Citrate selective electrodes for the flow injection analysis of soft drinks, beers and pharmaceutical products

Aiming the establishment of simple and accurate readings of citric acid (CA) in complex samples, citrate (CIT) selective electrodes with tubular configuration and polymeric membranes plus a quaternary ammonium ion exchanger were constructed. Several selective membranes were prepared for this purpose, having distinct mediator solvents (with quite different polarities) and, in some cases, p-tert-octylphenol (TOP) as additive. The latter was used regarding a possible increase in selectivity. The general working characteristics of all prepared electrodes were evaluated in a low dispersion flow injection analysis (FIA) manifold by injecting 500µl of citrate standard solutions into an ionic strength (IS) adjuster carrier (10−2 mol l−1) flowing at 3ml min−1. Good potentiometric response, with an average slope and a repeatability of 61.9mV per decade and ±0.8%, respectively, resulted from selective membranes comprising additive and bis(2-ethylhexyl)sebacate (bEHS) as mediator solvent. The same membranes conducted as well to the best selectivity characteristics, assessed by the separated solutions method and for several chemical species, such as chloride, nitrate, ascorbate, glucose, fructose and sucrose. Pharmaceutical preparations, soft drinks and beers were analyzed under conditions that enabled simultaneous pH and ionic strength adjustment (pH = 3.2; ionic strength = 10−2 mol l−1), and the attained results agreed well with the used reference method (relative error < 4%). The above experimental conditions promoted a significant increase in sensitivity of the potentiometric response, with a supra-Nernstian slope of 80.2mV per decade, and allowed the analysis of about 90 samples per hour, with a relative standard deviation <1.0%.

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%.

Remediation efficiency of vapour extraction of sandy soils contaminated with cyclohexane: influence of air flow rate, water and natural organic matter content

Abstract This work reports the analysis of the efficiency and time of soil remediation using vapour extraction as well as provides comparison of results using both, prepared and real soils. The main objectives were: (i) to analyse the efficiency and time of remediation according to the water and natural organic matter content of the soil; and (ii) to assess if a previous study, performed using prepared soils, could help to preview the process viability in real conditions. For sandy soils with negligible clay content, artificially contaminated with cyclohexane before vapour extraction, it was concluded that (i) the increase of soil water content and mainly of natural organic matter content influenced negatively the remediation process, making it less efficient, more time consuming, and consequently more expensive; and (ii) a previous study using prepared soils of similar characteristics has proven helpful for previewing the process viability in real conditions.

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 determination of chlorpromazine

New chlorpromazine selective electrodes with a tubular arrangement and no internal reference solution are proposed. Selective membranes are of poly(vinyl chloride) (PVC) with the tetraphenylborate•chlorpromazine (TPB•CPZ) ion-exchanger dissolved in o-nitrophenyl octyl ether (oNPOE). Analytical features of the electrodes were evaluated on a single-channel flow assembly having 500 µl injection volumes and flow-rates of 4.5 ml min−1. For a carrier solution of 3.3×10−3Min sodium sulphate, Nernstian responsewas observed over the concentration range 1.0×10−5 to 1.0×10−2 M. Average slopes were about 59mVdecade−1 and squared correlation coefficients were >0.9984. Slight hiper-Nernstian behaviour was observed in buffer solutions of 4.4 pH; average slopes were of 62.06mVdecade−1. The electrode displayed a good selectivity for CPZ, with respect to, several foreign inorganic and organic species. The selective electrodes were successfully applied to the analysis of pure solutions and pharmaceutical preparations. Proposed method allows the analysis of 84 samples h−1, producing wastewaters of low toxicity. The proposed method offers the advantage of simplicity, accuracy, applicability to coloured and turbid samples, and automation feasibility.

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.

Quais os motivos do insucesso de algumas crianças na aprendizagem musical? Motivação e Flow Theory

Este artigo aborda a natureza da motivação na sua relação com a aprendizagem musical. Um dos objectivos principais é problematizar a questão das diferenças no sucesso da aprendizagem musical quando nos encontramos perante indivíduos com níveis aparentemente semelhantes de capacidade e potencial musicais. Começa por apresentar um conjunto de modelos teóricos que oferecem uma visão acerca das razões que podem explicar as variações e mudanças na motivação. Refere-se investigação recente que sugere que os processos motivacionais não são pré-determinados mas podem ser aprendidos e que os indivíduos, para atingir níveis elevados de sucesso, necessitam de uma focagem no processo por oposição a uma focagem no produto. São introduzidos e explorados processos cognitivos fundamentais relacionados com a aprendizagem musical (por exemplo, comportamento au to-regulado, papel da motivação intrínseca e extrínseca) . Como conclusão, sugerem-se algumas práticas específicas para que os professores possam reflectir acerca da melhor forma de encorajar e aumentar a motivação dos seus alunos para aprender música.

Characterizations of power indices based on null player free winning coalitions

In this paper, we characterize two power indices introduced in [1] using two different modifications of the monotonicity property first stated by [2]. The sets of properties are easily comparable among them and with previous characterizations of other power indices.

Power law and entropy analysis of catastrophic phenomena

Catastrophic events, such as wars and terrorist attacks, tornadoes and hurricanes, earthquakes, tsunamis, floods and landslides, are always accompanied by a large number of casualties. The size distribution of these casualties has separately been shown to follow approximate power law (PL) distributions. In this paper, we analyze the statistical distributions of the number of victims of catastrophic phenomena, in particular, terrorism, and find double PL behavior. This means that the data sets are better approximated by two PLs instead of a single one. We plot the PL parameters, corresponding to several events, and observe an interesting pattern in the charts, where the lines that connect each pair of points defining the double PLs are almost parallel to each other. A complementary data analysis is performed by means of the computation of the entropy. The results reveal relationships hidden in the data that may trigger a future comprehensive explanation of this type of phenomena.

A new MILP based approach for unit commitment in power production planning

This paper presents a complete, quadratic programming formulation of the standard thermal unit commitment problem in power generation planning, together with a novel iterative optimisation algorithm for its solution. The algorithm, based on a mixed-integer formulation of the problem, considers piecewise linear approximations of the quadratic fuel cost function that are dynamically updated in an iterative way, converging to the optimum; this avoids the requirement of resorting to quadratic programming, making the solution process much quicker. From extensive computational tests on a broad set of benchmark instances of this problem, the algorithm was found to be flexible and capable of easily incorporating different problem constraints. Indeed, it is able to tackle ramp constraints, which although very important in practice were rarely considered in previous publications. Most importantly, optimal solutions were obtained for several well-known benchmark instances, including instances of practical relevance, that are not yet known to have been solved to optimality. Computational experiments and their results showed that the method proposed is both simple and extremely effective.

Subacute effects of the thiodicarb pesticide on target organs of male wistar rats: biochemical, histological, and flow cytometry studies

Thiodicarb, a carbamate pesticide widely used on crops, may pose several environmental and health concerns. This study aimed to explore its toxicological profile on male rats using hematological, biochemical, histopathological, and flow cytometry markers. Exposed animals were dosed daily at 10, 20, or 40 mg/kg/body weight (group A, B, and C, respectively) during 30 d. No significant changes were observed in hematological parameters among all groups. After 10 d, a decrease of total cholesterol levels was noted in rats exposed to 40 mg/kg. Aspartate aminotransferase (AST) activity increased (group A at 20 d; groups A and B at 30 d) and alkaline phosphatase (ALP) (group B at 30 d) activity significantly reduced. At 30 d a decrease of some of the other evaluated parameters was observed with total cholesterol and urea levels in group A as well as total protein and creatinine levels in groups A and B. Histological results demonstrated multi-organ dose-related damage in thiodicarb-exposed animals, evidenced as hemorrhagic and diffuse vacuolation in hepatic tissue; renal histology showed disorganized glomeruli and tubular cell degeneration; spleen was ruptured with white pulp and clusters of iron deposits within red pulp; significant cellular loss was noted at the cortex of thymus; and degenerative changes were observed within testis. The histopathologic alterations were most prominent in the high-dose group. Concerning flow cytometry studies, an increase of lymphocyte number, especially T lymphocytes, was seen in blood samples from animals exposed to the highest dose. Taken together, these results indicate marked systemic organ toxicity in rats after subacute exposure to thiodicarb.

Demand response management in power systems using a particle swarm optimization approach

Competitive electricity markets have arisen as a result of power-sector restructuration and power-system deregulation. The players participating in competitive electricity markets must define strategies and make decisions using all the available information and business opportunities.

Characterizing the timing behaviour of power-line communication by means of simulation

Although power-line communication (PLC) is not a new technology, its use to support communication with timing requirements is still the focus of ongoing research. Recently, a new infrastructure was presented, intended for communication using power lines from a central location to geographically dispersed nodes using inexpensive devices. This new infrastructure uses a two-level hierarchical power-line system, together with an IP-based network. Within this infrastructure, in order to provide end-toend communication through the two levels of the powerline system, it is necessary to fully understand the behaviour of the underlying network layers. The masterslave behaviour of the PLC MAC, together with the inherent dynamic topology of power-line networks are important issues that must be fully characterised. Therefore, in this paper we present a simulation model which is being used to study and characterise the behaviour of power-line communication.

A power line communication stack for metering, SCADA and large-scale domotic applications

This paper describes the communication stack of the REMPLI system: a structure using power-lines and IPbased networks for communication, for data acquisition and control of energy distribution and consumption. It is furthermore prepared to use alternative communication media like GSM or analog modem connections. The REMPLI system provides communication service for existing applications, namely automated meter reading, energy billing and domotic applications. The communication stack, consisting of physical, network, transport, and application layer is described as well as the communication services provided by the system. We show how the peculiarities of the power-line communication influence the design of the communication stack, by introducing requirements to efficiently use the limited bandwidth, optimize traffic and implement fair use of the communication medium for the extensive communication partners.

Power Over Ethernet – a solução de vanguarda nas comunicações baseadas em IP

Mal sabia o Italiano Antonio Santi Giuseppe Meucci na segunda metade do século XIX (1870-1876), que a sua invenção iria alcançar um êxito sem precedente e que mudaria por completo o estilo de vida das gerações vindouras: o “Telettrofono” (telégrafo falante). Porém, e por necessidade, acabou por vender o protótipo e seus respetivos direitos, a Alexander Graham Bell, o qual ficou historicamente conhecido como o inventor do telefone. Com efeito, o telefone quase que dispensa apresentação. É um dispositivo de telecomunicações que entrou paulatinamente nas vidas das pessoas, seja no lazer, no exercícios das suas profissões, em situações de emergência, em teatro de guerra, num infindável número de situações, e que foi simplesmente planeado para transmitir sons por meio de sinais elétricos em condutores próprios para o efeito (vias telefónicas). Por definição, é um aparelho eletroacústico que permite a transformação, no ponto emissor, de energia acústica em energia elétrica e, no ponto recetor, a transformação da energia elétrica em acústica, permitindo assim a troca de informações (falada e ouvida) entre dois ou mais assinantes. Ora, a ideia de Power over Ethernet (PoE) teve, forçosamente, seu marco nos finais do século XIX, quando Alexander Bell (“Bell Telephone Company”) teve de refletir/decidir se o telefone a instalar em cada residência, seria alimentado localmente por uma bateria (fonte de energia local), ou se deveria alimentar cada dispositivo telefónico remotamente através de fios condutores. Esta é a noção de Power over Ethernet na sua vanguarda de aplicação no início do século XXI, e objeto de uma breve apresentação, à qual o convido à leitura das restantes secções.