O2 activation at bioinspired complexes: dinuclear copper systems and mononuclear non-heme iron compounds. Mechanisms and catalytic applications in oxidative transformations

L'activació d'oxigen que té lloc en els éssers vius constitueix una font d'inspiració pel desenvolupament d'alternatives als oxidants tradicionals, considerats altament tòxics i nocius. En aquesta treball s'utilitzen compostos sintètics com a models del centre actiu de proteïnes dinuclears de coure i mononuclears de ferro de tipus no-hemo que participen en l'activació d'oxigen en els éssers vius. Els sistemes dinuclears de coure mostren un centre de tipus coure(III) bis(oxo) que és capaç de dur a terme l'ortho-hidroxilació de fenols de manera similar a la reacció que catalitza la proteïna tirosinasa. Per altra banda, els sistemes de ferro desenvolupats en aquest treball actuen com a models de les dioxigenases de Rieske i poden dur a terme l'hidroxilació estereoespecífica d'alcans i l'epoxidació i cis-dihidroxilació d'olefines utilitzant peròxid d'hidrogen com a agent oxidant. Tot plegat demostra que el desenvolupament de sistemes model constitueix una bona estratègia per l'estudi dels sistemes naturals.

Optimal control of nonlinear differential algebraic equation systems

A novel iterative procedure is described for solving nonlinear optimal control problems subject to differential algebraic equations. The procedure iterates on an integrated modified linear quadratic model based problem with parameter updating in such a manner that the correct solution of the original non-linear problem is achieved. The resulting algorithm has a particular advantage in that the solution is achieved without the need to solve the differential algebraic equations . Convergence aspects are discussed and a simulation example is described which illustrates the performance of the technique. 1. Introduction When modelling industrial processes often the resulting equations consist of coupled differential and algebraic equations (DAEs). In many situations these equations are nonlinear and cannot readily be directly reduced to ordinary differential equations.

Participatory research approaches in the development of improved management practices in indigenous chickens production systems with smallholder farmers in Kenya

This thesis is concerned with development of improved management practices in indigenous chicken production systems in a research process that includes participatory approaches with smallholder farmers and other stakeholders in Kenya. The research process involved a wide range of activities that included on-station experiments, field surveys, stakeholder consultations in workshops, seminars and visits, and on-farm farmer participatory research to evaluate the effect of some improved management interventions on production performance of indigenous chickens. The participatory research was greatly informed from collective experiences and lessons of the previous activities. The on-station studies focused on hatching, growth and nutritional characteristics of the indigenous chickens. Four research publications from these studies are included in this thesis. Quantitative statistical analyses were applied and they involved use of growth models estimated with non-linear regressions for the growth characteristics, chi-square determinations to investigate differences among different reciprocal crosses of indigenous chickens and general linear models and covariance determination for the nutrition study. The on-station studies brought greater understanding of performance and production characteristics of indigenous chickens and the influence of management practices on these characteristics. The field surveys and stakeholder consultations helped in understanding the overarching issues affecting the productivity of the indigenous chickens systems and their place in the livelihoods of smallholder farmers. These activities created strong networking opportunities with stakeholders from a wide spectrum. The on-farm farmer participatory research involved selection of 200 farmers in five regions followed by training and introduction of interventions on improved management practices which included housing, vaccination, deworming and feed supplementation. Implementation and monitoring was mainly done by individual farmers continuously for close to one and half years. Six quarterly visits to the farms were made by the research team to monitor and provide support for on-going project activities. The data collected has been analysed for 5 consecutive 3-monthly periods. Descriptive and inferential statistics were applied to analyse the data collected involving treatment applications, production characteristics and flock demography characteristics. Out of the 200 farmers initially selected, 173 had records on treatment applications and flock demography characteristics while 127 farmers had records on production characteristics. The demographic analysis with a dissimilarity index of flock size produced 7 distinct farm groups from among the 173 farms. Two of these farm groups were represented in similar numbers in each of the five regions. The research process also involved a number of dissemination and communication strategies that have brought the process and project outcomes into the domain of accessibility by wider readership locally and globally. These include workshops, seminars, field visits and consultations, local and international conferences, electronic conferencing, publications and personal communication via emailing and conventional posting. A number of research and development proposals were also developed based on the knowledge and experiences gained from the research process. The thesis captures the research process activities and outcomes in 8 chapters which include in ascending order – introduction, theoretical concepts underpinning FPR, research methodology and process, on-station research output, FPR descriptive statistical analysis, FPR inferential statistical analysis on production characteristics, FPR demographic analysis and conclusions. Various research approaches both quantitative and qualitative have been applied in the research process indicating the possibilities and importance of combining both systems for greater understanding of issues being studied. In our case, participatory studies of the improved management of indigenous chickens indicates their potential importance as livelihood assets for poor people.

PHA(MCL) biosynthesis systems in Pseudomonas aeruginosa and Pseudomonas putida strains show differences on monomer specificities

The production of PHA from plant oils by Pseudomonas species soil isolated from a sugarcane crop was evaluated. Out of 22 bacterial strains three were able to use efficiently plant oils to grow and to accumulate PHA. Pseudomonas putida and Pseudomonas aeruginosa strains produced PHA presenting differences on monomer composition compatible with variability on monomer specificity of their PHA biosynthesis system. The molar fraction of 3-hydroxydodecanoate detected in the PHA was linearly correlated to the oleic acid supplied. A non-linear relationship between the molar fractions of 3-hydroxy-6-dodecenoate (3HDd Delta(6)) detected in PHA and the linoleic acid supplied was observed, compatible with saturation in the biosynthesis system capability to channel intermediate of P-oxidation to PHA synthesis. Although P. putida showed a higher 3HDd Delta(6) yield from linoleic acid when compared to P. aeruginosa, in both species it was less than 10% of the maximum theoretical value. These results contribute to the knowledge about the biosynthesis of PHA with a controlled composition from plant oils allowing in the future establishing the production of these polyesters as tailor-made polymers. (C) 2009 Elsevier B.V. All rights reserved.

Reaction-diffusion systems coupled at the boundary and the Morse-Smale property

We study an one-dimensional nonlinear reaction-diffusion system coupled on the boundary. Such system comes from modeling problems of temperature distribution on two bars of same length, jointed together, with different diffusion coefficients. We prove the transversality property of unstable and stable manifolds assuming all equilibrium points are hyperbolic. To this end, we write the system as an equation with noncontinuous diffusion coefficient. We then study the nonincreasing property of the number of zeros of a linearized nonautonomous equation as well as the Sturm-Liouville properties of the solutions of a linear elliptic problem. (C) 2008 Elsevier Inc. All rights reserved.

Controlador preditivo não linear aplicado ao controle de golfadas em processos de produção de petróleo

Slugging is a well-known slugging phenomenon in multiphase flow, which may cause problems such as vibration in pipeline and high liquid level in the separator. It can be classified according to the place of its occurrence. The most severe, known as slugging in the riser, occurs in the vertical pipe which feeds the platform. Also known as severe slugging, it is capable of causing severe pressure fluctuations in the flow of the process, excessive vibration, flooding in separator tanks, limited production, nonscheduled stop of production, among other negative aspects that motivated the production of this work . A feasible solution to deal with this problem would be to design an effective method for the removal or reduction of the system, a controller. According to the literature, a conventional PID controller did not produce good results due to the high degree of nonlinearity of the process, fueling the development of advanced control techniques. Among these, the model predictive controller (MPC), where the control action results from the solution of an optimization problem, it is robust, can incorporate physical and /or security constraints. The objective of this work is to apply a non-conventional non-linear model predictive control technique to severe slugging, where the amount of liquid mass in the riser is controlled by the production valve and, indirectly, the oscillation of flow and pressure is suppressed, while looking for environmental and economic benefits. The proposed strategy is based on the use of the model linear approximations and repeatedly solving of a quadratic optimization problem, providing solutions that improve at each iteration. In the event where the convergence of this algorithm is satisfied, the predicted values of the process variables are the same as to those obtained by the original nonlinear model, ensuring that the constraints are satisfied for them along the prediction horizon. A mathematical model recently published in the literature, capable of representing characteristics of severe slugging in a real oil well, is used both for simulation and for the project of the proposed controller, whose performance is compared to a linear MPC

Application of neural networks to identify features of dynamical grounding systems

The accurate identification of features of dynamical grounding systems are extremely important to define the operational safety and proper functioning of electric power systems. Several experimental tests and theoretical investigations have been carried out to obtain characteristics and parameters associated with the technique of grounding. The grounding system involves a lot of non-linear parameters. This paper describes a novel approach for mapping characteristics of dynamical grounding systems using artificial neural networks. The network acts as identifier of structural features of the grounding processes. So that output parameters can be estimated and generalized from an input parameter set. The results obtained by the network are compared with other approaches also used to model grounding systems.

Comparative degradation of ZnO- and SnO(2)-based polycrystalline non-ohmic devices by current pulse stress

The degradation behaviour of SnO(2)-based varistors (SCNCr) due to current pulses (8/20 mu s) is reported here for the first time in comparison with the ZnO-based commercial varistors (ZnO). Puncturing and/or cracking failures were observed in ZnO-based varistors possessing inferior thermo-mechanical properties in comparison with that found in a SCNCr system free of failures. Both systems presented electric degradation related to the increase in the leakage current and decrease in the electric breakdown field, non-linear coefficient and average value of the potential barrier height. However, it was found that a more severe degradation occurred in the ZnO-based varistors concerning their non-ohmic behaviour, while in the SCNCr system, a strong non-ohmic behaviour remained after the degradation. These results indicate that the degradation in the metal oxide varistors is controlled by a defect diffusion process whose rate depends on the mobility, the concentration of meta-stable defects and the amount of electrically active interfaces. The improved behaviour of the SCNCr system is then inferred to be associated with the higher amount of electrically active interfaces (85%) and to a higher energy necessary to activate the diffusion of the specific defects.

Optimised placement of control and protective devices in electric distribution systems through reactive tabu search algorithm

Optimised placement of control and protective devices in distribution networks allows for a better operation and improvement of the reliability indices of the system. Control devices (used to reconfigure the feeders) are placed in distribution networks to obtain an optimal operation strategy to facilitate power supply restoration in the case of a contingency. Protective devices (used to isolate faults) are placed in distribution systems to improve the reliability and continuity of the power supply, significantly reducing the impacts that a fault can have in terms of customer outages, and the time needed for fault location and system restoration. This paper presents a novel technique to optimally place both control and protective devices in the same optimisation process on radial distribution feeders. The problem is modelled through mixed integer non-linear programming (MINLP) with real and binary variables. The reactive tabu search algorithm (RTS) is proposed to solve this problem. Results and optimised strategies for placing control and protective devices considering a practical feeder are presented. (c) 2007 Elsevier B.V. All rights reserved.

Efficient heuristic algorithm used for optimal capacitor placement in distribution systems

An efficient heuristic algorithm is presented in this work in order to solve the optimal capacitor placement problem in radial distribution systems. The proposal uses the solution from the mathematical model after relaxing the integrality of the discrete variables as a strategy to identify the most attractive bus to add capacitors to each step of the heuristic algorithm. The relaxed mathematical model is a nonlinear programming problem and is solved using a specialized interior point method, The algorithm still incorporates an additional strategy of local search that enables the finding of a group of quality solutions after small alterations in the optimization strategy. Proposed solution methodology has been implemented and tested in known electric systems getting a satisfactory outcome compared with metaheuristic methods.The tests carried out in electric systems known in specialized literature reveal the satisfactory outcome of the proposed algorithm compared with metaheuristic methods. (C) 2009 Elsevier Ltd. All rights reserved.

Strategic capacitor placement in distribution systems by minimisation of harmonics amplification because of resonance

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

Primary power distribution systems planning taking into account reliability, operation and expansion costs

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A reducing of a chaotic movement to a periodic orbit, of a micro-electro-mechanical system, by using an optimal linear control design

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

Generalização de um modelo linear de impedância eletroquímica

Em geral, a função de um modelo de impedância para processos de eletrodo simples é deduzida de um modelo elétrico equivalente, denominado circuito de Randles. Neste trabalho estudou-se a generalização dessa função, mediante a introdução de um parâmetro não-elétrico, relacionado com a flexibilidade do ângulo de fase e da magnitude. A função foi ajustada às medidas experimentais de impedância obtidas de um sistema constituído de uma liga Ti-10%Al (m/m) em solução de cloreto de sódio 0,9%, variando-se a amplitude de perturbação. Verificou-se que a função generalizada foi adequada para descrever a impedância do sistema analisado, reduzindo as distorções entre a curva experimental e a curva teórica. Além disso, os melhores resultados foram obtidos para sinais de perturbação do sistema com amplitude igual a 10 mV.

Electrical and micro structural properties of (Zn, Nb, Fe)-doped SnO2 varistor systems

The electrical and microstructural properties of SnO2-based varistors with the addition of 0.025 and 0.050 mol% of Fe2O3 have been characterised. Electric field (E) versus current density (J) curves showed that the effect of Fe2O3 addition is to increase both the non-linear coefficient and the breakdown voltage. Variations in the potential barrier height were inferred from impedance spectroscopy (IS) analysis. Through transmission electron microscopy (TEM), the presence of precipitates of secondary phases was confirmed. Samples with precipitates displayed poor electrical properties. (c) 2004 Elsevier Ltd and Techna Group S.r.l. All rights reserved.