Determination of polyphenols in wines by reaction with 4-aminoantipyrine and photometric flow-injection analysis

A new flow-injection analytical procedure is proposed for the determination of the total amount of polyphenols in wines; the method is based on the formation of a colored complex between 4-aminoantipyrine and phenols, in the presence of an oxidizing reagent. The oxidizing agents hexacyanoferrate(III), peroxodisulfate, and tetroxoiodate(VII) were tested. Batch trials were first performed to select appropriate oxidizing agents, pH, and concentration ratios of reagents, on the basis of their effect on the stability of the colored complex. Conditions selected as a result of these trials were implemented in a flow-injection analytical system in which the influence of injection volume, flow rate, and reaction- coil length, was evaluated. Under the optimum conditions the total amount of polyphenols, expressed as gallic acid, could be determined within a concentration range of 36 to 544 mg L–1, and with a sensitivity of 344 L mol–1 cm–1 and an RSD <1.1%. The reproducibility of analytical readings was indicative of standard deviations <2%. Interference from sugars, tartaric acid, ascorbic acid, methanol, ammonium sulfate, and potassium chloride was negligible. The proposed system was applied to the determination of total polyphenols in red wines, and enabled analysis of approximately 55 samples h–1. Results were usually precise and accurate; the RSD was <3.9% and relative errors, by the Folin–Ciocalteu method, <5.1%.

Study of the voltammetric behaviour of metam and its application to an amperometric flow system

The electrochemical behaviour of the pesticide metam (MT) at a glassy carbon working electrode (GCE) and at a hanging mercury drop electrode (HMDE) was investigated. Different voltammetric techniques, including cyclic voltammetry (CV) and square wave voltammetry (SWV), were used. An anodic peak (independent of pH) at +1.46 V vs AgCl/Ag was observed in MTaqueous solution using the GCE. SWV calibration curves were plotted under optimized conditions (pH 2.5 and frequency 50 Hz), which showed a linear response for 17–29 mg L−1. Electrochemical reduction was also explored, using the HMDE. A well defined cathodic peak was recorded at −0.72 V vs AgCl/ Ag, dependent on pH. After optimizing the operating conditions (pH 10.1, frequency 150 Hz, potential deposition −0.20 V for 10 s), calibration curves was measured in the concentration range 2.5×10−1 to 1.0 mg L−1 using SWV. The electrochemical behaviour of this compound facilitated the development of a flow injection analysis (FIA) system with amperometric detection for the quantification of MT in commercial formulations and spiked water samples. An assessment of the optimal FIA conditions indicated that the best analytical results were obtained at a potential of +1.30 V, an injection volume of 207 μL and an overall flow rate of 2.4 ml min−1. Real samples were analysed via calibration curves over the concentration range 1.3×10−2 to 1.3 mg L−1. Recoveries from the real samples (spiked waters and commercial formulations) were between 97.4 and 105.5%. The precision of the proposed method was evaluated by assessing the relative standard deviation (RSD %) of ten consecutive determinations of one sample (1.0 mg L−1), and the value obtained was 1.5%.

Flow-injection potentiometric method for the routine determination of chloride: application to bread analysis

Bread is consumed worldwide by man, thus contributing to the regular ingestion of certain inorganic species such as chloride. It controls the blood pressure if associated to a sodium intake and may increase the incidence of stomach ulcer. Its routine control should thus be established by means of quick and low cost procedures. This work reports a double- channel flow injection analysis (FIA) system with a new chloride sensor for the analysis of bread. All solutions are prepared in water and necessary ionic strength adjustments are made on-line. The body of the indicating electrode is made from a silver needle of 0.8 mm i.d. with an external layer of silver chloride. These devices were constructed with different lengths. Electrodes of 1.0 to 3.0 cm presented better analytical performance. The calibration curves under optimum conditions displayed Nernstian behaviour, with average slopes of 56 mV decade-1, with sampling rates of 60 samples h-1. The method was applied to analyze several kinds of bread, namely pão de trigo, pão integral, pão de centeio, pão de mistura, broa de milho, pão sem sal, pão meio sal, pão-de-leite, and pão de água. The accuracy and precision of the potentiometric method were ascertained by comparison to a spectrophotometric method of continuous segmented flow. These methods were validated against ion-chromatography procedures.

FIA potentiometric system based on periodate polymeric membrane sensors for the assessment of ascorbic acid in commercial drinks

Ascorbic acid is found in many food samples. Its clinical and technological importance demands an easyto- use, rapid, robust and inexpensive method of analysis. For this purpose, this work proposes a new flow procedure based on the oxidation of ascorbic acid by periodate. A new potentiometric periodate sensor was constructed to monitor this reaction. The selective membranes were of PVC with porphyrin-based sensing systems and a lipophilic cation as additive. The sensor displayed a near-Nernstian response for periodate over 1.0x10-2–6.0x10-6 M, with an anionic slope of 73.9 ± 0.9 mV decade-1. It was pH independent in acidic media and presented good selectivity features towards several inorganic anions. The flow set-up operated in double-channel, carrying a 5.0x10-4 M IO- 4 solution and a suitable buffer; these were mixed in a 50-cm reaction coil. The overall flow rate was 7 ml min-1 and the injection volume 70 µl. Under these conditions, a linear behaviour against concentration was observed for 17.7–194.0 µg ml-1, presenting slopes of 0.169 mV (mg/l)-1, a reproducibility of ±1.1 mV (n = 5), and a sampling rate of ~96 samples h-1. The proposed method was applied to the analysis of beverages and pharmaceuticals.

Influence of long-term wearing of unstable shoes on compensatory control of posture: An electromyography-based analysis

Purpose: This study investigated the influence of long-term wearing of unstable shoes (WUS) on compensatory postural adjustments (CPA) to an external perturbation. Methods: Participants were divided into two groups: one wore unstable shoes while the other wore conventional shoes for 8 weeks. The ground reaction force signal was used to calculate the anterior– posterior (AP) displacement of the centre of pressure (CoP) and the electromyographic signal of gastrocnemius medialis (GM), tibialis anterior (TA), rectus femoris (RF) and biceps femoris (BF) muscles was used to assess individual muscle activity, antagonist co-activation and reciprocal activation at the joint (TA/GM and RF/(BF + GM) pairs) and muscle group levels (ventral (TA + RF)/dorsal (GM + BF) pair) within time intervals typical for CPA. The electromyographic signal was also used to assess muscle latency. The variables described were evaluated before and after the 8-week period while wearing the unstable shoes and barefoot. Results: Long-term WUS led to: an increase of BF activity in both conditions (barefoot and wearing the unstable shoes); a decrease of GM activity; an increase of antagonist co-activation and a decrease of reciprocal activation level at the TA/GM and ventral/dorsal pairs in the unstable shoe condition. Additionally, WUS led to a decrease in CoP displacement. However, no differences were observed in muscle onset and offset. Conclusion: Results suggest that the prolonged use of unstable shoes leads to increased ankle and muscle groups’ antagonist co-activation levels and higher performance by the postural control system.

Analysis of the combined exposure to noise and ototoxic substances—pilot study

Abstract: Ototoxic substances have been associated to damage of the auditory system, and its effects are potentiated by noise exposure. The present study aims at analyzing auditory changes from combined exposure to noise and organic solvents, through a pilot study in the furniture industry sector. Audiological tests were performed on 44 workers, their levels of exposure to toluene, xylene and ethylbenzene were determined and the levels of noise exposure were evaluated. The results showed that workers are generally exposed to high noise levels and cabin priming filler and varnish sector workers have high levels of exposure to toluene. However, no hearing loss was registered among the workers. Workers exposed simultaneously to noise and ototoxic substances do not have a higher degree of hearing loss than those workers exposed only to noise. Thus, the results of this study did not show that the combined exposure to noise and the organic solvent is associated with hearing disorders.

Strategic bidding in electricity markets: an agent-based simulator with game theory for scenario analysis

Electricity markets are complex environments, involving a large number of different entities, with specific characteristics and objectives, making their decisions and interacting in a dynamic scene. Game-theory has been widely used to support decisions in competitive environments; therefore its application in electricity markets can prove to be a high potential tool. This paper proposes a new scenario analysis algorithm, which includes the application of game-theory, to evaluate and preview different scenarios and provide players with the ability to strategically react in order to exhibit the behavior that better fits their objectives. This model includes forecasts of competitor players’ actions, to build models of their behavior, in order to define the most probable expected scenarios. Once the scenarios are defined, game theory is applied to support the choice of the action to be performed. Our use of game theory is intended for supporting one specific agent and not for achieving the equilibrium in the market. MASCEM (Multi-Agent System for Competitive Electricity Markets) is a multi-agent electricity market simulator that models market players and simulates their operation in the market. The scenario analysis algorithm has been tested within MASCEM and our experimental findings with a case study based on real data from the Iberian Electricity Market are presented and discussed.

On the development of an automatic voice pleasantness classification and intensity estimation system

In the last few years, the number of systems and devices that use voice based interaction has grown significantly. For a continued use of these systems, the interface must be reliable and pleasant in order to provide an optimal user experience. However there are currently very few studies that try to evaluate how pleasant is a voice from a perceptual point of view when the final application is a speech based interface. In this paper we present an objective definition for voice pleasantness based on the composition of a representative feature subset and a new automatic voice pleasantness classification and intensity estimation system. Our study is based on a database composed by European Portuguese female voices but the methodology can be extended to male voices or to other languages. In the objective performance evaluation the system achieved a 9.1% error rate for voice pleasantness classification and a 15.7% error rate for voice pleasantness intensity estimation.

Root-locus practical sketching rules for fractional-order system

For integer-order systems, there are well-known practical rules for RL sketching. Nevertheless, these rules cannot be directly applied to fractional-order (FO) systems. Besides, the existing literature on this topic is scarce and exclusively focused on commensurate systems, usually expressed as the ratio of two noninteger polynomials. The practical rules derived for those do not apply to other symbolic expressions, namely, to transfer functions expressed as the ratio of FO zeros and poles. However, this is an important case as it is an extension of the classical integer-order problem usually addressed by control engineers. Extending the RL practical sketching rules to such FO systems will contribute to decrease the lack of intuition about the corresponding system dynamics. This paper generalises several RL practical sketching rules to transfer functions specified as the ratio of FO zeros and poles. The subject is presented in a didactic perspective, being the rules applied to several examples.

Distributed active traction control system applied to the RoboCup middle size league

This work addresses the problem of traction control in mobile wheeled robots in the particular case of the RoboCup Middle Size League (MSL). The slip control problem is formulated using simple friction models for ISePorto Team robots with a differential wheel configuration. Traction was also characterized experimentally in the MSL scenario for relevant game events. This work proposes a hierarchical traction control architecture which relies in local slip detection and control at each wheel, with relevant information being relayed to a higher level responsible for global robot motion control. A dedicated one axis control embedded hardware subsystem allowing complex local control, high frequency current sensing and odometric information procession was developed. This local axis control board is integrated in a distributed system using CAN bus communications. The slipping observer was implemented in the axis control hardware nodes integrated in the ISePorto robots and was used to control and detect loss of for traction. %and to detect the ball in the kicking device. An external vision system was used to perform a qualitative analysis of the slip detection and observer performance results are presented.

Evaluation of dynamic pass-through of carbon prices into electricity prices – a cointegrated VECM analysis

This paper addresses the impact of the CO2 opportunity cost on the wholesale electricity price in the context of the Iberian electricity market (MIBEL), namely on the Portuguese system, for the period corresponding to the Phase II of the European Union Emission Trading Scheme (EU ETS). In the econometric analysis a vector error correction model (VECM) is specified to estimate both long–run equilibrium relations and short–run interactions between the electricity price and the fuel (natural gas and coal) and carbon prices. The model is estimated using daily spot market prices and the four commodities prices are jointly modelled as endogenous variables. Moreover, a set of exogenous variables is incorporated in order to account for the electricity demand conditions (temperature) and the electricity generation mix (quantity of electricity traded according the technology used). The outcomes for the Portuguese electricity system suggest that the dynamic pass–through of carbon prices into electricity prices is strongly significant and a long–run elasticity was estimated (equilibrium relation) that is aligned with studies that have been conducted for other markets.

From simulation to statistical analysis: timeliness assessment of ethernet/IP-based distributed systems

A number of characteristics are boosting the eagerness of extending Ethernet to also cover factory-floor distributed real-time applications. Full-duplex links, non-blocking and priority-based switching, bandwidth availability, just to mention a few, are characteristics upon which that eagerness is building up. But, will Ethernet technologies really manage to replace traditional Fieldbus networks? Ethernet technology, by itself, does not include features above the lower layers of the OSI communication model. In the past few years, it is particularly significant the considerable amount of work that has been devoted to the timing analysis of Ethernet-based technologies. It happens, however, that the majority of those works are restricted to the analysis of sub-sets of the overall computing and communication system, thus without addressing timeliness at a holistic level. To this end, we are addressing a few inter-linked research topics with the purpose of setting a framework for the development of tools suitable to extract temporal properties of Commercial-Off-The-Shelf (COTS) Ethernet-based factory-floor distributed systems. This framework is being applied to a specific COTS technology, Ethernet/IP. In this paper, we reason about the modelling and simulation of Ethernet/IP-based systems, and on the use of statistical analysis techniques to provide usable results. Discrete event simulation models of a distributed system can be a powerful tool for the timeliness evaluation of the overall system, but particular care must be taken with the results provided by traditional statistical analysis techniques.

Engineering real-time applications with WorldFIP: tools and analysis

WorldFIP is standardised as European Norm EN 50170 - General Purpose Field Communication System. Field communication systems (fieldbuses) started to be widely used as the communication support for distributed computer-controlled systems (DCCS), and are being used in all sorts of process control and manufacturing applications within different types of industries. There are several advantages in using fieldbuses as a replacement of for the traditional point-to-point links between sensors/actuators and computer-based control systems. Indeed they concern economical ones (cable savings) but, importantly, fieldbuses allow an increased decentralisation and distribution of the processing power over the field. Typically DCCS have real-time requirements that must be fulfilled. By this, we mean that process data must be transferred between network computing nodes within a maximum admissible time span. WorldFIP has very interesting mechanisms to schedule data transfers. It explicit distinguishes to types of traffic: periodic and aperiodic. In this paper we describe how WorldFIP handles these two types of traffic, and more importantly, we provide a comprehensive analysis for guaranteeing the real-time requirements of both types of traffic. A major contribution is made in the analysis of worst-case response time of aperiodic transfer requests.

Laxity dynamics and LLF schedulability analysis on multiprocessor platforms

LLF (Least Laxity First) scheduling, which assigns a higher priority to a task with a smaller laxity, has been known as an optimal preemptive scheduling algorithm on a single processor platform. However, little work has been made to illuminate its characteristics upon multiprocessor platforms. In this paper, we identify the dynamics of laxity from the system’s viewpoint and translate the dynamics into LLF multiprocessor schedulability analysis. More specifically, we first characterize laxity properties under LLF scheduling, focusing on laxity dynamics associated with a deadline miss. These laxity dynamics describe a lower bound, which leads to the deadline miss, on the number of tasks of certain laxity values at certain time instants. This lower bound is significant because it represents invariants for highly dynamic system parameters (laxity values). Since the laxity of a task is dependent of the amount of interference of higher-priority tasks, we can then derive a set of conditions to check whether a given task system can go into the laxity dynamics towards a deadline miss. This way, to the author’s best knowledge, we propose the first LLF multiprocessor schedulability test based on its own laxity properties. We also develop an improved schedulability test that exploits slack values. We mathematically prove that the proposed LLF tests dominate the state-of-the-art EDZL tests. We also present simulation results to evaluate schedulability performance of both the original and improved LLF tests in a quantitative manner.

Optimizing the renewable generation mix in the Portuguese power system based on temporal and spatial diversity

Renewable energy sources (RES) have unique characteristics that grant them preference in energy and environmental policies. However, considering that the renewable resources are barely controllable and sometimes unpredictable, some challenges are faced when integrating high shares of renewable sources in power systems. In order to mitigate this problem, this paper presents a decision-making methodology regarding renewable investments. The model computes the optimal renewable generation mix from different available technologies (hydro, wind and photovoltaic) that integrates a given share of renewable sources, minimizing residual demand variability, therefore stabilizing the thermal power generation. The model also includes a spatial optimization of wind farms in order to identify the best distribution of wind capacity. This methodology is applied to the Portuguese power system.