INSECT CHYMOTRYPSINS: CHLOROMETHYL KETONE INACTIVATION AND SUBSTRATE SPECIFICITY RELATIVE TO POSSIBLE COEVOLUTIONAL ADAPTATION OF INSECTS AND PLANTS

Insect digestive chymotrypsins are present in a large variety of insect orders but their substrate specificity still remains unclear. Ewer insect chymotrypsins from 3 different insect orders (Dictyoptera, Coleoptera and two Lepidoptera) were isolated using affinity chromatography. Enzymes presented molecular masses in the range of 20 to 31 kDa and pH optima in the range of 7.5 to 10.0. Kinetic characterization. using different, colorimetric and fluorescent substrates indicated that insect chymotrypsins differ from, bovine chymotrypsin in their primary specificity toward small substrates (like N-benzoyl-L-Tyr p-nitroanilide) rather than on their preference for large substrates (exemplified by Succynil-Ala-Ala-Pro-Phe P-nitroanilide). Chloromethyl ketones (TPCK, N-alpha-tosyl-L-Phe chloromethyl ketone and Z-GGF-CK, N-carbobenzoxy-Gly-Gly-phe-CK) inactivated all chymotrypsins legated. Inactivation rates follow apparent first-order kinetics with variable second order rates (TPCK, 42 to 130 M(-1)s(-1); Z-GGF-CK, 150 to 450 M(-1)s(-1) that may be remarkably low for S. frugiperda chymotrypsin (TPCK, 6 M(-1)s(-1); Z-GGF-CK, 6.1 M(-1) s(-1)). Homology modelling and sequence alignment showed that. in lepidopteran chymotrypsins, differences in the amino acid residues in the neighborhood of the catalytic His 57 may affect its pKa, value. This is Proposed as the cause of the decrease in His 57 reactivity toward chloromethyl ketones. Such amino acid replacement in the active site is proposed. to be an adaptation to the presence of dietary ketones. (C) 2009 Wiley Periodicals, Inc.

Thermo-solvatochromism of merocyanine polarity probes - What are the consequences of increasing probe lipophilicity through annelation?

The question raised in the title has been answered by comparing the solvatochromism of two series of polarity probes, the lipophilicities of which were increased either by increasing the length of an alkyl group (R) attached to a fixed pyridine-based structure or through annelation (i.e., by fusing benzene rings onto a central pyridine-based structure). The following novel solvatochromic probes were synthesized: 2,6-dibromo-4-[(E)-2-(1-methylquinolinium-4-yl)ethenyl]-phenolate (MeQMBr(2)) and 2,6-dibromo-4-[(E)-2-(1-methyl-acridinium-4- yl) ethenyl)]phenolate (MeAMBr(2) The solvatochromic behavior of these probes, along with that of 2,6dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl]phenol-ate(MePMBr(2)) was analyzed in terms of increasing probe lipophilicity, through annelation. Values of the empirical solvent polarity scale [E(T)(MePMBr(2))] in kcalmol(-1) correlated linearly with ET(30), the corresponding values for the extensively employed probe 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (RB). On the other hand, the nonlinear correlations of ET(MeQMBr(2)) or ET(MeAMBr(2)) with E(T)(30) are described by second-order polynomials. Possible reasons for this behavior include: i) self-aggregation of the probe, ii) photoinduced cis/trans isomerization of the dye, and iii) probe structure- and solvent-dependent contributions of the quinonoid and zwitterionic limiting formulas to the ground and excited states of the probe. We show that mechanisms (i) and (ii) are not operative under the experimental conditions employed; experimental evidence (NMR) and theoretical calculations are presented to support the conjecture that the length of the central ethenylic bond in the dye increases in the order MeAMBr(2) > MeQMBr(2) > MePMBr(2), That is, the contribution of the zwitterionic limiting formula predominates for the latter probe, as is also the case for RB, this being the reason for the observed linear correlation between the ET(MePMBr2) and the ET(30) scales. The effect of increasing probe lipophilicity on solvatochromic behavior therefore depends on the strategy employed. Increasing the length of R affects solvatochromism much less than annelation, because the former structural change hardly perturbs the energy of the intramolecular charge-transfer transition responsible for solvatochromism. The thermo-solvatochromic behavior (effect of temperature on solvatochromism) of the three probes was studied in mixtures of water with propanol and/or with DMSO. The solvation model used explicitly considers the presence of three ""species"" in the system: bulk solution and probe solvation shell [namely, water (W), organic solvent (Solv)], and solvent-water hydrogen-bonded aggregate (Solv-W). For aqueous propanol, the probe is efficiently solvated by Solv-W; the strong interaction of DMSO with W drastically decreases the efficiency of Solv-W in solvating the probe, relative to its precursor solvents. Temperature increases resulted in desolvation of the probes, due to the concomitant reduction in the structured characters of the components of the binary mixtures.

Design/Evaluation of A Methodology For Performance Optimization Of Indexable Carbide Inserts

In this project, two broad facets in the design of a methodology for performance optimization of indexable carbide inserts were examined. They were physical destructive testing and software simulation.For the physical testing, statistical research techniques were used for the design of the methodology. A five step method which began with Problem definition, through System identification, Statistical model formation, Data collection and Statistical analyses and results was indepthly elaborated upon. Set-up and execution of an experiment with a compression machine together with roadblocks and possible solution to curb road blocks to quality data collection were examined. 2k factorial design was illustrated and recommended for process improvement. Instances of first-order and second-order response surface analyses were encountered. In the case of curvature, test for curvature significance with center point analysis was recommended. Process optimization with method of steepest ascent and central composite design or process robustness studies of response surface analyses were also recommended.For the simulation test, AdvantEdge program was identified as the most used software for tool development. Challenges to the efficient application of this software were identified and possible solutions proposed. In conclusion, software simulation and physical testing were recommended to meet the objective of the project.

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.

Ensaios em gestão de risco e regulação bancária

Esta tese é constituída por três ensaios. O primeiro ensaio analisa a informação pública disponível sobre o risco das carteiras de crédito dos bancos brasileiros, sendo dividido em dois capítulos. O primeiro analisa a limitação da informação pública disponibilizada pelos bancos e pelo Banco Central, quando comparada a informação gerencial disponível internamente pelos bancos. Concluiu-se que existe espaço para o aumento da transparência na divulgação das informações, fato que vem ocorrendo gradativamente no Brasil através de novas normas relacionadas ao Pilar 3 de Basileia II e à divulgação de informações mais detalhas pelo Bacen, como, por exemplo, aquelas do “Top50” . A segunda parte do primeiro ensaio mostra a discrepância entre o índice de inadimplência contábil (NPL) e a probabilidade de inadimplência (PD) e também discute a relação entre provisão e perda esperada. Através da utilização de matrizes de migração e de uma simulação baseada na sobreposição de safras de carteira de crédito de grandes bancos, concluiu-se que o índice de inadimplência subestima a PD e que a provisão constituída pelos bancos é menor que a perda esperada do SFN. O segundo ensaio relaciona a gestão de risco à discriminação de preço. Foi desenvolvido um modelo que consiste em um duopólio de Cournot em um mercado de crédito de varejo, em que os bancos podem realizar discriminação de terceiro grau. Neste modelo, os potenciais tomadores de crédito podem ser de dois tipos, de baixo ou de alto risco, sendo que tomadores de baixo risco possuem demanda mais elástica. Segundo o modelo, se o custo para observar o tipo do cliente for alto, a estratégia dos bancos será não discriminar (pooling equilibrium). Mas, se este custo for suficientemente baixo, será ótimo para os bancos cobrarem taxas diferentes para cada grupo. É argumentado que o Acordo de Basileia II funcionou como um choque exógeno que deslocou o equilíbrio para uma situação com maior discriminação. O terceiro ensaio é divido em dois capítulos. O primeiro discute a aplicação dos conceitos de probabilidade subjetiva e incerteza Knigthiana a modelos de VaR e a importância da avaliação do “risco de modelo”, que compreende os riscos de estimação, especificação e identificação. O ensaio propõe que a metodologia dos “quatro elementos” de risco operacional (dados internos, externos, ambiente de negócios e cenários) seja estendida à mensuração de outros riscos (risco de mercado e risco de crédito). A segunda parte deste último ensaio trata da aplicação do elemento análise de cenários para a mensuração da volatilidade condicional nas datas de divulgação econômica relevante, especificamente nos dias de reuniões do Copom.

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.

Rejeito de xisto como adsorvente para remoção de fenol em águas produzidas na indústria de petróleo

Produced water is the main effluent linked to the activity of extraction of oil and their caring management is necessary due to the large volume involved, to ensure to minimize the negative impacts of discharges of these waters in the environment. This study aimed to analyze the use of retorted shale, which is a reject from the pyrolysis of pirobituminous shale, as adsorbent for the removal of phenols in produced water. The material was characterized by different techniques (grain sized analysis, thermal analysis, BET, FRX, FT-IR, XRD and SEM), showing the heterogeneity in their composition, showing its potential for the removal of varied compounds, as well as the phenols and their derivatives. For the analysis of the efficiency of the oil shale for the adsorption process, assays of adsorption balance were carried through, and also kinetic studies and dynamics adsorption, in the ETE of the UTPF of Petrobras, in Guamaré-RN. The balance assays shown a bigger conformity with the model of Langmuir and the kinetic model more adjusted to describe the adsorption of phenols in retorted shale was of pseudo-second order. The retorted shale presented a low capacity of adsorption of phenols (1,3mg/g), when related to others conventional adsorbents, however it is enough to the removal of these composites in concentrations presented in the produced water of the UTPF of Guamaré. The assays of dynamics adsorption in field had shown that the concentration of phenol in the effluent was null until reaching its rupture (58 hours). The results showed the possibility of use of the reject for removal of phenols in the final operations of the treatment process, removing as well, satisfactorily, the color and turbidity of the produced water, with more than 90% of removal

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.

Structural and Biochemical Characterization of Peroxiredoxin Q beta from Xylella fastidiosa CATALYTIC MECHANISM and HIGH REACTIVITY

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Repercussão geral e súmula vinculante: os efeitos no controle difuso

Brazil since its first republican constitution has adopted systems of laws control. The review activity was given to three state powers or functions state, Executive, Legislative and Judiciary. However, it appears that in the country along the constitutional history, has stood considerably the jurisdictional control of the most important control. Initially, back in 1891, Brazil adopted the jurisdictional control of diffuse from U.S, whose role in monitoring of standards is delivered to all organs of the judiciary, which may face a case, put on trial, ascertain whether or not the possibility of applying a law, removing its impact in case of unconstitutionality. In 1969, entered in the second legal model of judicial review, the concentrated control of constitutionality, whose inspiration comes from the positivist theory of Hans Kelsen, and was adopted by the Austrian Constitution of 1920. According to the abstract control the supervision of law is given to a Court or Constitutional Court, responsible for the analysis of the legal constitutionality independent of its application to a specific case. In Brazil the role of concentrated control was handed over exclusively to the Supreme Court, which serves as the Constitutional Court, which accumulates that function with other constitutionally provided jurisdiction. Throughout this period, from 1891 until today, Brazil has maintained a dual system of judicial control of legal constitutionality, where they coexist and harmonize the diffuse control exercised by any organ of the Judiciary, and concentrated control of competence the Supreme Court. However, one must recognize that with the advent of the Federal Constitution of 1988, the concentrated control has emerged on the national stage due to two important factors: the expansion of the legal capacity to sue and the inclusion of other ways control, besides the already known Direct Claim of Unconstitutionality. This concentrated control and projection of the Supreme Court s attempt to become a true constitutional court, led to a relative weakening of diffuse control even when performed by the Brazilian Constitutional Court. In order to become a true constitutional court, all decisions handed down by the Supreme in the exercise of constitutional jurisdiction should have the same weight and the same measure, or at least bring improvement to similar effects, once is the responsible for the final word when it comes to constitutional interpretation. Thus, the writs of certiorari and stare decisis were responsible for profound changes in the diffuse control, allowing the Supreme Court can strengthen its decisions even in the diffuse control. These two institutions have substantially changed the legal status of diffuse control, allowing an extension of the effects of decisions handed down by the Supreme Court, so that you can no longer be said that the effects of this control to restrict the disputing parties in the process

Morfometria de microbacias do Córrego Rico, afluente do Rio Mogi-Guaçu, Estado de São Paulo, Brasil

Este trabalho teve como objetivo avaliar as características morfométricas das microbacias (2ª, 3ª, 4ª e 5ª ordens de magnitude) da bacia hidrográfica do córrego Rico, sub-bacia do Rio Mogi-Guaçu, localizada na região administrativa de Ribeirão Preto, Estado de São Paulo, Brasil. Para tanto, foram determinados os parâmetros físicos e a configuração topográfica natural do sistema de drenagem. Os procedimentos para a obtenção dos dados foram fundamentados em técnicas de sensoriamento remoto e geoprocessamento. A partir da vetorização das cartas topográficas correspondentes à área de estudo, realizou-se a análise morfométrica quanto às características dimensionais, do padrão de drenagem e do relevo no sistema de informação geográfica ArcView. A microbacia é considerada de sexta ordem de magnitude, com área estimada de 542 km², com 85 microbacias de segunda ordem, 22 de terceira, sete de quarta ordem e duas de quinta. Utilizando o critério geométrico, na disposição fluvial das sub-bacias de cabeceiras observou-se a predominância dos modelos dendríticos e subdendríticos, enquanto a jusante predominava o modelo subparalelo, respectivamente, nas áreas de ocorrências dos arenitos Bauru e rochas efusivas básicas.

Bayesian analysis of random regression models using B-splines to model test-day milk yield of Holstein cattle in Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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

Modelagem linear e identificação do modelo dinâmico de um robô móvel com acionamento diferencial

This work presents a modelling and identification method for a wheeled mobile robot, including the actuator dynamics. Instead of the classic modelling approach, where the robot position coordinates (x,y) are utilized as state variables (resulting in a non linear model), the proposed discrete model is based on the travelled distance increment Delta_l. Thus, the resulting model is linear and time invariant and it can be identified through classical methods such as Recursive Least Mean Squares. This approach has a problem: Delta_l can not be directly measured. In this paper, this problem is solved using an estimate of Delta_l based on a second order polynomial approximation. Experimental data were colected and the proposed method was used to identify the model of a real robot

Simulador computacional para poços de petróleo com método de elevação artificial por bombeio mecânico

This work proposes a computer simulator for sucker rod pumped vertical wells. The simulator is able to represent the dynamic behavior of the systems and the computation of several important parameters, allowing the easy visualization of several pertinent phenomena. The use of the simulator allows the execution of several tests at lower costs and shorter times, than real wells experiments. The simulation uses a model based on the dynamic behavior of the rod string. This dynamic model is represented by a second order partial differencial equation. Through this model, several common field situations can be verified. Moreover, the simulation includes 3D animations, facilitating the physical understanding of the process, due to a better visual interpretation of the phenomena. Another important characteristic is the emulation of the main sensors used in sucker rod pumping automation. The emulation of the sensors is implemented through a microcontrolled interface between the simulator and the industrial controllers. By means of this interface, the controllers interpret the simulator as a real well. A "fault module" was included in the simulator. This module incorporates the six more important faults found in sucker rod pumping. Therefore, the analysis and verification of these problems through the simulator, allows the user to identify such situations that otherwise could be observed only in the field. The simulation of these faults receives a different treatment due to the different boundary conditions imposed to the numeric solution of the problem. Possible applications of the simulator are: the design and analysis of wells, training of technicians and engineers, execution of tests in controllers and supervisory systems, and validation of control algorithms