Deactivation of Ferrylmyoglobin by Vanillin as Affected by Vanillin Binding to beta-Lactoglobulin

Vanillin was found to be efficient as a deactivator of ferrylmyoglobin with a second-order rate constant of k(2) = S7 +/- 1 L mol(-1) s(-1) for reduction to metmyoglobin with Delta H(double dagger) = 58.3 +/- 0.3 kJ mol(-1) and Delta S(double dagger) = -14 +/- 1 J mol(-1) K(-1) in aqueous pH 7.4 solution at 25 degrees C. Binding to beta-lactoglobulin (AG) was found to affect the reactivity of vanillin at 25 degrees C only slightly to k(2) = 48 +/- 2 L mol(-1) s(-1) (Delta H(double dagger) = 68.4 +/- 0.4 kJ mol(-1) and Delta S(double dagger) = 17 +/- 1 J mol(-1) K(-1)) for deactivation of ferrylmyoglobin. Binding of vanillin to beta LG was found to have a binding stoichiometry vanillin/beta LG > 10 with K(A) = 6 x 10(2) L mol(-1) and an apparent total Delta H degrees of approximately -38 kJ mol(-1) and Delta S degrees = -S5.4 +/- 4J mol(-1) K(-1) at 25 degrees C and Delta C(p), (obs) = -1.02 kJ mol(-1) K(-1) indicative of increasing ordering in the complex, as determined by isothermal titration microcalorimetry. From tryptophan fluorescence quenching for beta LG by vanillin, approximately one vanillin was found to bind to each beta LG far stronger with K(A) = 5 x 10(4) L, mol(-1) and a Delta H degrees = 10.2 kJ mol(-1) and Delta S degrees = 55J mol(-1) K(-1) at 25 degrees C. The kinetic entropy/enthalpy compensation effect seen for vanillin reactivity by binding to beta LG is concluded to relate to the weakly bound vanillin oriented through hydrogen bonds on the beta LG surface with the phenolic group pointing toward the solvent, in effect making both Delta H(double dagger) and Delta S(double dagger) more positive. The more strongly bound vanillin capable of tryptophan quenching in the fiLG calyx seems less or nonreactive.

Reactivity of Beer Bitter Acids Toward the 1-Hydroxyethyl Radical as Probed by Spin-Trapping Electron Paramagnetic Resonance (EPR) and Electrospray Ionization-Tandem Mass Spectrometry (ESI-MS/MS)

The iso-alpha-acids or isohumulones are the major contributors to the bitter taste of beer, and it is well-recognized that they are degraded during beer aging. In particular, the trans-isohumulones seem to be less stable than the cis-isohumulones. The major radical identified in beer is the 1-hydroxyethyl radical; however, the reactivity between this radical and the isohumulones has not been reported until now. Therefore, we studied the reactivity of isohumulones toward the 1-hydroxyethyl radical through a competitive kinetic approach. It was observed that both cis- and trans-isohumulones and dihydroisohumulones are decomposed in the presence of 1-hydroxyethyl radicals, while the reactivities are comparable. On the other hand, the tetrahydroisohumulones did not react with 1-hydroxyethyl radicals. The apparent second-order rate constants for the reactions between the 1-hydroxyethyl radical and these compounds were determined by electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization-tandem mass spectrometry [ESI(+)-MS/MS]. It follows that degradation of beer bitter acids is highly influenced by the presence of 1-hydroxyethyl radicals. The reaction products were detected by liquid chromatography electrospray ionization-ion trap-tandem mass spectrometry (LC-ESI-IT-MS/MS), and the formation of oxidized derivatives of the isohumulones was confirmed. These data help to understand the mechanism of beer degradation upon aging.

Quenching of excited states of red-pigment zinc protoporphyrin IX by hemin and natural reductors in dry-cured hams

Zinc protoporphyrin IX (ZnPP), the major red pigment in hams dry-cured without nitrates/nitrites, is an efficient photosensitizer, which upon absorption of visible light forms short-lived excited singlet state ((1)ZnPP*) and by intersystem crossing yields the very reactive triplet-excited state ((3)ZnPP*). Using nano-second laser flash photolysis and transient absorption spectroscopy NADH, ascorbic acid, hemin and dehydroascorbic acid were each found to be efficient quenchers of (3)ZnPP*. The deactivation followed, in homogeneous dimethyl sulfoxide (DMSO) or DMSO:water (1:1) solutions, second-order kinetics. The rate constant for ascorbic acid and NADH for reductive quenching of (3)ZnPP* was at 25 A degrees C found to be 7.5 +/- A 0.1 x 10(4) L mol(-1) s(-1) and 6.3 +/- A 0.1 x 10(5) L mol(-1) s(-1), respectively. The polyphenols catechin and quercetin had no effect on (3)ZnPP*. The quenching rate constant for oxidative deactivation of (3)ZnPP* by dehydroascorbic acid and hemin was at 25 A degrees C: 1.6 +/- A 0.1 x 10(5) L mol(-1) s(-1) and 1.47 +/- A 0.1 x 10(9) L mol(-1) s(-1), respectively. Oxidized glutathione did not act as an oxidative quencher for (3)ZnPP*. After photoexcitation of ZnPP to (1)ZnPP*, fluorescence was only found to be quenched by the presence of hemin in a diffusion-controlled reaction. The efficient deactivation of (3)ZnPP* and (1)ZnPP* by the metalloporphyrin (hemin) naturally present in meat may accordingly inherently protect meat proteins and lipids against ZnPP photosensitized oxidation.

Light-Induced Oxidation of Unsaturated Lipids as Sensitized by Flavins

Triplet-excited riboflavin ((3)RF*) was found by laser flash photolysis to be quenched by polyunsaturated fatty acid methyl esters in tert-butanol/water (7:3, v/v) in a second-order reaction with k similar to 3.0 x 10(5) L mol(-1) s(-1) at 25 degrees C for methyl linoleate and 3.1 x 10(6) L mol(-1) s(-1), with Delta H double dagger = 22.6 kJ mol(-1) and Delta S double dagger = -62.3 J K(-1) mol(-1), for methyl linolenate in acetonitrile/water (8:2, v/v). For methyl oleate, k was <10(4) L mol(-1) s(-1). For comparison, beta-casein was found to have a rate constant k similar to 4.9 x 10(8) L mol(-1) s(-1). Singlet-excited flavin was not quenched by the esters as evidenced by insensitivity of steady-state fluorescence to their presence. Density functional theory (DFT) calculations showed that electron transfer from unsaturated fatty acid esters to triplet-excited flavins is endergonic, while a formal hydrogen atom transfer is exergonic (Delta G(HAT)degrees = -114.3, -151.2, and -151.2 kJ mol(-1) for oleate, linoleate, and linolenate, respectively, in acetonitrile). The reaction is driven by acidity of the lipid cation radical for which a pK(a) similar to -0.12 was estimated by DFT calculations. Absence of electrochemical activity in acetonitrile during cyclic voltammetry up to 2.0 V versus NHE confirmed that Delta G(ET)degrees > 0 for electron transfer. Interaction of methyl esters with (3)RF* is considered as initiation of the radical chain, which is subsequently propagated by combination reactions with residual oxygen. In this respect, carbon-centered and alkoxyl radicals were detected using the spin trapping technique in combination with electron paramagnetic resonance spectroscopy. Moreover, quenching of 3RF* yields, directly or indirectly, radical species which are capable of initiating oxidation in unsaturated fatty acid methyl esters. Still, deactivation of triplet-excited flavins by lipid derivatives was slower than by proteins (factor up to 10(4)), which react preferentially by electron transfer. Depending on the reaction environment in biological systems (including food), protein radicals are expected to interfere in the mechanism of light-induced lipid oxidation.

Quantitative Information Flow, Relations and Polymorphic Types

This paper uses Shannon's information theory to give a quantitative definition of information flow in systems that transform inputs to outputs. For deterministic systems, the definition is shown to specialise to a simpler form when the information source and the known inputs jointly determine the inputs. For this special case, the definition is related to the classical security condition of non-interference and an equivalence is established between non-interference and independence of random variables. Quantitative information flow for deterministic systems is then presented in relational form. With this presentation, it is shown how relational parametricity can be used to derive upper and lower bounds on information flows through families of functions defined in the second order lambda calculus.

Stock Markets and Household Wealth: Can a Stock Market Crash Cause a Recession in The U.S. Economy?

Stock market wealth effects on the level of consumption in the United States economy have been constantly debated; there is evidence for arguments for and against its prominence and its symmetry. This paper seeks to investigate the strength of its negative effect by creating models to analyze unexpected shocks to the Standard and Poor's 500 index. First, a transmission mechanism between the stock market and GDP is established through the use of second-order vector autoregressive models. Following which, theory from the life cycle model and adaptations of previous researchers' models are used to create a structural model. This paper finds that stock market wealth effects are small, but important to consider, especially if markets are overpriced; this claim is corroborated by evidence from simulation of 'alternative scenarios' and the historical experiences of 1987 and 2001.

Regulação e defesa da concorrência: bases conceituais e aplicações do sistema de competências compartilhadas

Esta pesquisa discute configurações institucionais ótimas e sugere, nas atuais circunstâncias brasileiras, mecanismos de cooperação inter-institucional, de sorte a maximizar a eficiência de ações conjuntas entre agências regulatórias e de defesa da concorrência, minimizando os custos de coordenação. A pesquisa contém três partes. A primeira discute aspectos teóricos de um sistema de competências complementares entre a autoridade de defesa da concorrência e a agência regulatória, destacando suas eventuais vantagens comparativamente às possíveis configurações institucionais alternativas. A segunda contém breve sumário da experiência histórico-concreta nos planos mundial e nacional, procurando situar, na medida do possível, diferentes países e setores em tipologia sugerida na primeira parte. A terceira apresenta algumas recomendações de política.

A general lagrangian approach for non-concave moral hazard problems

We establish a general Lagrangian for the moral hazard problem which generalizes the well known first order approach (FOA). It requires that besides the multiplier of the first order condition, there exist multipliers for the second order condition and for the binding actions of the incentive compatibility constraint. Some examples show that our approach can be useful to treat the finite and infinite state space cases. One of the examples is solved by the second order approach. We also compare our Lagrangian with 1\1irrlees'.

Welfare characterization of monetary-applied models and three implications

This paper demonstrates that the applied monetary models - the Sidrauski-type models and the cash-in-advance models, augmented with a banking sector that supplies money substitutes services - imply trajectories which are Pareto-Optimum restricted to a given path of the real quantity of money. As a consequence, three results follow: First, Bailey’s formula to evaluate the welfare cost of inflation is indeed accurate, if the longrun capital stock does not depend on the inflation rate and if the compensate demand is considered. Second, the relevant money demand concept for this issue - the impact of inflation on welfare - is the monetary base. Third, if the long-run capital stock depends on the inflation rate, this dependence has a second-order impact on welfare, and, conceptually, it is not a distortion from the social point of view. These three implications moderate some evaluations of the welfare cost of the perfect predicted inflation.

A general lagrangian approach for non-concave moral hazard problems

We establish a general Lagrangian for the moral hazard problem which generalizes the well known first order approach (FOA). It requires that besides the multiplier of the first order condition, there exist multipliers for the second order condition and for the binding actions of the incentive compatibility constraint. Some examples show that our approach can be useful to treat the finite and infinite state space cases. One of the examples is solved by the second order approach. We also compare our Lagrangian with 1\1irrlees'.

Operacionalização dos objetivos educacionais nos cursos de engenharia

Para a consecução das finalidades de uma disciplina de um curso , várias estratégias de ensino podem ser utilizadas. A estratégia de ensino por objetivos operacionalizados adota, como princípio fundamental, a descrição dos objetivos educacionais em termos do desempenho esperado do aluno e a fixação de padrões mínimos de rendimento aceitável nesse desempenho. A programação de ensino por objetivos operacionalizados deve ser dada a conhecer ao educando, e deve servir de base para o planejamento das atividades docentes e discentes , orientando o aluno nos seus esforços para aprender, e o professor na escolha das técnicas e recursos de ensino que permitam tornar o ensino eficaz. Os resultados da pesquisa empírica realizada mostram que, no nível de efeito principal, o ensino por objetivos operacionalizados é ligeiramente superior ao ensino tradicional . Três turmas foram objeto do experimento, cujo propósito foi comparar , no ensino de Geometria Descritiva, a eficácia relativa das estratégias de ensino com programação por objetivos operacionalizados e a do ensino tradicional. Resultaram os Índices representativos daquela variável: 5,63 para o ensino tradicional, 7,48 para o ensino por objetivos operacionalizados com programação rígida e 7,29 para o ensino por objetivos operacionalizados em que os alunos tiveram liberdade de alguns dos objetivos educacionais. Fortes efeitos de interação foram detectados entre a variável Estratégia de Ensino e as variáveis Escores do Concurso Vestibular, Caracterização Sócio-Econômica e Cultural e Assiduidade, mostrando que, para algumas categorias de alunos, o ensino por objetivos operacionalizados tem rendimento significativamente maior que o ensino tradicional. Os resultados mostram que para algumas categorias a liberdade dada ao aluno para escolher alguns dos objetivos educacionais prejudica o seu nível de aproveitamento no curso, relativamente à mesma estratégia de ensino, porém, com programação totalmente fixada pelo professor. Mesmo nesses casos, o rendimento do ensino por objetivos operacionalizados revela-se superior ao do ensino tradicional.

Welfare characterization of monetary-applied models and three implications

This paper demonstrates that the applied monetary mo deIs - the Sidrauski-type models and the cash-in-advance models, augmented with a banking sector that supplies money substitutes services - imply trajectories which are P8,reto-Optimum restricted to a given path of the real quantity of money. As a consequence, three results follow: First, Bailey's formula to evaluate the wclfare cost of inflation is indeed accurate, if the long-run capital stock does not depend on the inflation rate and if the compensate demand is considered. Second, the relevant money demand concept for this issue - the impact of inflation on welfare - is the monetary base, Third, if the long-run capital stock depends on the inflation rate, this dependence has a second-order impact ou wclfare, and, conceptually, it is not a distortion from tite social point of vicw. These three implications moderatc some evaluations of the wclfare cost of the perfect predicted inflation.

Estudo comparativo do desempenho de controladores robustos aplicados a um sistema de tanques acoplados.

Currently the uncertain system has attracted much academic community from the standpoint of scientific research and also practical applications. A series of mathematical approaches emerge in order to troubleshoot the uncertainties of real physical systems. In this context, the work presented here focuses on the application of control theory in a nonlinear dynamical system with parametric variations in order and robustness. We used as the practical application of this work, a system of tanks Quanser associates, in a configuration, whose mathematical model is represented by a second order system with input and output (SISO). The control system is performed by PID controllers, designed by various techniques, aiming to achieve robust performance and stability when subjected to parameter variations. Other controllers are designed with the intention of comparing the performance and robust stability of such systems. The results are obtained and compared from simulations in Matlab-simulink.

Modelagem e medições de ondas de rádio para predição de perda de propagação em ambientes urbanos

In this dissertation new models of propagation path loss predictions are proposed by from techniques of optimization recent and measures of power levels for the urban and suburban areas of Natal, city of Brazilian northeast. These new proposed models are: (i) a statistical model that was implemented based in the addition of second-order statistics for the power and the altimetry of the relief in model of linear losses; (ii) a artificial neural networks model used the training of the algorithm backpropagation, in order to get the equation of propagation losses; (iii) a model based on the technique of the random walker, that considers the random of the absorption and the chaos of the environment and than its unknown parameters for the equation of propagation losses are determined through of a neural network. The digitalization of the relief for the urban and suburban areas of Natal were carried through of the development of specific computational programs and had been used available maps in the Statistics and Geography Brazilian Institute. The validations of the proposed propagation models had been carried through comparisons with measures and propagation classic models, and numerical good agreements were observed. These new considered models could be applied to any urban and suburban scenes with characteristic similar architectural to the city of Natal

Metodologia para re-sintonia de controladores PID industriais

The present work has as objective to present a method of project and implementation of controllers PID, based on industrial instrumentation. An automatic system of auto-tunning of controllers PID will be presented, for systems of first and second order. The software presented in this work is applied in controlled plants by PID controllers implemented in a CLP. Software is applied to make the auto-tunning of the parameters of controller PID of plants that need this tunning. Software presents two stages, the first one is the stage of identification of the system using the least square recursive algorithm and the second is the stage of project of the parameters of controller PID using the root locus algorithm. An important fact of this work is the use of industrial instrumentation for the accomplishment of the experiments. The experiments had been carried through in controlled real plants for controllers PID implemented in the CLP. Thus has not only one resulted obtained with theoreticians experiments made with computational programs, and yes resulted obtained of real systems. The experiments had shown good results gotten with developed software