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.

Experimental design methodologies for the identification of Michaelis-Menten type kinetics

The main objective of this work was to investigate the application of experimental design techniques for the identification of Michaelis-Menten kinetic parameters. More specifically, this study attempts to elucidate the relative advantages/disadvantages of employing complex experimental design techniques in relation to equidistant sampling when applied to different reactor operation modes. All studies were supported by simulation data of a generic enzymatic process that obeys to the Michaelis-Menten kinetic equation. Different aspects were investigated, such as the influence of the reactor operation mode (batch, fed-batch with pulse wise feeding and fed-batch with continuous feeding) and the experimental design optimality criteria on the effectiveness of kinetic parameters identification. The following experimental design optimality criteria were investigated: 1) minimization of the sum of the diagonal of the Fisher information matrix (FIM) inverse (A-criterion), 2) maximization of the determinant of the FIM (D-criterion), 3) maximization of the smallest eigenvalue of the FIM (E-criterion) and 4) minimization of the quotient between the largest and the smallest eigenvalue (modified E-criterion). The comparison and assessment of the different methodologies was made on the basis of the Cramér-Rao lower bounds (CRLB) error in respect to the parameters vmax and Km of the Michaelis-Menten kinetic equation. In what concerns the reactor operation mode, it was concluded that fed-batch (pulses) is better than batch operation for parameter identification. When the former operation mode is adopted, the vmax CRLB error is lowered by 18.6 % while the Km CRLB error is lowered by 26.4 % when compared to the batch operation mode. Regarding the optimality criteria, the best method was the A-criterion, with an average vmax CRLB of 6.34 % and 5.27 %, for batch and fed-batch (pulses), respectively, while presenting a Km’s CRLB of 25.1 % and 18.1 %, for batch and fed-batch (pulses), respectively. As a general conclusion of the present study, it can be stated that experimental design is justified if the starting parameters CRLB errors are inferior to 19.5 % (vmax) and 45% (Km), for batch processes, and inferior to 42 % and to 50% for fed-batch (pulses) process. Otherwise equidistant sampling is a more rational decision. This conclusion clearly supports that, for fed-batch operation, the use of experimental design is likely to largely improve the identification of Michaelis-Menten kinetic parameters.

Estimação de cobertura rádio em GSM-R através de redes neuronais

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia de Eletrónica e Telecomunicações

A ingerência do conhecimento explícito no conhecimento tácito: a técnica Alexander e a prática e ensino da flauta

Doutoramento em Música

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.

Reabilitação de um imóvel industrial em Marvila: projeto de investimento

Trabalho de Projeto para obtenção do grau de Mestre em Engenharia Civil

Socioeconomic inequality in catastrophic health expenditure in Brazil

OBJECTIVE To analyze the evolution of catastrophic health expenditure and the inequalities in such expenses, according to the socioeconomic characteristics of Brazilian families.METHODS Data from the National Household Budget 2002-2003 (48,470 households) and 2008-2009 (55,970 households) were analyzed. Catastrophic health expenditure was defined as excess expenditure, considering different methods of calculation: 10.0% and 20.0% of total consumption and 40.0% of the family’s capacity to pay. The National Economic Indicator and schooling were considered as socioeconomic characteristics. Inequality measures utilized were the relative difference between rates, the rates ratio, and concentration index.RESULTS The catastrophic health expenditure varied between 0.7% and 21.0%, depending on the calculation method. The lowest prevalences were noted in relation to the capacity to pay, while the highest, in relation to total consumption. The prevalence of catastrophic health expenditure increased by 25.0% from 2002-2003 to 2008-2009 when the cutoff point of 20.0% relating to the total consumption was considered and by 100% when 40.0% or more of the capacity to pay was applied as the cut-off point. Socioeconomic inequalities in the catastrophic health expenditure in Brazil between 2002-2003 and 2008-2009 increased significantly, becoming 5.20 times higher among the poorest and 4.17 times higher among the least educated.CONCLUSIONS There was an increase in catastrophic health expenditure among Brazilian families, principally among the poorest and those headed by the least-educated individuals, contributing to an increase in social inequality.

Energy and delay trade-off of the GTS allocation mechanism in IEEE 802.15.4 for wireless sensor networks

The IEEE 802.15.4 protocol proposes a flexible communication solution for Low-Rate Wireless Personal Area Networks (LR-WPAN) including wireless sensor networks (WSNs). It presents the advantage to fit different requirements of potential applications by adequately setting its parameters. When in beaconenabled mode, the protocol can provide timeliness guarantees by using its Guaranteed Time Slot (GTS) mechanism. However, power-efficiency and timeliness guarantees are often two antagonistic requirements in wireless sensor networks. The purpose of this paper is to analyze and propose a methodology for setting the relevant parameters of IEEE 802.15.4-compliant WSNs that takes into account a proper trade-off between power-efficiency and delay bound guarantees. First, we propose two accurate models of service curves for a GTS allocation as a function of the IEEE 802.15.4 parameters, using Network Calculus formalism. We then evaluate the delay bound guaranteed by a GTS allocation and express it as a function of the duty cycle. Based on the relation between the delay requirement and the duty cycle, we propose a power-efficient superframe selection method that simultaneously reduces power consumption and enables meeting the delay requirements of real-time flows allocating GTSs. The results of this work may pave the way for a powerefficient management of the GTS mechanism in an IEEE 802.15.4 cluster.

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.

Neighbour list optimization for real LTE radio network

With the increasing complexity of current networks, it became evident the need for Self-Organizing Networks (SON), which aims to automate most of the associated radio planning and optimization tasks. Within SON, this paper aims to optimize the Neighbour Cell List (NCL) for Long Term Evolution (LTE) evolved NodeBs (eNBs). An algorithm composed by three decisions were were developed: distance-based, Radio Frequency (RF) measurement-based and Handover (HO) stats-based. The distance-based decision, proposes a new NCL taking account the eNB location and interference tiers, based in the quadrants method. The last two algorithms consider signal strength measurements and HO statistics, respectively; they also define a ranking to each eNB and neighbour relation addition/removal based on user defined constraints. The algorithms were developed and implemented over an already existent radio network optimization professional tool. Several case studies were produced using real data from a Portuguese LTE mobile operator. © 2014 IEEE.

Feasibility of the extended finite element method for the simulation of composite bonded joints

Adhesive-bonding for the unions in multi-component structures is gaining momentum over welding, riveting and fastening. It is vital for the design of bonded structures the availability of accurate damage models, to minimize design costs and time to market. Cohesive Zone Models (CZM’s) have been used for fracture prediction in structures. The eXtended Finite Element Method (XFEM) is a recent improvement of the Finite Element Method (FEM) that relies on traction-separation laws similar to those of CZM’s but it allows the growth of discontinuities within bulk solids along an arbitrary path, by enriching degrees of freedom. This work proposes and validates a damage law to model crack propagation in a thin layer of a structural epoxy adhesive using the XFEM. The fracture toughness in pure mode I (GIc) and tensile cohesive strength (sn0) were defined by Double-Cantilever Beam (DCB) and bulk tensile tests, respectively, which permitted to build the damage law. The XFEM simulations of the DCB tests accurately matched the experimental load-displacement (P-d) curves, which validated the analysis procedure.