The role of an insulating surface layer on the relaxation time of the ionic redistribution in an electrolytic cell

We analyze the influence of a surface dielectric layer on the transient phenomena related to the ionic redistribution in an electrolytic cell submitted to a step-like external voltage. The adsorption-desorption phenomenon is taken into account in the famework of the Gouy-Chapman approximation, where the ions are assumed dimensionless. In the limit of small amplitude of the applied voltage, where the equations of the problem can be linearized, we obtain an analytical solution for the surface densities of ions, for the electrical potential and for the relaxation time for the transient phenomena. In the general case, when the linearized analysis is no longer valid, the solution of the problem is obtained numerically. The role of the thickness of the dielectric layer on the relaxation time is also discussed.

Optimization of incubation time of protein Tc85 in the construction of biosensor: Is the EIS a good tool?

Electrochemical impedance spectroscopy (EIS) in pH 6.9 phosphate buffer solution was used to investigate each step of the procedure employed to modify a screen-printed electrode (SPE). The SPE was modified with self-assembled monolayers (SAMs) of cystamine (CYS, deposited from 20 mM solution), followed by glutaraldehyde (GA, 0.3 M solution). The Trypanosoma cruzi antigen was immobilized using different deposition times. The influence of incubation time (2-18 h) of protein was also investigated. The topography of modified electrode with this protein was investigated by atomic force microscopy (AFM). Interpretation of impedance data was based on physical and chemical adsorption, and degradation of the layer at high and meddle frequencies, and charge transfer reaction involving mainly the reduction of oxygen at low frequencies. EIS studies on modified electrodes with Tc85 protein immobilized for different incubation times indicated that the optimum incubation time was 6-8 h. It was demonstrated that EIS is a good technique to evaluate the different steps and the integrity of the surface modifications, and to optimize the incubation time of protein in the development of biosensors. (C) 2010 Elsevier B.V. All rights reserved.

Amazonian Vegetable Oils and Fats: Fast Typification and Quality Control via Triacylglycerol (TAG) Profiles from Dry Matrix-Assisted Laser Desorption/Ionization Time-of-Flight (MALDI-TOF) Mass Spectrometry Fingerprinting

Amazonian oils and fats display unique triacylglycerol (TAG) profiles and, because of their economic importance as renewable raw materials and use by the cosmetic and food industries, are often subject to adulteration and forgery. Representative samples of these oils (andiroba, Brazil nut, buriti, and passion fruit) and fats (cupuacu, murumuru, and ucuba) were characterized without pre-separation or derivatization via dry (solvent-free) matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). Characteristic profiles of TAG were obtained for each oil and tat. Dry MALDI-TOF MS provides typification and direct and detailed information, via TAG profiles, of their variable combinations of fatty acids. A database from spectra could be developed and may be used for their fast and reliable typification, application screening, and quality control.

Evaluation of Postpolymerization as a Function of the Storage Time of Triethylene Glycol Dimethacrylate/2,2-Bis[4-(2-Hydroxy-3-Methacryloxy-Prop-1-Oxy)-Phenyl]-propane Bisphenyl-alpha-Glycidyl Ether Dimethacrylate Copolymers Used in Dental Resins by Differential Scanning Calorimetry and Dynamic Mechanical Analysis

The aim of this work was to evaluate the effect of the storage time on the thermal properties of triethylene glycol dimethacrylate/2,2-bis[4-(2-hydroxy-3-methacryloxy-prop-1-oxy)-phenyl]propane bisphenyl-alpha-glycidyl ether dimethacrylate (TB) copolymers used in formulations of dental resins after photopolymerization. The TB copolymers were prepared by photopolymerization with an Ultrablue IS light-emitting diode, stored in the dark for 160 days at 37 degrees C, and characterized with differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and Fourier transform infrared spectroscopy with attenuated total reflection. DSC curves indicated the presence of an exothermic peak, confirming that the reaction was not completed during the photopolymerization process. This exothermic peak became smaller as a function of the storage time and was shifted at higher temperatures. In DMA studies, a plot of the loss tangent versus the temperature initially showed the presence of two well-defined peaks. The presence of both peaks confirmed the presence of residual monomers that were not converted during the photopolymerization process. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 679-684, 2009

Franchisor-franchisee relationship and performance: influence of personality traits, entrepreneurial drive, and time of relationship

A literatura em franchising tem virtualmente ignorado o papel de aspectos psicologicos nos resultados interorganizacionais das empresas, a despeito de sua influencia nos resultados das organizações e da qualidade de relacionamento. Este estudo, portanto, tem por objetivo analisar a influência da personalidade e do potencial empreendedor na qualidade de relacionamento e desempenho financeiro na relação franqueador-franqueado, ao longo do tempo, sob a perspectiva dos franqueados. Este estudo analisa também o papel do tempo de relacionamento sobre a qualidade de relacionamento e o desempenho financeiro. Foi utilizado neste estudo um questionário de auto-preenchimento, enviado por e-mail, com o objetivo de recolher dados de uma amostra de 342 franqueados de 3 redes de franquias. A personalidade foi mensurada por meio dos “Cinco Grandes” traços de personalidade (escalas IPIP-B5): extroversão, agradabilidade, consciencia, estabilidade emocional e imaginação. O potencial empreendedor foi mensurado por meio do índice CEI (Carland Entrepreneurship Index). A qualidade do relacionamento foi estruturada como um constructo de segunda ordem, composto por 23 itens (incorporando confiança, comprometimento e satisfação com o relacionamento), e o desempenho financeiro foi representado por meio de uma escala de mensuração de crescimento de vendas e de rentabilidade. O tempo de relacionamento foi medido por meio dos meses de relacionamento entre franqueado e franqueador. As hipoteses foram testadas por meio de modelagem por equações estruturais, com a utilização do método de mínimos quadrados parciais (PLS), análise de regressão e análise de médias. Três das cinco dimensões da personalidade apresentaram o efeito previsto sobre as variáveis qualidade do relacionamento – agradabilidade (positivamente), estabilidade emocional (positivamente), e imaginação (positivamente). O desempenho financeiro foi influenciado, como previsto por consciência (positivamente), estabilidade emocional (positivamente), e imaginação (positivamente). Como esperado, a qualidade do relacionamento apresentou efeito positivo e significativo em relação ao desempenho financeiro. O potencial empreendedor apresentou o efeito positivo previsto apenas sobre desempenho. O tempo de relacionamento teve o efeito positivo esperado sobre o relacionamento franqueador-franqueado, em relação à qualidade do relacionamento e o desempenho financeiro, mas as diferenças entre as fases de relacionamento propostas foram apenas parcialmente confirmadas, uma vez que em somente duas fases (rotina e estabilização) a análise de médias mostrou diferenças significativas. Os resultados indicam que a personalidade influencia a qualidade de relacionamento e o desempenho, mas a meneira pela qual isso ocorre é diferente no contexto brasileiro, onde esta pesquisa foi realizada, dos achados da pesquisa conduzida na Austrália, sugerindo que fatores como cultura e estabilidade de mercado podem ter influencia sobre a relação entre traços de personalidade e qualidade de relacionamento, e traços de personalidade e desempenho financeiro. O potencial empreendedor parece influenciar positivamente o desempenho do franqueado, mas a sua influência não foi significativa em relação à qualidade do relacionamento. Os resultados também indicam a importância do tempo no desenvolvimento da qualidade de relacionamento e desempenho. Além disso, os relacionamentos de longo prazo estão relacionados a melhores avaliações de qualidade de relacionamento e desempenho financeiros por parte dos franqueados. As limitações do trabalho e sugestões para estudos futuros também são discutidos.

Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextraction as a powerful tool for quantification of ethyl carbamate in fortified wines. The case study of Madeira wine

An analytical methodology based on headspace solid phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography—time-of-flight mass spectrometry (GC × GC–ToFMS) was developed for the identification and quantification of the toxic contaminant ethyl carbamate (EC) directly in fortified wines. The method performance was assessed for dry/medium dry and sweet/medium sweet model wines, and for quantification purposes, calibration plots were performed for both matrices using the ion extraction chromatography (IEC) mode (m/z 62). Good linearity was obtained with a regression coefficient (r2) higher than 0.981. A good precision was attained (R.S.D. <20%) and low detection limits (LOD) were achieved for dry (4.31 μg/L) and sweet (2.75 μg/L) model wines. The quantification limits (LOQ) and recovery for dry wines were 14.38 μg/L and 88.6%, whereas for sweet wines were 9.16 μg/L and 99.4%, respectively. The higher performance was attainted with sweet model wine, as increasing of glucose content improves the volatile compound in headspace, and a better linearity, recovery and precision were achieved. The analytical methodology was applied to analyse 20 fortified Madeira wines including different types of wine (dry, medium dry, sweet, and medium sweet) obtained from several harvests in Madeira Island (Portugal). The EC levels ranged from 54.1 μg/L (medium dry) to 162.5 μg/L (medium sweet).

In-depth search focused on furans, lactones, volatile phenols, and acetals as potential age markers of Madeira wines by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextraction

The establishment of potential age markers of Madeira wine is of paramount significance as it may contribute to detect frauds and to ensure the authenticity of wine. Considering the chemical groups of furans, lactones, volatile phenols, and acetals, 103 volatile compounds were tentatively identified; among these, 71 have been reported for the first time in Madeira wines. The chemical groups that could be used as potential age markers were predominantly acetals, namely, diethoxymethane, 1,1-diethoxyethane, 1,1-diethoxy-2-methyl-propane, 1-(1-ethoxyethoxy)-pentane, trans-dioxane and 2-propyl-1,3-dioxolane, and from the other chemical groups, 5-methylfurfural and cis-oak-lactone, independently of the variety and the type of wine. GC × GC-ToFMS system offers a more useful approach to identify these compounds compared to previous studies using GC−qMS, due to the orthogonal systems, that reduce coelution, increase peak capacity and mass selectivity, contributing to the establishment of new potential Madeira wine age markers. Remarkable results were also obtained in terms of compound identification based on the organized structure of the peaks of structurally related compounds in the GC × GC peak apex plots. This information represents a valuable approach for future studies, as the ordered-structure principle can considerably help the establishment of the composition of samples. This new approach provides data that can be extended to determine age markers of other types of wines.

The Predation of Artemia Nauplii by the Larvae of the Amazon River Prawn, Macrobrachium amazonicum (Heller, 1862), is Affected by Prey Density, Time of Day, and Ontogenetic Development

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)