Solvent-free microwave-assisted peroxidative oxidation of alcohols catalyzed by Iron(III)-TEMPO catalytic systems

The iron(III) complexes [H(EtOH)][FeCl2(L)(2)] (1), [H(2)bipy](1/2)[FeCl2(L)(2)].DMF (2) and [FeCl2(L)(2,2'-bipy)] (3) (L = 3-amino-2-pyrazinecarboxylate; H(2)bipy = doubly protonated 4,4'-bipyridine; 2,2'-bipy = 2,2'-bipyridine, DMF = dimethylformamide) have been synthesized and fully characterized by IR, elemental and single-crystal X-ray diffraction analyses, as well as by electrochemical methods. Complexes 1 and 2 have similar mononuclear structures containing different guest molecules (protonated ethanol for 1 and doubly protonated 4,4'-bipyridine for 2) in their lattices, whereas the complex 3 has one 3-amino-2-pyrazinecarboxylate and a 2,2'-bipyridine ligand. They show a high catalytic activity for the low power (10 W) solvent-free microwave assisted peroxidative oxidation of 1-phenylethanol, leading, in the presence of TEMPO, to quantitative yields of acetophenone [TOFs up to 8.1 x 10(3) h(-1), (3)] after 1 h. Moreover, the catalysts are of easy recovery and reused, at least for four consecutive cycles, maintaining 83 % of the initial activity and concomitant rather high selectivity. 3-Amino-2-pyrazinecarboxylic acid is used to synthesize three new iron(III) complexes which act as heterogeneous catalysts for the solvent-free microwave-assisted peroxidative oxidation of 1-phenylethanol.

Nonautonomous Graphs and Topological Entropy of Nonautonomous Lorenz Systems

In this work, we associate a p-periodic nonautonomous graph to each p-periodic nonautonomous Lorenz system with finite critical orbits. We develop Perron-Frobenius theory for nonautonomous graphs and use it to calculate their entropy. Finally, we prove that the topological entropy of a p-periodic nonautonomous Lorenz system is equal to the entropy of its associated nonautonomous graph.

Building intelligence open systems (BIOS)

Os edifícios estão a ser construídos com um número crescente de sistemas de automação e controlo não integrados entre si. Esta falta de integração resulta num caos tecnológico, o que cria dificuldades nas três fases da vida de um edifício, a fase de estudo, a de implementação e a de exploração. O desenvolvimento de Building Automation System (BAS) tem como objectivo assegurar condições de conforto, segurança e economia de energia. Em edifícios de grandes dimensões a energia pode representar uma percentagem significativa da factura energética anual. Um BAS integrado deverá contribuir para uma diminuição significativa dos custos de desenvolvimento, instalação e gestão do edifício, o que pode também contribuir para a redução de CO2. O objectivo da arquitectura proposta é contribuir para uma estratégia de integração que permita a gestão integrada dos diversos subsistemas do edifício (e.g. aquecimento, ventilação e ar condicionado (AVAC), iluminação, segurança, etc.). Para realizar este controlo integrado é necessário estabelecer uma estratégia de cooperação entre os subsistemas envolvidos. Um dos desafios para desenvolver um BAS com estas características consistirá em estabelecer a interoperabilidade entre os subsistemas como um dos principais objectivos a alcançar, dado que o fornecimento dos referidos subsistemas assenta normalmente numa filosofia multi-fornecedor, sendo desenvolvidos usando tecnologias heterogéneas. Desta forma, o presente trabalho consistiu no desenvolvimento de uma plataforma que se designou por Building Intelligence Open System (BIOS). Na implementação desta plataforma adoptou-se uma arquitectura orientada a serviços ou Service Oriented Architecture (SOA) constituída por quatro elementos fundamentais: um bus cooperativo, denominado BIOSbus, implementado usando Jini e JavaSpaces, onde todos os serviços serão ligados, disponibilizando um mecanismo de descoberta e um mecanismo que notificada as entidades interessadas sobre alterações do estado de determinado componente; serviços de comunicação que asseguram a abstracção do Hardware utilizado da automatização das diversas funcionalidades do edifício; serviços de abstracção de subsistemas no acesso ao bus; clientes, este podem ser nomeadamente uma interface gráfica onde é possível fazer a gestão integrada do edifício, cliente de coordenação que oferece a interoperabilidade entre subsistemas e os serviços de gestão energética que possibilita a activação de algoritmos de gestão racional de energia eléctrica.

A systematic procedure to enhance reproducibility of SWASV cycles in the determination of toxic metals in real samples

This work presents for the first time a systematic study on the optimization of the electrochemical cleaning time of a mercury film when it is used as a working electrode material in the analysis of toxic metals, such as Pb2+, used as model metal, in real samples by SWASV. The optimization study for the film’s cleaning time aimed at attaining a Pb2+ minimum value in the film after the re-oxidation step of the pre-concentrated metal, given the impossibility of complete removal of traces of the electroactive species from the film. This value was kept constant in each concentration range studied ensuring thus that all assays were performed in initial identical conditions. An assay performed on a synthetic sample was taken as reference. In it, given the absence of matrix effects, and after the electrochemical cleaning step, a direct proportionality was observed between the residual amounts of Pb2+ in the film (which for the cleaning time used was never completely removed) and Pb2+ concentration in the solution. This fact determined a high correlation between Pb2+ peak current and Pb2+ concentration which was not observed when real samples (tree leaves) were analyzed. This behavior may result from the presence of the interfering surfactants always present in real samples of complex matrix. Cleaning time optimization was performed for the following Pb2+ concentration ranges in the real samples of complex matrix: 0.006-0.020, 0.020-0.080, 0.060-0.200 and 0.100-0.600 ppb. As expected, in order to obtain identical levels of film’s cleaning efficiency, the need for longer cleaning times has been observed for higher concentrations. The optimized cleaning times for the concentration ranges under study were 120, 150, 180 e 300 s, respectively.

Quantifying chaos for ecological stoichiometry

The theory of ecological stoichiometry considers ecological interactions among species with different chemical compositions. Both experimental and theoretical investigations have shown the importance of species composition in the outcome of the population dynamics. A recent study of a theoretical three-species food chain model considering stoichiometry [B. Deng and I. Loladze, Chaos 17, 033108 (2007)] shows that coexistence between two consumers predating on the same prey is possible via chaos. In this work we study the topological and dynamical measures of the chaotic attractors found in such a model under ecological relevant parameters. By using the theory of symbolic dynamics, we first compute the topological entropy associated with unimodal Poincareacute return maps obtained by Deng and Loladze from a dimension reduction. With this measure we numerically prove chaotic competitive coexistence, which is characterized by positive topological entropy and positive Lyapunov exponents, achieved when the first predator reduces its maximum growth rate, as happens at increasing delta(1). However, for higher values of delta(1) the dynamics become again stable due to an asymmetric bubble-like bifurcation scenario. We also show that a decrease in the efficiency of the predator sensitive to prey's quality (increasing parameter zeta) stabilizes the dynamics. Finally, we estimate the fractal dimension of the chaotic attractors for the stoichiometric ecological model.

Synthesis and Coordination Chemistry of a New N-4-Polydentate Class of Pyridyl-Functionalized Scorpionate Ligands: Complexes of Fe-II, Zn-II, V-IV, Pd-II and Use for Heterobimetallic Systems

The new potentially N-4-multidentate pyridyl-functionalized scorpionates 4-((tris-2,2,2-(pyrazol-1-ypethoxy)methyl)pyridine (TpmPy, (1)) and 4-((tris-2,2,2-(3-phenylpyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy(Ph), (2)) have been synthesized and their coordination behavior toward Fe-II, Ni-II, Zn-II, Cu-II, Pd-II, and V-III centers has been studied. Reaction of (1) with Fe(BF4)(2)center dot 6H(2)O yields [Fe(TpmPy)(2)](BF4)(2) (3), that, in the solid state, shows the sandwich structure with trihapto ligand coordination via the pyrazolyl arms, and is completely low spin (LS) until 400 K. Reactions of 2 equiv of (1) or (2) with Zn-II or Ni-II chlorides give the corresponding metal complexes with general formula [MCl2(TpmPy*)(2)] (M = Zn, Ni; TpmPy* = TpmPy, TpmPy(Ph)) (4-7) where the ligand is able to coordinate through either the pyrazolyl rings (in case of [Ni(TpmPy)(2)Cl-2 (5)) or the pyridyl-side (for [ZnCl2(TpmPy)(2)] (4), [ZnCl2(TpmPy(Ph))(2)] (6) and [NiCl2(TpmPy(Ph))(2)] (7)). The reaction of (1) with VCl3 gives [VOCl2(TpmPy)] (8) that shows the N-3-pyrazolyl coordination-mode. Moreover, (1) and react with cis-[PdCl2(CH3CN)(2)] to give the disubstituted complexes [PdCl2(TprnPy)(2)] (9) and [PdCl2(TpmPy(Ph))(2)] (10), respectively, bearing the scorpionate coordinated via the pyridyl group. Compounds (9) and (10) react with Fe(BF4)(2) to give the heterobimetallic Pd/Fe systems [PdCl2(mu-TpmPy)(2)-Fe](BF4)(2) (11) and [PdCl2(mu-TpmPy(Ph))(2)Fe-2(H2O)(6)]BF4)(4) (13), respectively. Compound (11) can also be formed from reaction of (3) with cis-[PdCl2(CH3CN)(2)], while reaction of (3) with Cu(NO3)(2).2.5H(2)O generates [Fe(mu-TpmPy)(2)-Cu(NO3)(2)](BF4)(2) (12), confirming the multidentate ability of the new chelating ligands. The X-ray diffraction analyses of compounds (1), (3), (4), (5), and (9) are also reported.

Power converter topologies for wind energy conversion systems: Integrated modeling, control strategy and performance simulation

This paper presents new integrated model for variable-speed wind energy conversion systems, considering a more accurate dynamic of the wind turbine, rotor, generator, power converter and filter. Pulse width modulation by space vector modulation associated with sliding mode is used for controlling the power converters. Also, power factor control is introduced at the output of the power converters. Comprehensive performance simulation studies are carried out with matrix, two-level and multilevel power converter topologies in order to adequately assert the system performance. Conclusions are duly drawn.

Radiological imaging in digital systems: the effect of exposure parameters in diagnostic quality and patient dose

Esta tese pretende contribuir para o estudo e análise dos factores relacionados com as técnicas de aquisição de imagens radiológicas digitais, a qualidade diagnóstica e a gestão da dose de radiação em sistema de radiologia digital. A metodologia encontra-se organizada em duas componentes. A componente observacional, baseada num desenho do estudo de natureza retrospectiva e transversal. Os dados recolhidos a partir de sistemas CR e DR permitiram a avaliação dos parâmetros técnicos de exposição utilizados em radiologia digital, a avaliação da dose absorvida e o índice de exposição no detector. No contexto desta classificação metodológica (retrospectiva e transversal), também foi possível desenvolver estudos da qualidade diagnóstica em sistemas digitais: estudos de observadores a partir de imagens arquivadas no sistema PACS. A componente experimental da tese baseou-se na realização de experiências em fantomas para avaliar a relação entre dose e qualidade de imagem. As experiências efectuadas permitiram caracterizar as propriedades físicas dos sistemas de radiologia digital, através da manipulação das variáveis relacionadas com os parâmetros de exposição e a avaliação da influência destas na dose e na qualidade da imagem. Utilizando um fantoma contraste de detalhe, fantomas antropomórficos e um fantoma de osso animal, foi possível objectivar medidas de quantificação da qualidade diagnóstica e medidas de detectabilidade de objectos. Da investigação efectuada, foi possível salientar algumas conclusões. As medidas quantitativas referentes à performance dos detectores são a base do processo de optimização, permitindo a medição e a determinação dos parâmetros físicos dos sistemas de radiologia digital. Os parâmetros de exposição utilizados na prática clínica mostram que a prática não está em conformidade com o referencial Europeu. Verifica-se a necessidade de avaliar, melhorar e implementar um padrão de referência para o processo de optimização, através de novos referenciais de boa prática ajustados aos sistemas digitais. Os parâmetros de exposição influenciam a dose no paciente, mas a percepção da qualidade de imagem digital não parece afectada com a variação da exposição. Os estudos que se realizaram envolvendo tanto imagens de fantomas como imagens de pacientes mostram que a sobreexposição é um risco potencial em radiologia digital. A avaliação da qualidade diagnóstica das imagens mostrou que com a variação da exposição não se observou degradação substancial da qualidade das imagens quando a redução de dose é efectuada. Propõe-se o estudo e a implementação de novos níveis de referência de diagnóstico ajustados aos sistemas de radiologia digital. Como contributo da tese, é proposto um modelo (STDI) para a optimização de sistemas de radiologia digital.

Fractional-order control and simulation of wind energy systems with PMSG/full-power converter topology

This paper presents a new integrated model for the simulation of wind energy systems. The proposed model is more realistic and accurate, considering a variable-speed wind turbine, two-mass rotor, permanent magnet synchronous generator (PMSG), different power converter topologies, and filters. Additionally, a new control strategy is proposed for the variable-speed operation of wind turbines with PMSG/full-power converter topology, based on fractional-order controllers. Comprehensive simulation studies are carried out with matrix and multilevel power converter topologies, in order to adequately assert the system performance in what regards the quality of the energy injected into the electric grid. Finally, conclusions are duly drawn.

Scheduling of head-dependent cascaded hydro systems: Mixed-integer quadratic programming approach

This paper is on the problem of short-term hydro, scheduling, particularly concerning head-dependent cascaded hydro systems. We propose a novel mixed-integer quadratic programming approach, considering not only head-dependency, but also discontinuous operating regions and discharge ramping constraints. Thus, an enhanced short-term hydro scheduling is provided due to the more realistic modeling presented in this paper. Numerical results from two case studies, based on Portuguese cascaded hydro systems, illustrate the proficiency of the proposed approach.

Measuring and Controlling the Chaotic Motion of Profits

The study of economic systems has generated deep interest in exploring the complexity of chaotic motions in economy. Due to important developments in nonlinear dynamics, the last two decades have witnessed strong revival of interest in nonlinear endogenous business chaotic models. The inability to predict the behavior of dynamical systems in the presence of chaos suggests the application of chaos control methods, when we are more interested in obtaining regular behavior. In the present article, we study a specific economic model from the literature. More precisely, a system of three ordinary differential equations gather the variables of profits, reinvestments and financial flow of borrowings in the structure of a firm. Firstly, using results of symbolic dynamics, we characterize the topological entropy and the parameter space ordering of kneading sequences, associated with one-dimensional maps that reproduce significant aspects of the model dynamics. The analysis of the variation of this numerical invariant, in some realistic system parameter region, allows us to quantify and to distinguish different chaotic regimes. Finally, we show that complicated behavior arising from the chaotic firm model can be controlled without changing its original properties and the dynamics can be turned into the desired attracting time periodic motion (a stable steady state or into a regular cycle). The orbit stabilization is illustrated by the application of a feedback control technique initially developed by Romeiras et al. [1992]. This work provides another illustration of how our understanding of economic models can be enhanced by the theoretical and numerical investigation of nonlinear dynamical systems modeled by ordinary differential equations.

Toplological Entropy in the Syncronization of Piecewise Linear and Monotone Maps. Coupled Duffing Oscillators

In this paper is presented a relationship between the synchronization and the topological entropy. We obtain the values for the coupling parameter, in terms of the topological entropy, to achieve synchronization of two unidirectional and bidirectional coupled piecewise linear maps. In addition, we prove a result that relates the synchronizability of two m-modal maps with the synchronizability of two conjugated piecewise linear maps. An application to the unidirectional and bidirectional coupled identical chaotic Duffing equations is given. We discuss the complete synchronization of two identical double-well Duffing oscillators, from the point of view of symbolic dynamics. Working with Poincare cross-sections and the return maps associated, the synchronization of the two oscillators, in terms of the coupling strength, is characterized.

RFID together with multi-agent systems to control global value chains

Nowadays, the cooperative intelligent transport systems are part of a largest system. Transportations are modal operations integrated in logistics and, logistics is the main process of the supply chain management. The supply chain strategic management as a simultaneous local and global value chain is a collaborative/cooperative organization of stakeholders, many times in co-opetition, to perform a service to the customers respecting the time, place, price and quality levels. The transportation, like other logistics operations must add value, which is achieved in this case through compression lead times and order fulfillments. The complex supplier's network and the distribution channels must be efficient and the integral visibility (monitoring and tracing) of supply chain is a significant source of competitive advantage. Nowadays, the competition is not discussed between companies but among supply chains. This paper aims to evidence the current and emerging manufacturing and logistics system challenges as a new field of opportunities for the automation and control systems research community. Furthermore, the paper forecasts the use of radio frequency identification (RFID) technologies integrated into an information and communication technologies (ICT) framework based on distributed artificial intelligence (DAI) supported by a multi-agent system (MAS), as the most value advantage of supply chain management (SCM) in a cooperative intelligent logistics systems. Logistical platforms (production or distribution) as nodes of added value of supplying and distribution networks are proposed as critical points of the visibility of the inventory, where these technological needs are more evident.

Surge damping analysis in pipe systems: modelling and experiments

The current study focuses on the analysis of pressure surge damping in single pipeline systems generated by a fast change of flow, conditions. A dimensionless form of pressurised transient flow equations was developed. presenting the main advantage of being independent of the system characteristics. In lack of flow velocity profiles. the unsteady friction in turbulent regimes is analysed based on two new empirical corrective-coefficients associated with local and convective acceleration terms. A new, surge damping approach is also presented taking into account the pressure peak time variation. The observed attenuation effect in the pressure wave for high deformable pipe materials can be described by a combination of the non-elastic behaviour of the pipe-wall with steady and unsteady friction effects. Several simulations and experimental tests have been carried out. in order to analyse the dynamic response of single pipelines with different characteristics, such as pipe materials. diameters. thickness. lengths and transient conditions.

Coexistence of Universal and Topological Anomalous Hall Effects in Metal CrO2 Thin Films in the Dirty Limit

The scaling exponent of 1.6 between anomalous Hall and longitudinal conductivity, characteristic of the universal Hall mechanism in dirty-metal ferromagnets, emerges from a series of CrO2 films as we systematically increase structural disorder. Magnetic disorder in CrO2 increases with temperature and this drives a separate topological Hall mechanism. We find that these terms are controlled discretely by structural and magnetic defect populations, and their coexistence leads to apparent divergence from exponent 1.6, suggesting that the universal term is more prevalent than previously realized.