na marca.

On testing the Phillips curves, the IS Curves, and the interaction between fiscal and monetary policies

Esta tese é composta por três ensaios sobre testes empíricos de curvas de Phillips, curvas IS e a interação entre as políticas fiscal e monetária. O primeiro ensaio ("Curvas de Phillips: um Teste Abrangente") testa curvas de Phillips usando uma especificação autoregressiva de defasagem distribuída (ADL) que abrange a curva de Phillips Aceleracionista (APC), a curva de Phillips Novo Keynesiana (NKPC), a curva de Phillips Híbrida (HPC) e a curva de Phillips de Informação Rígida (SIPC). Utilizamos dados dos Estados Unidos (1985Q1--2007Q4) e do Brasil (1996Q1--2012Q2), usando o hiato do produto e alternativamente o custo marginal real como medida de pressão inflacionária. A evidência empírica rejeita as restrições decorrentes da NKPC, da HPC e da SIPC, mas não rejeita aquelas da APC. O segundo ensaio ("Curvas IS: um Teste Abrangente") testa curvas IS usando uma especificação ADL que abrange a curva IS Keynesiana tradicional (KISC), a curva IS Novo Keynesiana (NKISC) e a curva IS Híbrida (HISC). Utilizamos dados dos Estados Unidos (1985Q1--2007Q4) e do Brasil (1996Q1--2012Q2). A evidência empírica rejeita as restrições decorrentes da NKISC e da HISC, mas não rejeita aquelas da KISC. O terceiro ensaio ("Os Efeitos da Política Fiscal e suas Interações com a Política Monetária") analisa os efeitos de choques na política fiscal sobre a dinâmica da economia e a interação entre as políticas fiscal e monetária usando modelos SVARs. Testamos a Teoria Fiscal do Nível de Preços para o Brasil analisando a resposta do passivo do setor público a choques no superávit primário. Para a identificação híbrida, encontramos que não é possível distinguir empiricamente entre os regimes Ricardiano (Dominância Monetária) e não-Ricardiano (Dominância Fiscal). Entretanto, utilizando a identificação de restrições de sinais, existe evidência que o governo seguiu um regime Ricardiano (Dominância Monetária) de janeiro de 2000 a junho de 2008.

Estudo comparado à respeito das diferenças entre o procedimento brasileiro de recall de automóveis e o procedimento norte-americano de recall de automóveis e em que medidas estas se justificam

O presente trabalho de conclusão de curso busca expor e estudar as etapas, características e aspectos entre o procedimento de recall (também denominado chamamento) de automóveis brasileiro e o procedimento de recall de automóveis norte-americano, país pioneiro na procedimentalização do chamamento de automóveis, a fim de comparar as diferenças percebidas entre cada um destes modelos e em que medidas estas se justificam, analisando o porquê de tais diferenças, bem como o que poderia ser aprimorado em cada um dos modelos.

Comparison of two extraction methods for evaluation of volatile constituents patterns in commercial whiskeys: Elucidation of the main odour-active compounds

An analytical procedure based on manual dynamic headspace solid-phase microextraction (HS-SPME) method and the conventional extraction method by liquid–liquid extraction (LLE), were compared for their effectiveness in the extraction and quantification of volatile compounds from commercial whiskey samples. Seven extraction solvents covering a wide range of polarities and two SPME fibres coatings, has been evaluated. The highest amounts extracted, were achieved using dichloromethane (CH2Cl2) by LLE method (LLECH2Cl2)(LLECH2Cl2) and using a CAR/PDMS fibre (SPMECAR/PDMS) in HS-SPME. Each method was used to determine the responses of 25 analytes from whiskeys and calibration standards, in order to provide sensitivity comparisons between the two methods. Calibration curves were established in a synthetic whiskey and linear correlation coefficient (r ) were greater than 0.9929 for LLECH2Cl2LLECH2Cl2 and 0.9935 for SPMECAR/PDMS, for all target compounds. Recoveries greater than 80% were achieved. For most compounds, precision (expressed by relative standard deviation, R.S.D.) are very good, with R.S.D. values lower than 14.78% for HS-SPME method and than 19.42% for LLE method. The detection limits ranged from 0.13 to 19.03 μg L−1 for SPME procedure and from 0.50 to 12.48 μg L−1 for LLE. A tentative study to estimate the contribution of a specific compound to the aroma of a whiskey, on the basis of their odour activity values (OAV) was made. Ethyl octanoate followed by isoamyl acetate and isobutyl alcohol, were found the most potent odour-active compounds.

Quantification of polyphenols with potential antioxidant properties in wines using reverse phase HPLC

A RP-HPLC method with photodiode array detection (DAD) was developed to separate, identify and quantify simultaneously the most representative phenolic compounds present in Madeira and Canary Islands wines. The optimized chromatographic method was carefully validated in terms of linearity, precision, accuracy and sensitivity. A high repeatability and a good stability of phenolics retention times (a3%) were obtained, as well as relative peak area. Also high recoveries were achieved, over 80.3%. Polyphenols calibration curves showed a good linearity (r2 A0.994) within test ranges. Detection limits ranged between 0.03 and 11.5 lg/mL for the different polyphenols. A good repeatability was obtained, with intra-day variations less than 7.9%. The described method was successfully applied to quantify several polyphenols in 26 samples of different kinds of wine (red, ros and white wines) from Madeira and Canary Islands. Gallic acid was by far the most predominant acid. It represents more than 65% of all phenolics, followed by p-coumaric and caffeic acids. The major flavonoid found in Madeira wines was trans-resveratrol. In some wines, (–)-epicatechin was also found in highest amount. Canary wines were shown to be rich in gallic, caffeic and p-coumaric acids and quercetin.

Mathematical analysis of maximum power generated by photovoltaic systems and fitting curves for standard test conditions

The rural electrification is characterized by geographical dispersion of the population, low consumption, high investment by consumers and high cost. Moreover, solar radiation constitutes an inexhaustible source of energy and in its conversion into electricity photovoltaic panels are used. In this study, equations were adjusted to field conditions presented by the manufacturer for current and power of small photovoltaic systems. The mathematical analysis was performed on the photovoltaic rural system I- 100 from ISOFOTON, with power 300 Wp, located at the Experimental Farm Lageado of FCA/UNESP. For the development of such equations, the circuitry of photovoltaic cells has been studied to apply iterative numerical methods for the determination of electrical parameters and possible errors in the appropriate equations in the literature to reality. Therefore, a simulation of a photovoltaic panel was proposed through mathematical equations that were adjusted according to the data of local radiation. The results have presented equations that provide real answers to the user and may assist in the design of these systems, once calculated that the maximum power limit ensures a supply of energy generated. This real sizing helps establishing the possible applications of solar energy to the rural producer and informing the real possibilities of generating electricity from the sun.

Nanosistemas de penicilina G benzatina para tratamento profilático da febre reumática: estudo analítico

Investigations in the field of pharmaceutical analysis and quality control of medicines require analytical procedures with good perfomance characteristics. Calibration is one of the most important steps in chemical analysis, presenting direct relation to parameters such as linearity. This work consisted in the development of a new methodology to obtain calibration curves for drug analysis: the stationary cuvette one. It was compared to the currently used methodology, and possible sources of variation between them were evaluated. The results demonstrated that the proposed technique presented similar reproducibility compared to the traditional methodology. In addition to that, some advantages were observed, such as user-friendliness, cost-effectiveness, accuracy, precision and robustness. Therefore, the stationary cuvette methodology may be considered the best choice to obtain calibration curves for drug analyis by spectrophotometry

Maturation and growth curves of Macrobrachium Carcinus (Linnaeus) (Crustacea, Decapoda, Palaemonidae) from Ribeira de Iguape River, southern Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Funções de pedotransferência para a curva de resistência do solo à penetração

Funções de pedotransferência são regressões utilizadas para estimar atributos edáficos dependentes a partir de atributos independentes e de fácil determinação. Nesse sentido, são propostas na literatura diversas funções de pedotransferência que visam predizer a resistência do solo à penetração. Objetivou-se, portanto, com este trabalho, desenvolver e comparar a eficiência de cinco funções de pedotransferência para a curva de resistência do solo à penetração, presentes na literatura, por meio do ajuste de dados obtidos tanto com o penetrômetro de impacto (campo) quanto com o penetrômetro eletrônico (laboratório), em um Latossolo manejado sob diferentes modos (convencional e plantio direto). Foram coletadas amostras indeformadas de solo na entrelinha das culturas, nas camadas de 0-0,10, 0,10-0,20 e 0,20-0,30 m, logo após a semeadura, no florescimento e na colheita, para determinação dos atributos físico-hídricos do solo e também da resistência do solo à penetração, com o uso do penetrômetro eletrônico. A resistência do solo à penetração, obtida com o penetrômetro de impacto, foi determinada conforme a variação do conteúdo de água no solo ao longo do ciclo das culturas. As curvas ajustadas de resistência do solo à penetração tiveram a precisão e a acurácia testadas por meio de parâmetros estatísticos e foram comparadas pelo teste F. Houve sobreposição dos valores estimados pelo ajuste das curvas, evidenciando que a maneira de obtenção da resistência do solo à penetração (campo ou laboratório) não influenciou a relação entre a resistência à penetração e os atributos do solo. As equações RP = aUg b; RP = a(1-Ug)b; RP = ae bUg e RP = a + be não diferiram e foram as mais precisas e acuradas na predição da resistência do solo à penetração.