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.

Rapid method for the determination. of organic acids in wine by capillary electrophoresis with indirect UV detection

A capillary electrophoresis method for organic acids in wine was developed and validated. The optimal electrolyte consisted of 10 mmol/L 3,5-dinitrobenzoic acid (DNB) at pH 3.6 containing 0.2 mmol/L cetyltrimethylammonium bromide as flow reverser. DNB was chosen because it has an effective mobility similar to the organic acids under investigation, good buffering capacity at pH 3.6, and good chromophoric characteristics for indirect UV-absorbance detection at 254 nm. Sample preparation involved dilution and filtration. The method showed good performance characteristics: Linearity at 6 to 285 mg/L (r > 0.99); detection and quantification limits of 0.64 to 1.55 and 2.12 to 5.15 mg/L, respectively; separation time of less than 5.5 min. Coefficients of variation for ten injections were less than 5% and recoveries varied from 95% to 102%. Application to 23 samples of Brazilian wine confirmed good repeatability and demonstrated wide variation in the organic acid concentrations. (C) 2008 Elsevier Ltd. All rights reserved.

Determination of carbaryl in tomato ""in natura"" using an amperometric biosensor based on the inhibition of acetylcholinesterase activity

This work reports the utilization of two methodologies for carbaryl determination in tomatoes. The measurements were carried out using an amperometric biosensor technique based on the inhibition of acetylcholinesterase activity due to carbaryl adsorption and a HPLC procedure. The electrochemical experiments were performed in 0.1 mol L-1 phosphate buffer solutions at pH 7.4 with an incubation time of 8 min. The analytical curve obtained in pure solutions showed excellent linearity in the 5.0 x 10(-5) to 75 x 10(-5) mol L-1 range, with the limit of detection at 0.4 x 10(-3) gL(-1). The application of such a methodology in tomato samples involved solely liquidising the samples, which were spiked with 6.0 x 10(-6) and 5.0 x 10(-5) mol L-1 carbaryl. Recovery in such samples presented values of 99.0 and 92.4%, respectively. In order to obtain a comparison, HPLC experiments were also conducted under similar conditions. However, the tomato samples have to be manipulated by an extraction procedure (MSPD), which yielded much lower recovery values (78.3 and 84.8%, respectively). On the other hand, the detection limit obtained was much lower than that for the biosensor, i.e., 3.2 x 10(-6) g L-1. Finally, the biosensor methodology was employed to analyze carbaryl directly inside the tomato, without any previous manipulation. In this case, the biosensor was immersed in the tomato pulp, which had previously been spiked with the pesticide for 8 min, removed and inserted in the electrochemical cell. A recovery of 83.4% was obtained, showing very low interference of the matrix constituents. (C) 2007 Elsevier B.V. All rights reserved.

Determination of fluoxetine in plasma by gas chromatography-mass spectrometry using stir bar sorptive extraction

This article presents a method employing stir bar sorptive extraction (SBSE) with in situ derivatization, in combination with either thermal or liquid desorption on-line coupled to gas chromatography-mass spectrometry for the analysis of fluoxetine in plasma samples. Ethyl chloroformate was employed as derivatizing agent producing symmetrical peaks. Parameters such as solvent polarity, time for analyte desorption, and extraction time, were evaluated. During the validation process, the developed method presented specificity, linearity (R-2 > 0.99), precision (R.S.D. < 15%), and limits of quantification (LOQ) of 30 and 1.37 pg mL(-1), when liquid and thermal desorption were employed, respectively. This simple and highly sensitive method showed to be adequate for the measurement-of fluoxetine in typical and trace concentration levels. (c) 2008 Elsevier B.V. All rights reserved.

Determination of amino acids by capillary electrophoresis-electrospray ionization-mass spectrometry: An evaluation of different protein hydrolysis procedures

In this work, a CE equipment, online hyphenated to an IT MS analyzer by a linear sheath liquid interface promoting ESI, was used to develop a method for quantitative determination of amino acids. Under appropriate conditions (BGE composition, 0.8% HCOOH, 20% CH(3)OH; sheath liquid composition, 0.8% HCOOH, 60% methanol; V(ESI), +4.50 W), analytical curves of all amino acids from 3 to 80 mg/L were recorded presenting acceptable linearity (r > 0.99). LODs in the range of 16-172 mu mol/L were obtained. BSA, a model protein, was submitted to different hydrolysis procedures (classical acid and basic, and catalyzed by the H(+) form of a cation exchanger resin) and its amino acid profiles determined. In general, the resin-mediated hydrolysis yields were overall similar or better than those obtained by classical acid or basic hydrolysis. The resulting experimental-to-theoretical BSA concentration ratios served as correction factors for the quantitation of amino acids in Brazil nut resin generated hydrolysates.

Quantification of isoorientin and total flavonoids in Passiflora edulis fruit pulp by HPLC-UV/DAD

A method is reported for the quantification of isoorientin (using a standard addition method) and total flavonoids (expressed as rutin, using the external standard method) in passion fruit pulp (Passiflora edulis Sims f. flavicarpa Degener, Passifloraceae). Extraction of flavonoids was optimized by experimental design methodology, and quantitative analysis was performed by high-performance liquid chromatography with photo-diode array detection (HPLC-UV/DAD). The method was developed and validated according to ICH requirements for specificity, linearity, accuracy, precision (repeatability and intermediate precision). LOD and LOQ. Rutin was chosen as standard for the quantification of total flavonoids in order to propose a HPLC method feasible for routine analysis of the flavonoids in the passion fruit pulp. The passion fruit pulp contained 16.226 +/- 0.050 mg L(-1) of isoorientin and 158.037 +/- 0.602 mg L(-1) of total flavonoid, suggesting that P. edulis fruits may be comparable with other flavonoid food sources such as orange juice or sugarcane juice. (C) 2010 Elsevier B.V. All rights reserved.

Analytical Assessment of a Home Made Capillary Electrophoresis Equipment with Linear Charge Coupled Device for Visible Light Absorption Detection in the Determination of Food Dyes

The performance of modular home made capillary electrophoresis equipment with spectrophotometric detection, at a visible region by means of a miniaturized linear charge coupled device, was evaluated for the determination of four food dyes. This system presents a simple but efficient home made cell detection scheme. A computer program that converts the spectral data after each run into the electropherograms was developed to evaluate the analytical parameters. The dyes selected for analytical evaluation of the system were Brilliant Blue FCF, Fast Green FCF, Sunset Yellow FCF, and Amaranth. Separation was carried out in a 29cm length and 75 mu m I.D fused silica capillary, using 10mmolL-1 borate buffer at pH 9, with separation voltage of 7.5kV. The detection limits for the dyes were between 0.3 and 1.5mgL-1 and the method presented adequate linearity over the ranges studied, with correlation coefficients greater than 0.99. The method was applied for determination and quantification of these dyes in fruit juices and candies.

Evaluation of the QuEChERS Method and Gas Chromatography-Mass Spectrometry for the Analysis Pesticide Residues in Water and Sediment

A method for the determination of pesticide residues in water and sediment was developed using the QuEChERS method followed by gas chromatography - mass spectrometry. The method was validated in terms of accuracy, specificity, linearity, detection and quantification limits. The recovery percentages obtained for the pesticides in water at different concentrations ranged from 63 to 116%, with relative standard deviations below 12%. The corresponding results from the sediment ranged from 48 to 115% with relative standard deviations below 16%. The limits of detection for the pesticides in water and sediment were below 0.003 mg L(-1) and 0.02 mg kg(-1), respectively.

Análise dinâmica de solos submetidos à ação simultânea das três componentes da excitação na base rochosa

Durante a análise sísmica de estruturas complexas, o modelo matemático empregado deveria incluir não só as distribuicões irregulares de massas e de rigidezes senão também à natureza tridimensional da ecitação sísmica. Na prática, o elevado número de graus de liberdade involucrado limita este tipo de análise à disponibilidade de grandes computadoras. Este trabalho apresenta um procedimento simplificado, para avaliar a amplificação do movimento sísmico em camadas de solos. Sua aplicação permitiria estabelecer critérios a partir dos quais avalia-se a necessidade de utilizar modelos de interação solo-estrutura mais complexos que os utilizados habitualmente. O procedimento proposto possui as seguientes características : A- Movimento rígido da rocha definido em termos de três componentes ortagonais. Direção de propagação vertical. B- A ecuação constitutiva do solo inclui as características de não linearidade, plasticidade, dependência da história da carga, dissipação de energia e variação de volume. C- O perfil de solos é dicretizado mediante um sistema de massas concentradas. Utiliza-se uma formulação incremental das equações de movimento com integração directa no domínio do tempo. As propriedades pseudo-elásticas do solo são avaliadas em cada intervalo de integração, em função do estado de tensões resultante da acção simultânea das três componentes da excitação. O correcto funcionamento do procedimento proposto é verificado mediante análises unidimensionais (excitação horizontal) incluindo estudos comparativos com as soluções apresentadas por diversos autores. Similarmente apresentam-se análises tridimensionais (acção simultânea das três componentes da excitação considerando registros sísmicos reais. Analisa-se a influência que possui a dimensão da análise (uma análise tridimensional frente a três análises unidimensionais) na resposta de camadas de solos submetidos a diferentes níveis de exçitação; isto é, a limitação do Princípio de Superposisão de Efeitos.

Detectando não-linearidades nos retornos dos fundos multimercados

Estudos recentes apontam que diversas estratégias implementadas em hedge funds geram retornos com características não lineares. Seguindo as sugestões encontradas no paper de Agarwal e Naik (2004), este trabalho mostra que uma série de hedge funds dentro da indústria de fundos de investimentos no Brasil apresenta retornos que se assemelham ao de uma estratégia em opções de compra e venda no índice de mercado Bovespa. Partindo de um modelo de fatores, introduzimos um índice referenciado no retorno sobre opções de modo que tal fator possa explicar melhor que os tradicionais fatores de risco a característica não linear dos retornos dos fundos de investimento.

Tempo no trabalho: a experiência dos gerentes médios

A sociologia das organizações ainda é realizada sob a construção de esquemas analíticos livres de tempo (CLARK, 1985; HASSARD, 2000; GIDDENS, 2003). No entanto, questões temporais permeiam toda e qualquer organização, o que torna o conceito de tempo de central importância para os estudos organizacionais. Com base nisso, esta pesquisa teve a ambição de abordar a dimensão temporal do trabalho nas organizações; sob a perspectiva dos indivíduos. E, dado que os gerentes médios vivenciam um duplo foco de pressão: originado da alta gerência e do nível operacional da organização, decidiu-se investigar como os gerentes médios experimentam o tempo no trabalho. Para desvendar a experiência temporal dos gerentes médios, foram analisadas, com a metodologia de análise de conteúdo, entrevistas com 20 profissionais de média gerência que trabalham em empresas que operam na cidade de São Paulo. A coleta do material de pesquisa ocorreu com entrevistas em profundidade semi-estruturadas. A análise das entrevistas sugere que embora o tempo no trabalho seja, por todos os profissionais entrevistados, definido como um recurso econômico, cuja utilização dever ser otimizada ao máximo, a experiência temporal entre os gerentes médios não é homogênea. Há fatores ambientais comuns a todos os entrevistados, que tendem a aproximar as experiências temporais dos mesmos. Tais fatores, que são a compressão do tempo, o sentido de urgência, as novas tecnologias, características intrínsecas ao papel de gerente e a organização de si próprios, das empresas e colaboradores, estão associados ao cenário econômico e social contemporâneo. No entanto, características relacionadas à idade, gênero, valores e experiências pessoais, além do segmento de atuação da empresa também impactam a experiência temporal dos gerentes médios e contribuem para a diversificação da maneira como os gerentes médios experimentam e lidam com as pressões temporais. Em síntese, a despeito dos fatores ambientais compartilhados, com destaque para a crescente compressão do tempo, a natureza humana e a impermanência dos fenômenos sociais desnudam a complexidade da experiência temporal dos gerentes médios no trabalho. E revelam que – apesar da homogeneidade, objetividade e linearidade representadas pelo relógio, ícone do tempo nas sociedades ocidentais contemporâneas – heterogeneidade, subjetividade e ciclicidade fazem parte da experiência temporal dos trabalhadores.

Models of complexity in Robert Coover's John's wife and the adventures of Lucky Pierre

This doctoral dissertation analyzes two novels by the American novelist Robert Coover as examples of hypertextual writing on the book bound page, as tokens of hyperfiction. The complexity displayed in the novels, John's Wife and The Adventures of Lucky Pierre, integrates the cultural elements that characterize the contemporary condition of capitalism and technologized practices that have fostered a different subjectivity evidenced in hypertextual writing and reading, the posthuman subjectivity. The models that account for the complexity of each novel are drawn from the concept of strange attractors in Chaos Theory and from the concept of rhizome in Nomadology. The transformations the characters undergo in the degree of their corporeality sets the plane on which to discuss turbulence and posthumanity. The notions of dynamic patterns and strange attractors, along with the concept of the Body without Organs and Rhizome are interpreted, leading to the revision of narratology and to analytical categories appropriate to the study of the novels. The reading exercised throughout this dissertation enacts Daniel Punday's corporeal reading. The changes in the characters' degree of materiality are associated with the stages of order, turbulence and chaos in the story, bearing on the constitution of subjectivity within and along the reading process. Coover's inscription of planes of consistency to counter linearity and accommodate hypertextual features to the paper supported narratives describes the characters' trajectory as rhizomatic. The study led to the conclusion that narrative today stands more as a regime in a rhizomatic relation with other regimes in cultural practice than as an exclusively literary form and genre. Besides this, posthuman subjectivity emerges as class identity, holding hypertextual novels as their literary form of choice.

Consumo de bens duráveis e poupança em uma nova trajetória de comportamento do consumidor brasileiro

O trabalho avalia a dinâmica descrita pelo consumo de bens duráveis e poupança dos consumidores brasileiros entre setembro de 2005 e abril de 2011 e contribui com a literatura ao utilizar como ferramenta de análise um modelo autoregressivo com valor limite endógeno e dados qualitativos da pesquisa Sondagem de Expectativas do Consumidor Brasileiro, da FGV. Indicadores qualitativos para essas duas variáveis foram calculados e a metodologia proposta permitiu investigar, simultaneamente, a linearidade e estacionaridade de suas trajetórias. Os resultados sugerem, em ambos os casos, uma dinâmica não-linear com raiz unitária parcial. Adicionalmente, a estacionaridade constatada a partir de um valor limite estimado de 3,3 pontos percentuais para o Indicador de Compras de Bens Duráveis e de 3,6 pontos percentuais para o Indicador de Poupança permitem classificar seus históricos com indícios de saturação da capacidade de poupança e consumo dos indivíduos.

Advertising new product categories to new geographical markets

Em um ambiente global dinâmico e competitivo, muitas empresas notam que constante desenvolvimento e lançamento de novos produtos são atividades-chave para seu crescimento e sobrevivência. Hoje, um dos maiores desafios enfrentados por tais empresas envolve saber como agir em um mundo em que tanto o escopo como a estrutura do ambiente competitivo estão em constante mudança, e em que reestruturações e mudanças de portfólio são centrais para as companhias que visam capitalizar com o crescimento global. Tanto o rápido ritmo de inovação tecnológica quando a crescente afluência de economias emergentes apresentam riscos e oportunidades para as empresas, o que torna importante não apenas que estas estejam atentas ao lançamento de produtos de última geração para mercados desenvolvidos: faz-se também necessário que saibam como lançar produtos antigos para novos mercados. Usando o mercado brasileiro como um exemplo, esta dissertação procurou estudar como multinacionais têm utilizado anúncios publicitários no lançamento, para novos mercados, de categorias e subcategorias de produtos já vendidas em outros países. Após uma revisão da literatura disponível, do desenvolvimento de proposições, e da avaliação destas através de três estudos de caso, foi possível verificar a existência de alguma linearidade entre os casos e a literatura estudada, incluindo: uma busca pela legitimação da categoria que precede àquela pela da marca; o uso de “especialistas” para a legitimação da categoria; o uso de apelos baseados em argumentos; e a divulgação de mais de uma característica de produto por anúncio. No entanto, dadas algumas discrepâncias entre o que foi observado nos casos e aquilo descrito na literatura consultada, também foi possível verificar que a maneira como os anúncios são feitos em diferentes lugares depende igualmente do cenário competitivo enfrentado pela empresa, bem como de variantes econômicas e culturais específicas da localidade em questão.