Quantification of endocrine disruptors and pesticides in water by gas chromatography–tandem mass spectrometry. Method validation using weighted linear regression schemes

Amulti-residue methodology based on a solid phase extraction followed by gas chromatography–tandem mass spectrometry was developed for trace analysis of 32 compounds in water matrices, including estrogens and several pesticides from different chemical families, some of them with endocrine disrupting properties. Matrix standard calibration solutions were prepared by adding known amounts of the analytes to a residue-free sample to compensate matrix-induced chromatographic response enhancement observed for certain pesticides. Validation was done mainly according to the International Conference on Harmonisation recommendations, as well as some European and American validation guidelines with specifications for pesticides analysis and/or GC–MS methodology. As the assumption of homoscedasticity was not met for analytical data, weighted least squares linear regression procedure was applied as a simple and effective way to counteract the greater influence of the greater concentrations on the fitted regression line, improving accuracy at the lower end of the calibration curve. The method was considered validated for 31 compounds after consistent evaluation of the key analytical parameters: specificity, linearity, limit of detection and quantification, range, precision, accuracy, extraction efficiency, stability and robustness.

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.

Espetroscopia (1H) por ressonância magnética do disco intervertebral lombar no adulto e sua aplicação na rotina imagiológica

Objetivos – Demonstrar o potencial da espetroscopia (1H) por ressonância magnética na doença degenerativa discal lombar e defender a integração desta técnica na rotina clínico‑imagiológica para a precisa classificação da involução vs degenerescência dos discos L4‑L5 e L5‑S1 em doentes com lombalgia não relacionável com causa mecânica. Material e métodos – O estudo incluiu 102 discos intervertebrais lombares de 123 doentes. Foram estudados 61 discos de L4‑L5, 41 discos de L5‑S1 e 34 discos de D12‑L1. Utilizou‑se um sistema de ressonância magnética de 1,5 T e técnica monovoxel. Obtiveram‑se os rácios [Lac/Nacetyl] e [Nacetyl/(Lac+Lípidos)] e aplicou‑se a ressonância de lípidos para avaliar a bioquímica do disco com o fim de conhecer o estado de involução vs degenerescência que o suscetibilizam para a instabilidade e sobrecarga. Avaliou‑se o comportamento dos rácios e do teor lipídico dos discos L4‑L5‑S1 e as diferenças apresentadas em relação a D12‑L1. Foi também realizada a comparação entre os discos L4‑L5, L5‑S1 e D12‑L1 na ponderação T2 (T2W), segundo a classificação ajustada (1‑4) de Pfirrmann. Resultados – Verificou‑se que os rácios e o valor dos lípidos dos discos L4‑L5‑S1 apresentaram diferenças estatisticamente significativas quando relacionados com os discos D12‑L1. O rácio [Lac/Nacetyl] em L4‑L5‑S1 mostrou‑se aumentado em relação a D12‑L1 (p=0,033 para os discos com grau de involução [1+2] e p=0,004 para os discos com grau [3+4]). Estes resultados sugerem que a involução vs degenerescência dos discos nos graus mais elevados condiciona um decréscimo do pico do Lactato. O rácio [Nacetyl/(Lac+Lip)] discrimina os graus de involução [1+2] do [3+4] no nível L4‑L5, apresentando os valores dos rácios (média 0,65 e 0,5 respetivamente com p=0,04). O rácio médio de [Nacetyl/(Lac+Lip)] dos discos L4‑L5 foi 1,8 vezes mais elevado do que em D12‑L1. O espetro lipídico em L4‑L5‑S1 nos graus mais elevados não mostrou ter uma prevalência constante quanto às frequências de ressonância. Conclusão – A espetroscopia (1H) dos discos intervertebrais poderá ter aplicação na discriminação dos graus de involução vs degenerescência e representar um contributo semiológico importante em suplemento à ponderação T2 convencional. As ressonâncias de lípidos dos discos L4‑L5 e L5‑S1, involuídos ou degenerados, devem ser avaliadas em relação a D12‑L1, utilizando este valor como referência, pois este último é o nível considerado estável e com baixa probabilidade de degenerescência.

Técnicas de rating em contexto de crise no setor bancário português

Dissertação para a obtenção do Grau de Mestre em Contabilidade e Finanças Orientador: Mestre Adalmiro Álvaro Malheiro de Castro Andrade Pereira

Development of a simple analytical method for the simultaneousdetermination of paracetamol, paracetamol-glucuronide andp-aminophenol in river water

Paracetamol is among the most worldwide consumed pharmaceuticals. Although its occurrence in the environment is well documented, data about the presence of its metabolites and transformation products is very scarce. The present work describes the development of an analytical method for the simultaneous determination of paracetamol, its principal metabolite (paracetamol-glucuronide) and its main transformation product (p-aminophenol) based on solid phase extraction (SPE) and high performance liquid chromatography coupled to diode array detection (HPLC-DAD). The method was applied to analysis of river waters, showing to be suitable to be used in routine analysis. Different SPE sorbents were compared and the use of two Oasis WAX cartridges in tandem proved to be the most adequate approach for sample clean up and pre-concentration. Under optimized conditions, limits of detection in the range 40–67 ng/L were obtained, as well as mean recoveries between 60 and 110% with relative standard deviations (RSD) below 6%. Finally, the developed SPE-HPLC/DAD method was successfully applied to the analysis of the selected compounds in samples from seven rivers located in the north of Portugal. Nevertheless all the compounds were detected, it was the first time that paracetamol-glucuronide was found in river water at concentrations up to 3.57 μg/L.

Tensile behaviour of a structural adhesive at high temperatures by the extended finite element method

Component joining is typically performed by welding, fastening, or adhesive-bonding. For bonded aerospace applications, adhesives must withstand high-temperatures (200°C or above, depending on the application), which implies their mechanical characterization under identical conditions. The extended finite element method (XFEM) is an enhancement of the finite element method (FEM) that can be used for the strength prediction of bonded structures. This work proposes and validates damage laws for a thin layer of an epoxy adhesive at room temperature (RT), 100, 150, and 200°C using the XFEM. The fracture toughness (G Ic ) and maximum load ( ); in pure tensile loading were defined by testing double-cantilever beam (DCB) and bulk tensile specimens, respectively, which permitted building the damage laws for each temperature. The bulk test results revealed that decreased gradually with the temperature. On the other hand, the value of G Ic of the adhesive, extracted from the DCB data, was shown to be relatively insensitive to temperature up to the glass transition temperature (T g ), while above T g (at 200°C) a great reduction took place. The output of the DCB numerical simulations for the various temperatures showed a good agreement with the experimental results, which validated the obtained data for strength prediction of bonded joints in tension. By the obtained results, the XFEM proved to be an alternative for the accurate strength prediction of bonded structures.

Queuing and routing in a hierarchical powerline communication system

Although power-line communication (PLC) is not a new technology, its use to support data communication with timing requirements is still the focus of ongoing research. A new infrastructure intended for communication using power lines from a central location to dispersed nodes using inexpensive devices was presented recently. This new infrastructure uses a two-level hierarchical power-line system, together with an IP-based network. Due to the master-slave behaviour of the PLC medium access, together with the inherent dynamic topology of power-line networks, a mechanism to provide end-to-end communication through the two levels of the power-line system must be provided. In this paper we introduce the architecture of the PLC protocol layer that is being implemented for this end.

A preliminary idea for an 8-competitive, log2 DMAX + log2 log2 1/U asymptotic-space, interface generation algorithm for two-level hierarchical scheduling of constrained-deadline sporadic tasks on a uniprocessor

Consider a single processor and a software system. The software system comprises components and interfaces where each component has an associated interface and each component comprises a set of constrained-deadline sporadic tasks. A scheduling algorithm (called global scheduler) determines at each instant which component is active. The active component uses another scheduling algorithm (called local scheduler) to determine which task is selected for execution on the processor. The interface of a component makes certain information about a component visible to other components; the interfaces of all components are used for schedulability analysis. We address the problem of generating an interface for a component based on the tasks inside the component. We desire to (i) incur only a small loss in schedulability analysis due to the interface and (ii) ensure that the amount of space (counted in bits) of the interface is small; this is because such an interface hides as much details of the component as possible. We present an algorithm for generating such an interface.

Analysis of temperature time-series: embedding dynamics into the MDS method

Global warming and the associated climate changes are being the subject of intensive research due to their major impact on social, economic and health aspects of the human life. Surface temperature time-series characterise Earth as a slow dynamics spatiotemporal system, evidencing long memory behaviour, typical of fractional order systems. Such phenomena are difficult to model and analyse, demanding for alternative approaches. This paper studies the complex correlations between global temperature time-series using the Multidimensional scaling (MDS) approach. MDS provides a graphical representation of the pattern of climatic similarities between regions around the globe. The similarities are quantified through two mathematical indices that correlate the monthly average temperatures observed in meteorological stations, over a given period of time. Furthermore, time dynamics is analysed by performing the MDS analysis over slices sampling the time series. MDS generates maps describing the stations’ locus in the perspective that, if they are perceived to be similar to each other, then they are placed on the map forming clusters. We show that MDS provides an intuitive and useful visual representation of the complex relationships that are present among temperature time-series, which are not perceived on traditional geographic maps. Moreover, MDS avoids sensitivity to the irregular distribution density of the meteorological stations.

Real-time tracking and reporting of dynamic events in hierarchical wireless sensor networks

Wireless Sensor Networks (WSNs) are highly distributed systems in which resource allocation (bandwidth, memory) must be performed efficiently to provide a minimum acceptable Quality of Service (QoS) to the regions where critical events occur. In fact, if resources are statically assigned independently from the location and instant of the events, these resources will definitely be misused. In other words, it is more efficient to dynamically grant more resources to sensor nodes affected by critical events, thus providing better network resource management and reducing endto- end delays of event notification and tracking. In this paper, we discuss the use of a WSN management architecture based on the active network management paradigm to provide the real-time tracking and reporting of dynamic events while ensuring efficient resource utilization. The active network management paradigm allows packets to transport not only data, but also program scripts that will be executed in the nodes to dynamically modify the operation of the network. This presumes the use of a runtime execution environment (middleware) in each node to interpret the script. We consider hierarchical (e.g. cluster-tree, two-tiered architecture) WSN topologies since they have been used to improve the timing performance of WSNs as they support deterministic medium access control protocols.

Ill-defined causes of death in Brazil: a redistribution method based on the investigation of such causes

OBJECTIVE To propose a method of redistributing ill-defined causes of death (IDCD) based on the investigation of such causes.METHODS In 2010, an evaluation of the results of investigating the causes of death classified as IDCD in accordance with chapter 18 of the International Classification of Diseases (ICD-10) by the Mortality Information System was performed. The redistribution coefficients were calculated according to the proportional distribution of ill-defined causes reclassified after investigation in any chapter of the ICD-10, except for chapter 18, and used to redistribute the ill-defined causes not investigated and remaining by sex and age. The IDCD redistribution coefficient was compared with two usual methods of redistribution: a) Total redistribution coefficient, based on the proportional distribution of all the defined causes originally notified and b) Non-external redistribution coefficient, similar to the previous, but excluding external causes.RESULTS Of the 97,314 deaths by ill-defined causes reported in 2010, 30.3% were investigated, and 65.5% of those were reclassified as defined causes after the investigation. Endocrine diseases, mental disorders, and maternal causes had a higher representation among the reclassified ill-defined causes, contrary to infectious diseases, neoplasms, and genitourinary diseases, with higher proportions among the defined causes reported. External causes represented 9.3% of the ill-defined causes reclassified. The correction of mortality rates by the total redistribution coefficient and non-external redistribution coefficient increased the magnitude of the rates by a relatively similar factor for most causes, contrary to the IDCD redistribution coefficient that corrected the different causes of death with differentiated weights.CONCLUSIONS The proportional distribution of causes among the ill-defined causes reclassified after investigation was not similar to the original distribution of defined causes. Therefore, the redistribution of the remaining ill-defined causes based on the investigation allows for more appropriate estimates of the mortality risk due to specific causes.

A straightforward method to obtain the cohesive laws of bonded joints under mode I loading

A simple procedure to measure the cohesive laws of bonded joints under mode I loading using the double cantilever beam test is proposed. The method only requires recording the applied load–displacement data and measuring the crack opening displacement at its tip in the course of the experimental test. The strain energy release rate is obtained by a procedure involving the Timoshenko beam theory, the specimen’s compliance and the crack equivalent concept. Following the proposed approach the influence of the fracture process zone is taken into account which is fundamental for an accurate estimation of the failure process details. The cohesive law is obtained by differentiation of the strain energy release rate as a function of the crack opening displacement. The model was validated numerically considering three representative cohesive laws. Numerical simulations using finite element analysis including cohesive zone modeling were performed. The good agreement between the inputted and resulting laws for all the cases considered validates the model. An experimental confirmation was also performed by comparing the numerical and experimental load–displacement curves. The numerical load–displacement curves were obtained by adjusting typical cohesive laws to the ones measured experimentally following the proposed approach and using finite element analysis including cohesive zone modeling. Once again, good agreement was obtained in the comparisons thus demonstrating the good performance of the proposed methodology.

Improvement of a filters method in a derivative free optimization

Constraints nonlinear optimization problems can be solved using penalty or barrier functions. This strategy, based on solving the problems without constraints obtained from the original problem, have shown to be e ective, particularly when used with direct search methods. An alternative to solve the previous problems is the lters method. The lters method introduced by Fletcher and Ley er in 2002, , has been widely used to solve problems of the type mentioned above. These methods use a strategy di erent from the barrier or penalty functions. The previous functions de ne a new one that combine the objective function and the constraints, while the lters method treat optimization problems as a bi-objective problems that minimize the objective function and a function that aggregates the constraints. Motivated by the work of Audet and Dennis in 2004, using lters method with derivative-free algorithms, the authors developed works where other direct search meth- ods were used, combining their potential with the lters method. More recently. In a new variant of these methods was presented, where it some alternative aggregation restrictions for the construction of lters were proposed. This paper presents a variant of the lters method, more robust than the previous ones, that has been implemented with a safeguard procedure where values of the function and constraints are interlinked and not treated completely independently.

Filters method in direct search optimization, new measures to admissibility

Constrained nonlinear optimization problems are usually solved using penalty or barrier methods combined with unconstrained optimization methods. Another alternative used to solve constrained nonlinear optimization problems is the lters method. Filters method, introduced by Fletcher and Ley er in 2002, have been widely used in several areas of constrained nonlinear optimization. These methods treat optimization problem as bi-objective attempts to minimize the objective function and a continuous function that aggregates the constraint violation functions. Audet and Dennis have presented the rst lters method for derivative-free nonlinear programming, based on pattern search methods. Motivated by this work we have de- veloped a new direct search method, based on simplex methods, for general constrained optimization, that combines the features of the simplex method and lters method. This work presents a new variant of these methods which combines the lters method with other direct search methods and are proposed some alternatives to aggregate the constraint violation functions.

Supplier's selection model based on an empirical study

The problem of selecting suppliers/partners is a crucial and important part in the process of decision making for companies that intend to perform competitively in their area of activity. The selection of supplier/partner is a time and resource-consuming task that involves data collection and a careful analysis of the factors that can positively or negatively influence the choice. Nevertheless it is a critical process that affects significantly the operational performance of each company. In this work, there were identified five broad selection criteria: Quality, Financial, Synergies, Cost, and Production System. Within these criteria, it was also included five sub-criteria. After the identification criteria, a survey was elaborated and companies were contacted in order to understand which factors have more weight in their decisions to choose the partners. Interpreted the results and processed the data, it was adopted a model of linear weighting to reflect the importance of each factor. The model has a hierarchical structure and can be applied with the Analytic Hierarchy Process (AHP) method or Value Analysis. The goal of the paper it's to supply a selection reference model that can represent an orientation/pattern for a decision making on the suppliers/partners selection process