Microscopic Theory of Anchoring Transitions at the Surfaces of Pure Liquid-Crystals and their Mixtures .1. The Fowler Approximation

We have generalized earlier work on anchoring of nematic liquid crystals by Sullivan, and Sluckin and Poniewierski, in order to study transitions which may occur in binary mixtures of nematic liquid crystals as a function of composition. Microscopic expressions have been obtained for the anchoring energy of (i) a liquid crystal in contact with a solid aligning surface; (ii) a liquid crystal in contact with an immiscible isotropic medium; (iii) a liquid crystal mixture in contact with a solid aligning surface. For (iii), possible phase diagrams of anchoring angle versus dopant concentration have been calculated using a simple liquid crystal model. These exhibit some interesting features including re-entrant conical anchoring, for what are believed to be realistic values of the molecular parameters. A way of relaxing the most drastic approximation implicit in the above approach is also briefly discussed.

Simulation and theory of hybrid aligned liquid crystal films

We present a study of the effects of nanoconfinement on a system of hard Gaussian overlap particles interacting with planar substrates through the hard-needle-wall potential, extending earlier work by two of us [D. J. Cleaver and P. I. C. Teixeira, Chem. Phys. Lett. 338, 1 (2001)]. Here, we consider the case of hybrid films, where one of the substrates induces strongly homeotropic anchoring, while the other favors either weakly homeotropic or planar anchoring. These systems are investigated using both Monte Carlo simulation and density-functional theory, the latter implemented at the level of Onsager's second-virial approximation with Parsons-Lee rescaling. The orientational structure is found to change either continuously or discontinuously depending on substrate separation, in agreement with earlier predictions by others. The theory is seen to perform well in spite of its simplicity, predicting the positional and orientational structure seen in simulations even for small particle elongations.

Square-wave voltametric method for determination of molinate concentration in a biological process using a hanging mercury drop electrode

A square-wave voltammetric (SWV) method using a hanging mercury drop electrode (HMDE) has been developed for determination of the herbicide molinate in a biodegradation process. The method is based on controlled adsorptive accumulation of molinate for 10 s at a potential of -0.8 V versus AgCl/Ag. An anodic peak, due to oxidation of the adsorbed pesticide, was observed in the cyclic voltammogram at ca. -0.320 V versus AgCl/Ag; a very small cathodic peak was also detected. The SWV calibration plot was established to be linear in the range 5.0x10-6 to 9.0x10-6 mol L-1; this corresponded to a detection limit of 3.5x10-8 mol L-1. This electroanalytical method was used to monitor the decrease of molinate concentration in river waters along a biodegradation process using a bacterial mixed culture. The results achieved with this voltammetric method were compared with those obtained by use of a chromatographic method (HPLC–UV) and no significant statistical differences were observed.

A class of singular first order differential equations with applications in reaction-diffusion

Agências Financiadoras: FCT e MIUR

Square-wave adsorptive-stripping voltammetric detection in the quality control of fluoxetine

Electroanalytical methods based on square-wave adsorptive-stripping voltammetry (SWAdSV) and flow-injection analysis with square-wave adsorptive-stripping voltammetric detection (FIA-SWAdSV) were developed for the determination of fluoxetine (FXT). The methods were based on the reduction of FXT at a mercury drop electrode at -1.2 V versus Ag/AgCl, in a phosphate buffer of pH 12.0, and on the possibility of accumulating the compound at the electrode surface. The SWAdSV method was successfully applied in the quantification of FXT in pharmaceutical products, human serum samples, and in drug dissolution studies. Because the presence of dissolved oxygen did not interfere significantly with the analysis, it was possible to quantify FXT in several pharmaceutical products using FIA-SWAdSV. This method enables analysis of up to 120 samples per hour at reduced costs.

Determination of ametryn in soils via microwave-assisted solvent extraction coupled to anodic stripping voltammetry with a gold ultramicroelectrode

An extraction-anodic adsorptive stripping voltammetric procedure using microwave-assisted solvent extraction and a gold ultramicroelectrode was developed for determining the pesticide ametryn in soil samples. The method is based on the use of acetonitrile as extraction solvent and on controlled adsorptive accumulation of the herbicide at the potential of 0.50 V (vs. Ag/AgCl) in the presence of Britton-Robinson buffer (pH 3.3). Soil sample extracts were analysed directly after drying and redissolution with the supporting electrolyte but without other pre-treatment. The limit of detection obtained for a 10 s collection time was 0.021 µg g-1. Recovery experiments for the global procedure, at the 0.500 µg g-1 level, gave satisfactory mean and standard deviation results which were comparable to those obtained by HPLC with UV detection.

Electroanalytical study of the pesticide asulam

The electrochemical behaviour of the herbicide Asulam was studied by cyclic and square wave voltammetry. Asulam may be irreversibly oxidised at a glassy carbon electrode. Maximum currents were obtained at pH=1.9 in aqueous electrolyte solution. Based on the electrochemical behaviour of Asulam, two analytical methodologies were developed for its determination in water samples, using square wave voltammetry (SWV) and flow injection analysis (FIA) coupled with an amperometric detector. Limits of detection of 7.1x10-6 mol L-1 and 1.2x10-8 mol L-1 for SWV and FIA respectively, were achieved. Repeatability was calculated by assessing the relative standard deviation (%) for 10 consecutive determinations of one sample. The found values were 2.1% for SWV and 5.0% for FIA. Validation of the results provided by SWV and FIA methodologies was performed by comparison with results from an HPLC-DAD technique. Good relative deviations were found (<5%). Recovery trials were performed to assess the accuracy of the results and the obtained values were between 84% and 107% for both methods.

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.

Weaving encounters: towards an art of participation

In the early 21st Century, with the phenomenon of digital convergence, the consecration of Web 2.0, the decrease of the cost of cameras and video recorders, the proliferation of mobile phones, laptops and wireless technologies, we witness the arising of a new wave of media, of an informal, personal and at times “minority” nature, facilitating social networks, a culture of fans, of sharing and remix. As digital networks become fully and deeply intricate in our experience, the idea of “participation” arises as one of the most complex and controversial themes of the contemporary critical discourse, namely in what concerns contemporary art and new media art. However, the idea of “participation” as a practice or postulate traverses the 20th century art playing an essential role in its auto-critic, in questioning the concept of author, and in the dilution of the frontiers between art, “life” and society, emphasizing the process, the everyday and a community sense. As such, questioning the new media art in light of a “participatory art” (Frieling, 2008) invokes a double gaze simultaneously attentive to the emerging figures of a “participatory aesthetics” in digital arts and of the genealogy in which it is included. In fact, relating the new media art with the complex and paradoxical phenomenon of “participation” allows us to, on the one hand, avoid “digital formalism” (Lovink, 2008) and analyse the relations between digital art and contemporary social movements; on the other hand, this angle of analysis contributes to reinforce the dialogue and the links between digital art and contemporary art, questioning the alleged frontiers that separate them.

Optimization of QuEChERS procedure coupled to GC-ECD for organochlorine pesticide determination in carrot samples

An optimised version of the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for simultaneous determination of 14 organochlorine pesticides in carrots was developed using gas chromatography coupled with electron-capture detector (GC-ECD) and confirmation by gas chromatography tandem mass spectrometry (GC-MS/MS). A citrate-buffered version of QuEChERS was applied for the extraction of the organochlorine pesticides, and for the extract clean-up, primary secondary amine, octadecyl-bonded silica (C18), magnesium sulphate (MgSO4) and graphitized carbon black were used as sorbents. The GC-ECD determination of the target compounds was achieved in less than 20 min. The limits of detection were below the EUmaximum residue limits (MRLs) for carrots, 10–50 μg kg−1, while the limit of quantification did exceed 10 μg kg−1 for hexachlorobenzene (HCB). The introduction of a sonication step was shown to improve the recoveries. The overall average recoveries in carrots, at the four tested levels (60, 80, 100 and 140 μg kg−1), ranged from 66 to 111% with relative standard deviations in the range of 2– 15 % (n03) for all analytes, with the exception of HCB. The method has been applied to the analysis of 21 carrot samples from different Portuguese regions, and β-HCH was the pesticide most frequently found, with concentrations oscillating between less than the limit of quantification to 14.6 μg kg−1. Only one sample had a pesticide residue (β-HCH) above the MRL, 14.6 μg kg−1. This methodology combines the advantages of both QuEChERS and GC-ECD, producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Determination of ochratoxin A in bread: evaluation of microwave-assisted extraction using an orthogonal composite design coupled with response surface methodology

An analytical method using microwave-assisted extraction (MAE) and liquid chromatography (LC) with fluorescence detection (FD) for the determination of ochratoxin A (OTA) in bread samples is described. A 24 orthogonal composite design coupled with response surface methodology was used to study the influence of MAE parameters (extraction time, temperature, solvent volume, and stirring speed) in order to maximize OTA recovery. The optimized MAE conditions were the following: 25 mL of acetonitrile, 10 min of extraction, at 80 °C, and maximum stirring speed. Validation of the overall methodology was performed by spiking assays at five levels (0.1–3.00 ng/g). The quantification limit was 0.005 ng/g. The established method was then applied to 64 bread samples (wheat, maize, and wheat/maize bread) collected in Oporto region (Northern Portugal). OTAwas detected in 84 % of the samples with a maximum value of 2.87 ng/g below the European maximum limit established for OTA in cereal products of 3 ng/g.

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.

Local fractional variational iteration and decomposition methods for wave equation on cantor sets within local fractional operators

We perform a comparison between the fractional iteration and decomposition methods applied to the wave equation on Cantor set. The operators are taken in the local sense. The results illustrate the significant features of the two methods which are both very effective and straightforward for solving the differential equations with local fractional derivative.

Towards a Unified Theory of Health-Disease: I. Health as a complex model-object

Theory building is one of the most crucial challenges faced by basic, clinical and population research, which form the scientific foundations of health practices in contemporary societies. The objective of the study is to propose a Unified Theory of Health-Disease as a conceptual tool for modeling health-disease-care in the light of complexity approaches. With this aim, the epistemological basis of theoretical work in the health field and concepts related to complexity theory as concerned to health problems are discussed. Secondly, the concepts of model-object, multi-planes of occurrence, modes of health and disease-illness-sickness complex are introduced and integrated into a unified theoretical framework. Finally, in the light of recent epistemological developments, the concept of Health-Disease-Care Integrals is updated as a complex reference object fit for modeling health-related processes and phenomena.

An implicit GTS allocation mechanism in IEEE 802.15.4 for time-sensitive wireless sensor networks: theory and practice

Timeliness guarantee is an important feature of the recently standardized IEEE 802.15.4 protocol, turning it quite appealing for Wireless Sensor Network (WSN) applications under timing constraints. When operating in beacon-enabled mode, this protocol allows nodes with real-time requirements to allocate Guaranteed Time Slots (GTS) in the contention-free period. The protocol natively supports explicit GTS allocation, i.e. a node allocates a number of time slots in each superframe for exclusive use. The limitation of this explicit GTS allocation is that GTS resources may quickly disappear, since a maximum of seven GTSs can be allocated in each superframe, preventing other nodes to benefit from guaranteed service. Moreover, the GTS may be underutilized, resulting in wasted bandwidth. To overcome these limitations, this paper proposes i-GAME, an implicit GTS Allocation Mechanism in beacon-enabled IEEE 802.15.4 networks. The allocation is based on implicit GTS allocation requests, taking into account the traffic specifications and the delay requirements of the flows. The i-GAME approach enables the use of one GTS by multiple nodes, still guaranteeing that all their (delay, bandwidth) requirements are satisfied. For that purpose, we propose an admission control algorithm that enables to decide whether to accept a new GTS allocation request or not, based not only on the remaining time slots, but also on the traffic specifications of the flows, their delay requirements and the available bandwidth resources. We show that our approach improves the bandwidth utilization as compared to the native explicit allocation mechanism defined in the IEEE 802.15.4 standard. We also present some practical considerations for the implementation of i-GAME, ensuring backward compatibility with the IEEE 801.5.4 standard with only minor add-ons. Finally, an experimental evaluation on a real system that validates our theoretical analysis and demonstrates the implementation of i-GAME is also presented