Enzymatic determination of choline in milk using a FIA system with potentiometric detection

The development of a FIA system for the determination of total choline content in several types of milk is described. The samples were submitted to hydrochloric acid digestion before injection into the system and passed through an enzymatic reactor containing choline oxidase immobilised on glass beads. This enzymatic reaction releases hydrogen peroxide which then reacts with a solution of iodide. The decrease in the concentration of iodide ion is quantified using an iodide ion selective tubular electrode based on a homogeneous crystalline membrane. Validation of the results obtained with this system was performed by comparison with results from a method described in the literature and applied to the determination of total choline in milks. The relative deviation was always < 5%. The repeatability of the method developed was assessed by calculation of the relative standard deviation (RSD) for 12 consecutive injections of one sample. The RSD obtained was < 0.6%.

Constructing Cultural Policies in Romania. A possible model for communicating the national value system

The premise of this paper is that a model for communicating the national value system must start from a strategy aimed at the identification, the cultivation and communication of values that give consistency to the value system. The analysis concentrates on the elements of such strategies and on the implications of applying a value communication program on the identity architecture of the community. The paper will also discuss the role of the national value system in the context of the emerging global culture, where the individual has the power to create his/her own hybrid cultural model.

Self-assembly in chains, rings, and branches: a single component system with two critical points

Agências financiadoras: FCT - PEstOE/FIS/UI0618/2011; PTDC/FIS/098254/2008 ERC-PATCHYCOLLOIDS e MIUR-PRIN

Development of an FIA system with amperometric detection for determination of bentazone in estuarine waters

On the basis of its electrochemical behaviour a new flow-injection analysis (FIA) method with amperometric detection has been developed for quantification of the herbicide bentazone (BTZ) in estuarine waters. Standard solutions and samples (200 µL) were injected into a water carrier stream and both pH and ionic strength were automatically adjusted inside the manifold. Optimization of critical FIA conditions indicated that the best analytical results were obtained at an oxidation potential of 1.10 V, pH 4.5, and an overall flow-rate of 2.4 mL min–1. Analysis of real samples was performed by means of calibration curves over the concentration range 2.5x10–6 to 5.0x10–5 mol L–1, and results were compared with those obtained by use of an independent method (HPLC). The accuracy of the amperometric determinations was ascertained; errors relative to the comparison method were below 4% and sampling rates were approximately 100 samples h–1. The repeatability of the proposed method was calculated by assessing the relative standard deviation (%) of ten consecutive determinations of one sample; the value obtained was 2.1%.

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%.

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.

10 kVp rule – An anthropomorphic pelvis phantom imaging study using a CR system: impact on image quality and effective dose using AEC and manual mode

Background - Pelvis and hip radiography are consistently found to be amongst the highest contributors to the collective effective dose (E) in all ten DOSE DATAMED countries in Europe, representing 2.8 to 9.4% of total collective dose (S) in the TOP 20 exams list. The level of image quality should provide all the diagnostic information in order not to jeopardise the diagnosis, but being able to provide the needed clinical information with the minimum dose. A recent study suggests further research to determine whether the “10 kVp rule” would have value for a range of examinations using Computed Radiography (CR) systems. As a “rule of thumb” increasing the kVp by 10 whilst halving the mAs is suggested to give a similar perceptual image quality when compared to the original exposure factors. Aims - In light of the 10kVp rule, this study aims to investigate the influence of tube potential (kVp) variation in relation to perceptual image quality and E for pelvis imaging using automatic exposure control (AEC) and non-AEC in a Computed Radiography (CR) system. Research questions - Does the 10kVp rule works for the pelvis in relation to image quality in a CR system? Does the image quality differs when the AEC is used instead of manual mode using the 10kVp rule and how this impacts on E?

Sistema pericial para suporte à decisão na alocação de recursos de emergência

O panorama atual da emergência e socorro de primeira linha em Portugal, carateriza-se por uma grande aposta ao longo dos últimos anos num incremento contínuo da qualidade e da eficiência que estes serviços prestam às populações locais. Com vista à prossecução do objetivo de melhoria contínua dos serviços, foram realizados ao longo dos últimos anos investimentos avultados ao nível dos recursos técnicos e ao nível da contratação e formação de recursos humanos altamente qualificados. Atualmente as instituições que prestam socorro e emergência de primeira linha estão bem dotadas ao nível físico e ao nível humano dos recursos necessários para fazerem face aos mais diversos tipos de ocorrências. Contudo, ao nível dos sistemas de informação de apoio à emergência e socorro de primeira linha, verifica-se uma inadequação (e por vezes inexistência) de sistemas informáticos capazes de suportar convenientemente o atual contexto de exigência e complexidade da emergência e socorro. Foi feita ao longo dos últimos anos, uma forte aposta na melhoria dos recursos físicos e dos recursos humanos encarregues da resposta àsemergência de primeira linha, mas descurou-se a área da gestão e análise da informação sobre as ocorrências, assim como, o delinear de possíveis estratégias de prevenção que uma análise sistematizada da informação sobre as ocorrências possibilita. Nas instituições de emergência e socorro de primeira linha em Portugal (bombeiros, proteção civil municipal, PSP, GNR, polícia municipal), prevalecem ainda hoje os sistemas informáticos apenas para o registo das ocorrências à posteriori e a total inexistência de sistemas de registo de informação e de apoio à decisão na alocação de recursos que operem em tempo real. A generalidade dos sistemas informáticos atualmente existentes nas instituições são unicamente de sistemas de backoffice, que não aproveitam a todas as potencialidades da informação operacional neles armazenada. Verificou-se também, que a geo-localização por via informática dos recursos físicos e de pontos de interesse relevantes em situações críticas é inexistente a este nível. Neste contexto, consideramos ser possível e importante alinhar o nível dos sistemas informáticos das instituições encarregues da emergência e socorro de primeira linha, com o nível dos recursos físicos e humanos que já dispõem atualmente. Dado que a emergência e socorro de primeira linha é um domínio claramente elegível para a aplicação de tecnologias provenientes dos domínios da inteligência artificial (nomeadamente sistemas periciais para apoio à decisão) e da geo-localização, decidimos no âmbito desta tese desenvolver um sistema informático capaz de colmatar muitas das lacunas por nós identificadas ao nível dos sistemas informáticos destas instituições. Pretendemos colocar as suas plataformas informáticas num nível similar ao dos seus recursos físicos e humanos. Assim, foram por nós identificadas duas áreas chave onde a implementação de sistemas informáticos adequados às reais necessidades das instituições podem ter um impacto muito proporcionar uma melhor gestão e otimização dos recursos físicos e humanos. As duas áreas chave por nós identificadas são o suporte à decisão na alocação dos recursos físicos e a geolocalização dos recursos físicos, das ocorrências e dos pontos de interesse. Procurando fornecer uma resposta válida e adequada a estas duas necessidades prementes, foi desenvolvido no âmbito desta tese o sistema CRITICAL DECISIONS. O sistema CRITICAL DECISIONS incorpora um conjunto de funcionalidades típicas de um sistema pericial, para o apoio na decisão de alocação de recursos físicos às ocorrências. A inferência automática dos recursos físicos, assenta num conjunto de regra de inferência armazenadas numa base de conhecimento, em constante crescimento e atualização, com base nas respostas bem sucedidas a ocorrências passadas. Para suprimir as carências aos nível da geo-localização dos recursos físicos, das ocorrências e dos pontos de interesse, o sistema CRITICAL DECISIONS incorpora também um conjunto de funcionalidades de geo-localização. Estas permitem a geo-localização de todos os recursos físicos da instituição, a geo-localização dos locais e as áreas das várias ocorrências, assim como, dos vários tipos de pontos de interesse. O sistema CRITICAL DECISIONS visa ainda suprimir um conjunto de outras carências por nós identificadas, ao nível da gestão documental (planos de emergência, plantas dos edifícios) , da comunicação, da partilha de informação entre as instituições de socorro e emergência locais, da contabilização dos tempos de serviço, entre outros. O sistema CRITICAL DECISIONS é o culminar de um esforço colaborativo e contínuo com várias instituições, responsáveis pela emergência e socorro de primeira linha a nível local. Esperamos com o sistema CRITICAL DECISIONS, dotar estas instituições de uma plataforma informática atual, inovadora, evolutiva, com baixos custos de implementação e de operação, capaz de proporcionar melhorias contínuas e significativas ao nível da qualidade da resposta às ocorrências, das capacidades de prevenção e de uma melhor otimização de todos os tipos de recursos que têm ao dispor.

Six thinking hats for electricity markets simulation: adapting meeting tools to agent decision

In almost all industrialized countries, the energy sector has suffered a severe restructuring that originated a greater complexity in market players’ interactions. The complexity that these changes brought made way for the creation of decision support tools that facilitate the study and understanding of these markets. MASCEM – “Multiagent Simulator for Competitive Electricity Markets” arose in this context providing a framework for evaluating new rules, new behaviour, and new participants in deregulated electricity markets. MASCEM uses game theory, machine learning techniques, scenario analysis and optimisation techniques to model market agents and to provide them with decision-support. ALBidS is a multiagent system created to provide decision support to market negotiating players. Fully integrated with MASCEM it considers several different methodologies based on very distinct approaches. The Six Thinking Hats is a powerful technique used to look at decisions from different perspectives. This tool’s goal is to force the thinker to move outside his habitual thinking style. It was developed to be used mainly at meetings in order to “run better meetings, make faster decisions”. This dissertation presents a study about the applicability of the Six Thinking Hats technique in Decision Support Systems, particularly with the multiagent paradigm like the MASCEM simulator. As such this work’s proposal is of a new agent, a meta-learner based on STH technique that organizes several different ALBidS’ strategies and combines the distinct answers into a single one that, expectedly, out-performs any of them.

A distributed system for learning programming on-line

Several Web-based on-line judges or on-line programming trainers have been developed in order to allow students to train their programming skills. However, their pedagogical functionalities in the learning of programming have not been clearly defined. EduJudge is a project which aims to integrate the “UVA On-line Judge”, an existing on-line programming trainer with an important number of problems and users, into an effective educational environment consisting of the e-learning platform Moodle and the competitive learning tool QUESTOURnament. The result is the EduJudge system which allows teachers to apply different pedagogical approaches using a proven e-learning platform, makes problems easy to search through an effective search engine, and provides an automated evaluation of the solutions submitted to these problems. The final objective is to provide new learning strategies to motivate students and present programming as an easy and attractive challenge. EduJudge has been tried and tested in three algorithms and programming courses in three different Engineering degrees. The students’ motivation and satisfaction levels were analysed alongside the effects of the EduJudge system on students’ academic outcomes. Results indicate that both students and teachers found that among other multiple benefits the EduJudge system facilitates the learning process. Furthermore, the experi- ment also showed an improvement in students’ academic outcomes. It must be noted that the students’ level of satisfaction did not depend on their computer skills or their gender.

Distribution system operation supported by contextual energy resource management based on intelligent SCADA

Future distribution systems will have to deal with an intensive penetration of distributed energy resources ensuring reliable and secure operation according to the smart grid paradigm. SCADA (Supervisory Control and Data Acquisition) is an essential infrastructure for this evolution. This paper proposes a new conceptual design of an intelligent SCADA with a decentralized, flexible, and intelligent approach, adaptive to the context (context awareness). This SCADA model is used to support the energy resource management undertaken by a distribution network operator (DNO). Resource management considers all the involved costs, power flows, and electricity prices, allowing the use of network reconfiguration and load curtailment. Locational Marginal Prices (LMP) are evaluated and used in specific situations to apply Demand Response (DR) programs on a global or a local basis. The paper includes a case study using a 114 bus distribution network and load demand based on real data.

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.

Integration of an automatic storage and retrieval system (ASRS) in a discrete-part automation system

This technical report describes the work carried out in a project within the ERASMUS programme. The objective of this project was the Integration of an Automatic Warehouse in a Discrete-Part Automation System. The discrete-part automation system located at the LASCRI (Critical Systems) laboratory at ISEP was extended with automatic storage and retrieval of the manufacturing parts, through the integration of an automatic warehouse and an automatic guided vehicle (AGV).