Development of electrochemical methods for determination of tramadol - analytical application to pharmaceutical dosage forms

A square-wave voltammetric (SWV) method and a flow injection analysis system with amperometric detection were developed for the determination of tramadol hydrochloride. The SWV method enables the determination of tramadol over the concentration range of 15-75 µM with a detection limit of 2.2 µM. Tramadol could be determined in concentrations between 9 and 50 µM at a sampling rate of 90 h-1, with a detection limit of 1.7 µM using the flow injection system. The electrochemical methods developed were successfully applied to the determination of tramadol in pharmaceutical dosage forms, without any pre-treatment of the samples. Recovery trials were performed to assess the accuracy of the results; the values were between 97 and 102% for both methods.

Celiac disease diagnosis and gluten-free food analytical control

Celiac disease (CD) is an autoimmune enteropathy, characterized by an inappropriate T-cell-mediated immune response to the ingestion of certain dietary cereal proteins in genetically susceptible individuals. This disorder presents environmental, genetic, and immunological components. CD presents a prevalence of up to 1% in populations of European ancestry, yet a high percentage of cases remain underdiagnosed. The diagnosis and treatment should be made early since untreated disease causes growth retardation and atypical symptoms, like infertility or neurological disorders. The diagnostic criteria for CD, which requires endoscopy with small bowel biopsy, have been changing over the last few decades, especially due to the advent of serological tests with higher sensitivity and specificity. The use of serological markers can be very useful to rule out clinical suspicious cases and also to help monitor the patients, after adherence to a gluten-free diet. Since the current treatment consists of a life-long glutenfree diet, which leads to significant clinical and histological improvement, the standardization of an assay to assess in an unequivocal way gluten in gluten-free foodstuff is of major importance.

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.

Comparação entre o pencil beam convolution algorithm e o analytical anisotropic algorithm em tumores de mama

Objectivo do estudo: comparar o desempenho dos algoritmos Pencil Beam Convolution (PBC) e do Analytical Anisotropic Algorithm (AAA) no planeamento do tratamento de tumores de mama com radioterapia conformacional a 3D.

analytical model and measurements of the target erosion depth profile of balanced and unbalanced planar magnetron cathodes

The erosion depth profile of planar targets in balanced and unbalanced magnetron cathodes with cylindrical symmetry is measured along the target radius. The magnetic fields have rotational symmetry. The horizontal and vertical components of the magnetic field B are measured at points above the cathode target with z = 2 x 10(-3) m. The experimental data reveal that the target erosion depth profile is a function of the angle. made by B with a horizontal line defined by z = 2 x 10(-3) m. To explain this dependence a simplified model of the discharge is developed. In the scope of the model, the pathway lengths of the secondary electrons in the pre-sheath region are calculated by analytical integration of the Lorentz differential equations. Weighting these lengths by using the distribution law of the mean free path of the secondary electrons, we estimate the densities of the ionizing events over the cathode and the relative flux of the sputtered atoms. The expression so deduced correlates for the first time the erosion depth profile of the target with the angle theta. The model shows reasonably good fittings to the experimental target erosion depth profiles confirming that ionization occurs mainly in the pre-sheath zone.

Electrochemical and analytical investigation of passive films formed on stainless steels in alkaline media

Passive films were grown in potentiodynamic mode, by cyclic voltammetry on AISI 316 and AISI 304 stainless steels. The composition of these films was investigated by X-ray photoelectron spectroscopy (XPS). The electrochemical behaviour and the chemical composition of the passive films formed by cyclic voltammetry were compared to those of films grown under natural conditions (by immersion at open circuit potential, OCP) in alkaline solutions simulating concrete. The study included the effect of pH of the electrolyte and the effect of the presence of chloride ions. The XPS results revealed important changes in the passive film composition, which becomes enriched in chromium and depleted in magnetite as the pH decreases. On the other hand, the presence of chlorides promotes a more oxidised passive layer. The XPS results also showed relevant differences on the composition of the oxide layers for the films formed under cyclic voltammetry and/or under OCP.

Optimization of HS-SPME analytical conditions using factorial design for trihalomethanes determination in swimming pool water samples

Trihalomethanes (THMs) are widely referred and studied as disinfection by-products (DBPs). The THMs that are most commonly detected are chloroform (TCM), bromodichloromethane (BDCM), chlorodibromomethane (CDBM), and bromoform (TBM). Several studies regarding the determination of THMs in swimming pool water and air samples have been published. This paper reviews the most recent work in this field, with a special focus on water and air sampling, sample preparation and analytical determination methods. An experimental study has been developed in order to optimize the headspace solid-phasemicroextraction (HS-SPME) conditions of TCM, BDCM, CDBM and TBM from water samples using a 23 factorial design. An extraction temperature of 45 °C, for 25min, and a desorption time of 5 min were found to be the best conditions. Analysis was performed by gas chromatography with an electron capture detector (GC-ECD). The method was successfully applied to a set of 27 swimming pool water samples collected in the Oporto area (Portugal). TCM was the only THM detected with levels between 4.5 and 406.5 μg L−1. Four of the samples exceeded the guideline value for total THMs in swimming pool water (100 μgL−1) indicated by the Portuguese Health Authority.

On the analytical solutions of the Hindmarsh-Rose neuronal model

In this article we analytically solve the Hindmarsh-Rose model (Proc R Soc Lond B221:87-102, 1984) by means of a technique developed for strongly nonlinear problems-the step homotopy analysis method. This analytical algorithm, based on a modification of the standard homotopy analysis method, allows us to obtain a one-parameter family of explicit series solutions for the studied neuronal model. The Hindmarsh-Rose system represents a paradigmatic example of models developed to qualitatively reproduce the electrical activity of cell membranes. By using the homotopy solutions, we investigate the dynamical effect of two chosen biologically meaningful bifurcation parameters: the injected current I and the parameter r, representing the ratio of time scales between spiking (fast dynamics) and resting (slow dynamics). The auxiliary parameter involved in the analytical method provides us with an elegant way to ensure convergent series solutions of the neuronal model. Our analytical results are found to be in excellent agreement with the numerical simulations.

New analytical methodologies for doping control – detection of anabolic androgenic steroids in human urine

Dissertation submitted to Faculdade de Ciências e Tecnologia - Universidade Nova de Lisboa in fulfilment of the requirements for the degree of Doctor of Philosophy (Biochemistry - Biotechnology)

Archaeological roman glasses: comparative characterisation by non-destructive analytical techniques

Dissertation presented in fulfilment of the requirements for the Master’s degree in Conservation and Restoration

Phenolic compounds from olive mill wastes: Health effects, analytical approach and application as food antioxidants

Background Over the years, food industry wastes have been the focus of a growing interest due to their content in high added-value compounds. A good example are the olive oil by-products (OOBP), which retain a great amount of phenolic compounds during olive oil production. Their structure and biological properties justify their potential use as antioxidants in other food products. The efficient recovery of phenolic compounds has been extensively studied and optimized in order to maximize their reintroduction in the food chain and contribute to a higher valorization and better management of wastes from olive oil industry. Scope and approach This paper reviews the most representative phenolic compounds described in OOBP and their biological properties. New extraction procedures to efficiently recover these compounds and the most advanced chromatographic techniques that have been used for a better understanding of the phenolic profile of these complex matrices are also referred. Finally, this paper reports the main applications of OOBP, with emphasis on their phenolic content as natural antioxidants for food applications. Key findings and conclusions Besides their antioxidant activity, phenolic compounds from OOBP have also shown antimicrobial and antitumoral properties. Their application as food antioxidants requires new extraction techniques, including the use of non-toxic solvents and, in a pilot scale, the use of filters and adsorbent resins. The inclusion of phenolic compounds from OOBP in some food matrices have improved not only their antioxidant capacity but also their sensory attributes.

A simplified four-branch model for the analytical study of the out-of-plane performance of regular stone URM walls

During the last years, several studies have been made aiming to assess the out-of-plane seismic response of unreinforced stone masonry structures. This fact led to the development of a wide variety of models and approaches, ranging from simple kinematic based analytical models up to complex numerical simulations. Nevertheless, for the sake of simplicity, the out-of-plane seismic response of a masonry wall pier may be obtained by means of a simple single-degree-of-freedom system while still providing good results. In fact, despite the assumptions associated with such a simple formulation, it is also true that the epistemic uncertainty inherent with the selection of appropriate input parameters in more complex models may render them truly ineffective. In this framework, this paper focuses on the study of the out-of-plane bending of unreinforced stone masonry walls (cantilevers) by proposing a simplified analytical approach based on the construction of a linearized four-branch model, which is used to characterize the linear and nonlinear response of such structural elements through an overturning moment-rotation relationship. The formulation of the four-branch model is presented and described in detail and the meaningful parameters used for its construction are obtained from a set of experimental laboratory tests performed on six full-scale unreinforced regular sacco stone masonry specimens. Moreover, a parametric analysis aiming to evaluate the effect of these parameters’ variation on the final configuration of the model is presented and critically discussed. Finally, the results obtained from the application of the developed four-branch model on real unreinforced regular sacco stone masonry walls are thoroughly analysed and the main conclusions obtained from its application are summarized.

A study on reducing digital piracy: an analytical network process approach with benefits, opportunities, costs and risks analysis

Dissertação para obtenção do Grau de Mestre em Engenharia e Gestão Industrial

SPf66 vaccine trial in Brazil: conceptual framework study design and analytical approach

This paper describes the study population and the study design of the phase III field trial of the SPf66 vaccine in Brazil. Assessment of validity and precision principles necessary for the appropriate evaluation of the protective effect of the vaccine are discussed, as well as the results of the preliminary analyses of the gathered data. The analytical approach for the estimation of the protective effect of the vaccine is presented. This paper provides the conceptual framework for future publications.

Predictive analytical and numerical modeling for orthogonal cutting

In this thesis, a predictive analytical and numerical modeling approach for the orthogonal cutting process is proposed to calculate temperature distributions and subsequently, forces and stress distributions. The models proposed include a constitutive model for the material being cut based on the work of Weber, a model for the shear plane based on Merchants model, a model describing the contribution of friction based on Zorev’s approach, a model for the effect of wear on the tool based on the work of Waldorf, and a thermal model based on the works of Komanduri and Hou, with a fraction heat partition for a non-uniform distribution of the heat in the interfaces, but extended to encompass a set of contributions to the global temperature rise of chip, tool and work piece. The models proposed in this work, try to avoid from experimental based values or expressions, and simplifying assumptions or suppositions, as much as possible. On a thermo-physical point of view, the results were affected not only by the mechanical or cutting parameters chosen, but also by their coupling effects, instead of the simplifying way of modeling which is to contemplate only the direct effect of the variation of a parameter. The implementation of these models was performed using the MATLAB environment. Since it was possible to find in the literature all the parameters for AISI 1045 and AISI O2, these materials were used to run the simulations in order to avoid arbitrary assumption.