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.

Dynamic whole system testing of combined renewable heating systems : the current state of the art

Objective: For the evaluation of the energetic performance of combined renewable heating systems that supply space heat and domestic hot water for single family houses, dynamic behaviour, component interactions, and control of the system play a crucial role and should be included in test methods. Methods: New dynamic whole system test methods were developed based on “hardware in the loop” concepts. Three similar approaches are described and their differences are discussed. The methods were applied for testing solar thermal systems in combination with fossil fuel boilers (heating oil and natural gas), biomass boilers, and/or heat pumps. Results: All three methods were able to show the performance of combined heating systems under transient operating conditions. The methods often detected unexpected behaviour of the tested system that cannot be detected based on steady state performance tests that are usually applied to single components. Conclusion: Further work will be needed to harmonize the different test methods in order to reach comparable results between the different laboratories. Practice implications: A harmonized approach for whole system tests may lead to new test standards and improve the accuracy of performance prediction as well as reduce the need for field tests.

Testing of combined heating systems for small houses: Improved procedures for whole system test methods : Deliverable 2.3

Dynamic system test methods for heating systems were developed and applied by the institutes SERC and SP from Sweden, INES from France and SPF from Switzerland already before the MacSheep project started. These test methods followed the same principle: a complete heating system – including heat generators, storage, control etc., is installed on the test rig; the test rig software and hardware simulates and emulates the heat load for space heating and domestic hot water of a single family house, while the unit under test has to act autonomously to cover the heat demand during a representative test cycle. Within the work package 2 of the MacSheep project these similar – but different – test methods were harmonized and improved. The work undertaken includes:  • Harmonization of the physical boundaries of the unit under test. • Harmonization of the boundary conditions of climate and load. • Definition of an approach to reach identical space heat load in combination with an autonomous control of the space heat distribution by the unit under test. • Derivation and validation of new six day and a twelve day test profiles for direct extrapolation of test results.   The new harmonized test method combines the advantages of the different methods that existed before the MacSheep project. The new method is a benchmark test, which means that the load for space heating and domestic hot water preparation will be identical for all tested systems, and that the result is representative for the performance of the system over a whole year. Thus, no modelling and simulation of the tested system is needed in order to obtain the benchmark results for a yearly cycle. The method is thus also applicable to products for which simulation models are not available yet. Some of the advantages of the new whole system test method and performance rating compared to the testing and energy rating of single components are:  • Interaction between the different components of a heating system, e.g. storage, solar collector circuit, heat pump, control, etc. are included and evaluated in this test. • Dynamic effects are included and influence the result just as they influence the annual performance in the field. • Heat losses are influencing the results in a more realistic way, since they are evaluated under "real installed" and representative part-load conditions rather than under single component steady state conditions.   The described method is also suited for the development process of new systems, where it replaces time-consuming and costly field testing with the advantage of a higher accuracy of the measured data (compared to the typically used measurement equipment in field tests) and identical, thus comparable boundary conditions. Thus, the method can be used for system optimization in the test bench under realistic operative conditions, i.e. under relevant operating environment in the lab.   This report describes the physical boundaries of the tested systems, as well as the test procedures and the requirements for both the unit under test and the test facility. The new six day and twelve day test profiles are also described as are the validation results.

A competitive growth model with endogenous fertility

This paper investigates the interaction between endogenous fertility behavior and the distribution of income and wealth arnong farnilies in a competitive market economy. We construct a growth model in which altruistic dynasties are heterogeneous in their initial stocks of physical capital. Dynasties make choices of farnily size along with decisions about consumption and intergenerational transfers. We show that if the rate of time preference is increasing in the number of children and preferences over nurnber of children satisfy a norrnality assumption, all steady states are characterized by equality of capital stocks and consumption arnong families. We also provide sufficient conditions for uniqueness of the steady state. In order to illustrate these results, we present an example in which preferences over number of children are logarithrnic and the technology is Cobb-Douglas. For this combination of preferences and technology, there exists a unique egalitarian steady state. Moreover, the economy converges to this steady state in only one generation .

Optimal monetary policy under administered prices

This work aims to analyze the interaction and the effects of administered prices in the economy, through a DSGE model and the derivation of optimal monetary policies. The model used is a standard New Keynesian DSGE model of a closed economy with two sectors companies. In the first sector, free prices, there is a continuum of firms, and in the second sector of administered prices, there is a single firm. In addition, the model has positive trend inflation in the steady state. The model results suggest that price movements in any sector will impact on both sectors, for two reasons. Firstly, the price dispersion causes productivity to be lower. As the dispersion of prices is a change in the relative price of any sector, relative to general prices in the economy, when a movement in the price of a sector is not followed by another, their relative weights will change, leading to an impact on productivity in both sectors. Second, the path followed by the administered price sector is considered in future inflation expectations, which is used by companies in the free sector to adjust its optimal price. When this path leads to an expectation of higher inflation, the free sector companies will choose a higher mark-up to accommodate this expectation, thus leading to higher inflation trend when there is imperfect competition in the free sector. Finally, the analysis of optimal policies proved inconclusive, certainly indicating that there is influence of the adjustment model of administered prices in the definition of optimal monetary policy, but a quantitative study is needed to define the degree of impact.

Controlador em modo dual adaptativo robusto - DMARC

The so-called Dual Mode Adaptive Robust Control (DMARC) is proposed. The DMARC is a control strategy which interpolates the Model Reference Adaptive Control (MRAC) and the Variable Structure Model Reference Adaptive Control (VS-MRAC). The main idea is to incorporate the transient performance advantages of the VS-MRAC controller with the smoothness control signal in steady-state of the MRAC controller. Two basic algorithms are developed for the DMARC controller. In the first algorithm the controller's adjustment is made, in real time, through the variation of a parameter in the adaptation law. In the second algorithm the control law is generated, using fuzzy logic with Takagi-Sugeno s model, to obtain a combination of the MRAC and VS-MRAC control laws. In both cases, the combined control structure is shown to be robust to the parametric uncertainties and external disturbances, with a fast transient performance, practically without oscillations, and a smoothness steady-state control signal

Kinetics of interface state-limited hole injection in alpha-naphthylphenylbiphenyl diamine (alpha-NPD) thin layers

Injection-limited operation is identified in thin-film, alpha-NPD-based diodes. A detailed model for the impedance of the injection process is provided which considers the kinetics of filling/releasing of interface states as the key factor behind the injection mechanism. The injection model is able to simultaneously account for the steady-state, current-voltage (J-V) characteristics and impedance response. and is based on the sequential injection of holes mediated by energetically distributed surface states at the metal-organic interface. The model takes into account the vacuum level offset caused by the interface dipole, along with the partial shift of the interface level distribution with bias voltage. This approach connects the low-frequency (similar to 1 Hz) capacitance spectra, which exhibits a transition between positive to negative values, to the change in the occupancy of interface states with voltage. Simulations based on the model allow to derive the density of interface states effectively intervening in the carrier injection (similar to 5 x 10(12) cm(-2)), which exhibit a Gaussian-like distribution. A kinetically determined hole barrier is calculated at levels located similar to 0.4 eV below the contact work function. (C) 2008 Elsevier B.V. All rights reserved.

Hydrogen oxidation on ordered intermetallic electrodes covered with CO

This describes an experimental evaluation of the electrocatalytic activity of the hydrogen oxidation reaction on electrodes of platinum and the ordered intermetallic phases PtSb and PtSn, on which CO has previously been deposited. The experiments were carried out in perchloric acid solution and the analysis based on steady-state polarization curves and Tafel plots derived from chronoamperometric data. Both intermetallics, PtSb and PtSn, performed better than Pt towards the HOR, when their surface was deliberately covered with CO. It is suggested that the intermetallic surfaces have a lower affinity for CO molecules, causing a lower CO coverage on these surfaces, and/or a weaker surface-CO interaction, compared to Pt under the same conditions. (C) 2007 Elsevier B.V. All rights reserved.

Efeito da recuperação na máxima fase estável de lactato sanguíneo

The objective of this study was to compare the power corresponding to maximal lactate steady state determined through continuous (MLSSC) and intermittent protocol with active recovery (MLSSI). Ten trained male cyclists (25 +/- 4 yr., 72.5 +/- 10.6 kg, 178.5 +/- 4.0 cm), performed the following tests on a cycle ergometer: (1) incremental test until voluntary exhaustion to determine the maximal power (Pmax); (2) two to five constant workload tests to determine MLSSC, and; 3) two to three constant workload tests to determine MLSSI, consisting on eight repetitions of four minutes interspersed by two minutes of recovery at 50% Pmax. The MLSSC (273.2 +/- 21.4 W) was significantly lower than MLSSI (300.5 +/- 23.9 W). With base on these data, it can be verified that the intermittent exercise mode utilized in this study, allows an increase of 10% approximately, in the exercise intensity corresponding to MLSS.

Comments on nonlinear dynamics of a non-ideal Duffing-Rayleigh oscillator: Numerical and analytical approaches

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

Síntese, caracterização e estudos de interação de um análogo da antitoxina CcdA empregando fluorescência no estado estacionário

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

Electrocatalysis of hydrogen evolution reaction on Pt electrode surface-modified by S-2 chemisorption

Kinetic studies of hydrogen evolution reaction (HER) at the surface of Pt in alkaline conditions, reported in this paper, show that electrocatalytic activity is enhanced after adsorption of S-2 ions. EIS and steady-state polarization curve data pointed to an undoubted improvement in performance with the Pt-S cathode that was attributed to higher adsorbed hydrogen coverage. Experimental findings suggested an increase in the electronic density of the modified surface sites that may strengthen the interaction between H2O and the adsorption site and, consequently, accelerates the Volmer step. (c) 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Harmonics filtering and detection of disturbances using wavelets

Traditional mathematical tools, like Fourier Analysis, have proven to be efficient when analyzing steady-state distortions; however, the growing utilization of electronically controlled loads and the generation of a new dynamics in industrial environments signals have suggested the need of a powerful tool to perform the analysis of non-stationary distortions, overcoming limitations of frequency techniques. Wavelet Theory provides a new approach to harmonic analysis, focusing the decomposition of a signal into non-sinusoidal components, which are translated and scaled in time, generating a time-frequency basis. The correct choice of the waveshape to be used in decomposition is very important and discussed in this work. A brief theoretical introduction on Wavelet Transform is presented and some cases (practical and simulated) are discussed. Distortions commonly found in industrial environments, such as the current waveform of a Switched-Mode Power Supply and the input phase voltage waveform of motor fed by inverter are analyzed using Wavelet Theory. Applications such as extracting the fundamental frequency of a non-sinusoidal current signal, or using the ability of compact representation to detect non-repetitive disturbances are presented.

On Nonlinear Dynamics and Control of A Particular Portal Frame Foundation Model, Excited by a Non-Ideal Motor

The nonlinear dynamic response and a nonlinear control method of a particular portal frame foundation for an unbalanced rotating machine with limited power (non-ideal motor) are examined. Numerical simulations are performed for a set of control parameters (depending on the voltage of the motor) related to the static and dynamic characteristics of the motor. The interaction of the structure with the excitation source may lead to the occurrence of interesting phenomena during the forward passage through the several resonance states of the systems. A mathematical model having two degrees of freedom simplifies the non-ideal system. The study of controlling steady-state vibrations of the non-ideal system is based on the saturation phenomenon due to internal resonance.

Horseradish peroxidase-catalyzed oxidation of rifampicin: Reaction rate enhancement by co-oxidation with anti-inflammatory drugs

The tuberculostatic drug rifampicin has been described as a scavenger of reactive species. Additionally, the recent demonstration that oral therapy with a complex of rifampicin and horseradish peroxidase (HRP) was more effective than rifampicin alone, in an animal model of experimental leprosy, suggested the importance of redox reactions involving rifampicin and their relevance to the mechanism of action. Hence, we studied the oxidation of rifampicin catalyzed by HRP, since this enzyme may represent the prototype of peroxidation-mediated reactions. We found that the antibiotic is efficiently oxidized and that rifampicin-quinone is the product, in a reaction dependent on both HRP and hydrogen peroxide. The steady-state kinetic constants Km app (101±23 mmol/l), Vmax app (0.78±0.09 μmol/l·s-1) and kcat (5.1±0.6 s-1) were measured (n=4). The reaction rate was increased by the addition of co-substrates such as tetramethylbenzidine, salicylic acid, 5-aminosalicylic acid and paracetamol. This effect was explained by invoking an electron-transfer mechanism by which these drugs acted as mediators of rifampicin oxidation. We suggested that this drug interaction might be important at the inflammatory site. © 2005 Pharmaceutical Society of Japan.