Ionic mobility of the solvated proton and acid-base titration in a four-compartment capillary electrophoresis system

Although H(+) and OH(-) are the most common ions in aqueous media, they are not usually observable in capillary electrophoresis (CE) experiments, because of the extensive use of buffer solutions as the background electrolyte. In the present work, we introduce CE equipment designed to allow the determination of such ions in a similar fashion as any other ion. Basically, it consists of a four-compartment piece of equipment for electrolysis-separated experiments (D. P. de Jesus et at, Anal. Chem., 2005, 77, 607). In such a system, the ends of the capillary are placed in two reservoirs, which are connected to two other reservoirs through electrolyte-filled tubes. The electrodes of the high-voltage power source are positioned in these reservoirs. Thus, the electrolysis products are kept away from the inputs of the capillary. The detection was provided by two capacitively coupled contactless conductivity detectors (CD), each one positioned about 11 cm from the end of the capillary. Two applications were demonstrated: titration-like procedures for nanolitre samples and mobility measurements. Strong and weak acids (pK(a) < 5), pure or mixtures, could be titrated. The analytical curve is linear from 50 mu M up to 10 mM of total dissociable hydrogen (r = 0.99899 for n =10) in 10-nL samples. By including D(2)O in the running electrolyte, we could demonstrate how to measure the mixed proton/deuteron mobility. When H(2)O/D(2)O (9 : 1 v/v) was used as the solvent, the mobility was 289.6 +/- 0.5 x 10(-5) cm(2) V(-1) s(-1). Due to the fast conversion of the species, this value is related to the overall behaviour of all isotopologues and isotopomers of the Zundel and Eigen structures, as well as the Stokesian mobility of proton and deuteron. The effect of neutral (o-phenanthroline) and negatively charged (chloroacetate) bases and aprotic solvent (DMSO) over the H(+) mobility was also demonstrated.

In vivo bioavailability of selenium in enriched Pleurotus ostreatus mushrooms

The in vivo bioavailability of Se was investigated in enriched Pleurotus ostreatus mushrooms. A bioavailability study was performed using 64 Wistar male rats separated in 8 groups and fed with different diets: without Se, with mushrooms without Se, with enriched mushrooms containing 0.15, 0.30 or 0.45 mg kg(-1) Se and a normal diet containing 0.15 mg kg(-1) of Se using sodium selenate. The experiment was performed in two periods: depletion (14 days) and repletion (21 days), according to the Association of Official Analytical Chemists. After five weeks, the rats were sacrificed under carbon dioxide, and blood was drawn by heart puncture. Blood plasma was separated by centrifugation. The total Se concentration in the plasma of rats fed with enriched mushrooms was higher than in rats fed with a normal diet containing sodium selenate. The plasma protein profiles were obtained using size exclusion chromatography (SEC) and UV detectors. Aliquots of effluents (0.5 mL per minute) were collected throughout in the end of the chomatographic column. However, Se was determined by graphite furnace atomic absorption spectrometry (GF AAS) only in the aliquots where proteins were detected by SEC-UV. The plasma protein pro. le of rats fed with different diets was similar. The highest Se concentration was observed in a peptide presenting 8 kDa. Furthermore, the higher Se concentration in this peptide was obtained for rats fed with a diet using enriched mushrooms (7 mu g L(-1) Se) compared to other diets (2-5 mu g L(-1) Se). These results showed that Se-enriched mushrooms can be considered as an alternative Se food source for humans, due to their high bioavailability.

k(0)-INAA for determining chemical elements in bird feathers

The k(0)-method instrumental neutron activation analysis (k(0)-INAA) was employed for determining chemical elements in bird feathers. A collection was obtained taking into account several bird species from wet ecosystems in diverse regions of Brazil. For comparison reason, feathers were actively sampled in a riparian forest from the Marins Stream, Piracicaba, Sao Paulo State, using mist nets specific for capturing birds. Biological certified reference materials were used for assessing the quality of analytical procedure. Quantification of chemical elements was performed using the k(0)-INAA Quantu Software. Sixteen chemical elements, including macro and micronutrients, and trace elements, have been quantified in feathers, in which analytical uncertainties varied from 2% to 40% depending on the chemical element mass fraction. Results indicated high mass fractions of Br (max=7.9 mgkg(-1)), Co (max= 0.47 mg kg(-1)), Cr (max =68 mg kg(-1)), Hg (max =2.79 mg kg(-1)), Sb (max= 0.20 mg kg(-1)), Se (max=1.3 mg kg(-1)) and Zn (max =192 mg kg(-1)) in bird feathers, probably associated with the degree of pollution of the areas evaluated. In order to corroborate the use of k(0)-INAA results in biomonitoring studies using avian community, different factor analysis methods were used to check chemical element source apportionment and locality clustering based on feather chemical composition. (C) 2010 Elsevier B.V. All rights reserved.

Characterizing suspended sediments from the Piracicaba River Basin by means of k(0)-INAA

The inorganic chemical characterization of suspended sediments is of utmost relevance for the knowledge of the dynamics and movement of chemical elements in the aquatic and wet ecosystems. Despite the complexity of the effective design for studying this ecological compartment, this work has tested a procedure for analyzing suspended sediments by instrumental neutron activation analysis, k(0) method (k(0)-INAA). The chemical elements As, Ba, Br, Ca, Ce, Co, Cr, Cs, Eu, Fe, Hf, Fig, K, La, Mo, Na, Ni, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, Yb and Zn were quantified in the suspended sediment compartment by means of k(0)-INAA. When compared with World Average for rivers, high mass fractions of Fe (222,900 mg/kg), Ba (4990 mg/kg), Zn (1350 mg/kg), Cr (646 mg/kg), Co (74.5 mg/kg), Br (113 mg/kg) and Mo (31.9 mg/kg) were quantified in suspended sediments from the Piracicaba River, the Piracicamirim Stream and the Marins Stream. Results of the principal component analysis for standardized chemical element mass fractions indicated an intricate correlation among chemical elements evaluated, as a response of the contribution of natural and anthropogenic sources of chemical elements for ecosystems. (C) 2010 Elsevier B.V. All rights reserved.

Sequential injection analysis implementing multiple standard additions for As speciation by liquid chromatography and atomic fluorescence spectrometry (SIA-HPLC-AFS)

An analytical procedure for multiple standard additions of arsenic species using sequential injection analysis (SIA) is proposed for their quantification in seafood extracts. SIA presented flexibility for generating multiple specie standards at the ng mL(-1) concentration level by adding different volumes of As(III), As(V), monomethylarsonic (MMA) and dimethylarsinic (DMA) to the sample. The mixed sample plus standard solutions were delivered from SIA to fill the HPLC injection loop. Subsequently, As species were separated by HPLC and analyzed by atomic fluorescence spectrometry (AFS). The proposed system comprised two independently controlled modules, with the HPLC loop acting as the intermediary device. The analytical frequency was enhanced by combining the actions of both modules. While the added sample was flowing through the chromatographic column towards the detection system, the SIA program started performing the standard additions to another sample. The proposed method was applied to spoiled seafood extracts. Detection limits based on 3 sigma for As(III), As(V), MMA and DMA were 0.023, 0.39, 0.45 and 1.0 ng mL(-1), respectively. (C) 2011 Elsevier B.V. All rights reserved.

INAA with gamma-gamma coincidence for selenium determination in food

Selenium detection limits of INAA are normally above its concentration in most biological materials. Gamma-gamma coincidence methodology can be used to improve the detection limits and uncertainties in the determination of selenium. Here, some edible parts of plants were measured using a HPGe detector equipped with a NaI(Tl) active shielding, producing spectra both in normal and coincidence modes. The results presented the reduction of the detection limits of selenium by a factor of 2 to 3 times and improvement in the uncertainty of up to 2 times.

Artificial Pinning Center Studies in BI2212 Tapes and Bulks With Zirconium Oxide Inclusion

Zirconium oxide inclusion in Bi2212 superconducting tapes and bulks was studied as possible artificial pinning centers (APC). In order to analyze the zirconium oxide APC addition in Bi2212 samples, magnetization measurements were performed in bulks and transport properties measurements were performed on tapes. In magnetization measurements, the critical current densities are proportional to the width of the magnetization loop at each applied magnetic field. Addition of ZrO(2) in Bi2212 superconductors broadened the magnetization loop and enhanced the critical current densities at 4.2 K in bulks, as a clear indication that ZrO(2) addition improved the pinning and acted as APCs. In contrast, the transport critical current densities decreased in tapes.

Fuzzy pole placement based on piecewise Lyapunov functions

This paper presents a controller design method for fuzzy dynamic systems based on piecewise Lyapunov functions with constraints on the closed-loop pole location. The main idea is to use switched controllers to locate the poles of the system to obtain a satisfactory transient response. It is shown that the global fuzzy system satisfies the requirements for the design and that the control law can be obtained by solving a set of linear matrix inequalities, which can be efficiently solved with commercially available softwares. An example is given to illustrate the application of the proposed method. Copyright (C) 2009 John Wiley & Sons, Ltd.

An algorithm for computerized automatic tuning of power system stabilizers

The main objective of this paper is to relieve the power system engineers from the burden of the complex and time-consuming process of power system stabilizer (PSS) tuning. To achieve this goal, the paper proposes an automatic process for computerized tuning of PSSs, which is based on an iterative process that uses a linear matrix inequality (LMI) solver to find the PSS parameters. It is shown in the paper that PSS tuning can be written as a search problem over a non-convex feasible set. The proposed algorithm solves this feasibility problem using an iterative LMI approach and a suitable initial condition, corresponding to a PSS designed for nominal operating conditions only (which is a quite simple task, since the required phase compensation is uniquely defined). Some knowledge about the PSS tuning is also incorporated in the algorithm through the specification of bounds defining the allowable PSS parameters. The application of the proposed algorithm to a benchmark test system and the nonlinear simulation of the resulting closed-loop models demonstrate the efficiency of this algorithm. (C) 2009 Elsevier Ltd. All rights reserved.

Ecodesign methods focused on remanufacturing

Understanding the product`s `end-of-life` is important to reduce the environmental impact of the products` final disposal. When the initial stages of product development consider end-of-life aspects, which can be established by ecodesign (a proactive approach of environmental management that aims to reduce the total environmental impact of products), it becomes easier to close the loop of materials. The `end-of-life` ecodesign methods generally include more than one `end-of-life` strategy. Since product complexity varies substantially, some components, systems or sub-systems are easier to be recycled, reused or remanufactured than others. Remanufacture is an effective way to maintain products in a closed-loop, reducing both environmental impacts and costs of the manufacturing processes. This paper presents some ecodesign methods focused on the integration of different `end-of-life` strategies, with special attention to remanufacturing, given its increasing importance in the international scenario to reduce the life cycle impacts of products. (C) 2009 Elsevier Ltd. All rights reserved.

A state-space modeling approach for active structural acoustic control

The demands for improvement in sound quality and reduction of noise generated by vehicles are constantly increasing, as well as the penalties for space and weight of the control solutions. A promising approach to cope with this challenge is the use of active structural-acoustic control. Usually, the low frequency noise is transmitted into the vehicle`s cabin through structural paths, which raises the necessity of dealing with vibro-acoustic models. This kind of models should allow the inclusion of sensors and actuators models, if accurate performance indexes are to be accessed. The challenge thus resides in deriving reasonable sized models that integrate structural, acoustic, electrical components and the controller algorithm. The advantages of adequate active control simulation strategies relies on the cost and time reduction in the development phase. Therefore, the aim of this paper is to present a methodology for simulating vibro-acoustic systems including this coupled model in a closed loop control simulation framework that also takes into account the interaction between the system and the control sensors/actuators. It is shown that neglecting the sensor/actuator dynamics can lead to inaccurate performance predictions.

Robust Control of Flight Simulator Motion Base

The purpose of this study is to apply robust inverse dynamics control for a six-degree-of-freedom flight simulator motion system. From an implementation viewpoint, simplification of the inverse dynamics control law is introduced by assuming control law matrices as constants. The robust control strategy is applied in the outer loop of the inverse dynamic control to counteract the effects of imperfect compensation due this simplification. The control strategy is designed using the Lyapunov stability theory. Forward and inverse kinematics and a full dynamic model of a six-degree-of-freedom motion base driven by electromechanical actuators are briefly presented. A describing function, acceleration step response and some maneuvers computed from the washout filter were used to evaluate the performance of the controllers.

Comparison Between Voltage Control Structures of Synchronous Machines

This paper compares the behaviour of two different control structures of automatic voltage regulators of synchronous machines equipped with static excitation systems. These systems have a fully controlled thyristor bridge that supplies DC current to the rotor winding. The rectifier bridge is fed by the stator terminals through a step-down transformer. The first control structure, named ""Direct Control"", has a single proportional-integral (PI) regulator that compares stator voltage setpoint with measured voltage and acts directly on the thyristor bridge`s firing angle. This control structure is usually employed in commercial excitation systems for hydrogenerators. The second structure, named ""Cascade Control"", was inspired on control loops of commercial DC motor drives. Such drives employ two PIs in a cascade arrangement, the external PI deals with the motor speed while the internal one regulates the armature current. In the adaptation proposed, the external PI compares setpoint with the actual stator voltage and produces the setpoint to the internal PI-loop which controls the field current.

Tiering strategic environmental assessment and project environmental impact assessment in highway planning in Sao Paulo, Brazil

Constructing highways in dense urban areas is always a challenge. In Sao Paulo Metropolitan Region, heavy truck traffic contributes to clog streets and expressways alike. As part of the traffic neither originates nor head to the region, a peripheral highway has been proposed to reduce traffic problems. This project called Rodoanel, is an expressway approximately 175 km long. The fact that the projected south and north sections would cross catchments that supply most of the metropolis water demand was strongly disputed and made the environmental permitting process particularly difficult. The agency in charge commissioned a strategic environmental assessment (SEA) of a revamped project, and called it the Rodoanel Programme. However, the SEA report failed to satisfactorily take account of significant strategic issues. Among these, the highway potential effect of inducing urban sprawl over water protection zones is the most critical issue, as it emerged later as a hurdle to project licensing. Conclusion is that, particularly where no agreed-upon framework for SEA exists, when vertical tiering with downstream project EIA is sought, then a careful scoping of strategic issues is more than necessary. If an agreement on `what is strategic` is not reached and not recognized by influential stakeholders, then the unsettled conflicts will be transferred to project EIA. In such a context, SEA will have added another loop to the usually long road to project approval. (c) 2008 Elsevier Inc. All rights reserved.

Modeling, control and experimental validation of a novel actuator based on shape memory alloys

The paper presents the development of a mechanical actuator using a shape memory alloy with a cooling system based on the thermoelectric effect (Seebeck-Peltier effect). Such a method has the advantage of reduced weight and requires a simpler control strategy as compared to other forced cooling systems. A complete mathematical model of the actuator was derived, and an experimental prototype was implemented. Several experiments are used to validate the model and to identify all parameters. A robust and nonlinear controller, based on sliding-mode theory, was derived and implemented. Experiments were used to evaluate the actuator closed-loop performance, stability, and robustness properties. The results showed that the proposed cooling system and controller are able to improve the dynamic response of the actuator. (C) 2009 Elsevier Ltd. All rights reserved.