Caracterização de antioxidantes com potencial interesse industrial

Mestrado em Engenharia Química

Pesticide residues in Portuguese strawberries grown in 2009–2010 using integrated pest management and organic farming

Pesticides are among the most widely used chemicals in the world. Because of the widespread use of agricultural chemicals in food production, people are exposed to low levels of pesticide residues through their diets. Scientists do not yet have a total understanding of the health effects of these pesticide residues. This work aims to determine differences in terms of pesticide residue content in Portuguese strawberries grown using different agriculture practices. The Quick, Easy, Cheap, Effective, Rugged, and Safe sample preparation method was conducted and shown to have good performance for multiclass pesticides extraction in strawberries. The screening of 25 pesticides residue was performed by gas chromatography–tandem mass spectrometry. In quantitative validation, acceptable performances were achieved with recoveries of 70–120 and <12 % residual standard deviation for 25 pesticides. Good linearity was obtained for all the target compounds, with highly satisfactory repeatability. The limits of detection were in the range of 0.1–28 μg/kg. The method was applied to analyze strawberry samples from organic and integrated pest management (IPM) practices harvested in 2009–2010. The results showed the presence of fludioxonil, bifenthrin, mepanipyrim, tolylfluanid, cyprodinil, tetraconazole, and malathion when using IPM below the maximum residue levels.

Preparation and characterization of beta-lactam antibiotic as Ionic liquids and salts

With the increase of bacterial resistance a large number of therapeutic strategies have been used to fight different kind of infections. In recent years ionic liquids (ILs) have been increasing the popularity and the number of applications. First ionic liquids were used mainly as solvent in organic synthesis, but now they are used in analytical chemistry, separation chemistry and material science among others. Additional to significant developments in their chemical properties and applications, ionic liquids are now bringing unexpected opportunities at the interface of chemistry with the life sciences Ionic liquids (ILs) are currently defined as salts that are composed solely of cations and anions which melt below 100ºC. Our goal in this work is to explore the dual activity of the ionic liquids, due to the presence of two different ions, an ion with bacterial activity as a beta-lactam antibiotic and different kinds of cations. In this work the anions of ILs and salts were derived from three different antibiotics: ampicillin, penicillin and amoxicillin. The cations were derived from substituted ammonium, phosphonium pyridinium and methylimidazolium salts, such as: tetraethyl ammonium, trihexiltetradecilphosphonium, cetylpyridinium, choline (an essential nutrient), 1-ethyl-3-methylimidazolium, and 1-ethanol-3-methyl imidazolium structures. Commercial ammonium and phosponium halogen salts were first transformed into hydroxides. on ionic exchange column (Amberlite IRA-400) in methanol. The prepared hydroxides were then neutralized with beta-lactam antibiotics. After crystallization we obtained pure ILs and salts containing beta-lactam antibiotics. This work presents a novel method for preparation of new salts of antibiotics with low melting point and their characterization.

Analysing organochlorine pesticides in strawberry jams using GC-ECD, GC-MS/MS and QuEChERS sample preparation

This paper describes a comparison of adaptations of the QuEChERS (quick, easy, cheap, effective, rugged and safe) approach for the determination of 14 organochlorine pesticide (OCP) residues in strawberry jam by concurrent use of gas chromatography (GC) coupled to electron capture detector (ECD) and GC tandem mass spectrometry (GC-MS/MS). Three versions were tested based on the original QuEChERS method. The results were good (overall average of 89% recoveries with 15% RSD) using the ultrasonic bath at five spiked levels. Performance characteristics, such as accuracy, precision, linear range, limits of detection (LOD) and quantification (LOQ), were determined for each pesticide. LOD ranged from 0.8 to 8.9 microg kg-1 ; LOQ was in the range of 2.5–29.8 microg kg- 1; and calibration curves were linear (r2>0.9970) in the whole range of the explored concentrations (5–100 microg kg- 1). The LODs of these pesticides were much lower than the maximum residue levels (MRLs) allowed in Europe for strawberries. The method was successfully applied to the quantification of OCP in commercially available jams. The OCPs were detected lower than the LOD.

QuEChERS: a new sample preparation approach for the determination of ibuprofen and its metabolites in soils

Ibuprofen is one of the most used active pharmaceutical ingredients worldwide. A new method for the analysis of ibuprofen and its metabolites, hydroxyibuprofen and carboxyibuprofen, in soils is presented. The extraction of these compounds from the soil matrices was performed by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. The method involves a single extraction of the investigated compounds with purified water (acidified at pH 2.5 with hydrochloric acid), and a slow and continuous addition of the QuEChERS content, followed by the addition of acidified acetonitrile (1% acetic acid), prior to the determination by liquid chromatography coupled with fluorescence detection (LC–FLD). Validation studies were carried out using soil samples with a range of organic carbon contents. Recoveries of the fortified samples ranged from 79.5% to 101%. Relative standard deviations for all matrix–compound combinations did not exceed 3%. The method quantification limits were ≤22.4 μg kg−1 in all cases. The developed method was applied to the analysis of sixteen real samples.

Shear strength of adhesively bonded polyolefins with minimal surface preparation

Interest in polyethylene and polypropylene bonding has increased in the last years. However, adhesive joints with adherends which are of low surface energy and which are chemically inert present several difficulties. Generally, their high degree of chemical resistance to solvents and dissimilar solubility parameters limit the usefulness of solvent bonding as a viable assembly technique. One successful approach to adhesive bonding of these materials involves proper selection of surface pre-treatment prior to bonding. With the correct pre-treatment it is possible to glue these materials with one or more of several adhesives required by the applications involved. A second approach is the use of adhesives without surface pre-treatment, such as hot melts, high tack pressure-sensitive adhesives, solvent-based specialty adhesives and, more recently, structural acrylic adhesives as such 3M DP-8005® and Loctite 3030®. In this paper, the shear strengths of two acrylic adhesives were evaluated using the lap shear test method ASTM D3163 and the block shear test method ASTM D4501. Two different industrial polyolefins (polyethylene and polypropylene) were used for adherends. However, the focus of this study was to measure the shear strength of polyethylene joints with acrylic adhesives. The effect of abrasion was also studied. Some test specimens were manually abraded using 180 and 320 grade abrasive paper. An additional goal of this work was to examine the effect of temperature and moisture on mechanical strength of adhesive joints.

The use of the boundary element method in the analysis of single lap joints

The most common techniques for stress analysis/strength prediction of adhesive joints involve analytical or numerical methods such as the Finite Element Method (FEM). However, the Boundary Element Method (BEM) is an alternative numerical technique that has been successfully applied for the solution of a wide variety of engineering problems. This work evaluates the applicability of the boundary elem ent code BEASY as a design tool to analyze adhesive joints. The linearity of peak shear and peel stresses with the applied displacement is studied and compared between BEASY and the analytical model of Frostig et al., considering a bonded single-lap joint under tensile loading. The BEM results are also compared with FEM in terms of stress distributions. To evaluate the mesh convergence of BEASY, the influence of the mesh refinement on peak shear and peel stress distributions is assessed. Joint stress predictions are carried out numerically in BEASY and ABAQUS®, and analytically by the models of Volkersen, Goland, and Reissner and Frostig et al. The failure loads for each model are compared with experimental results. The preparation, processing, and mesh creation times are compared for all models. BEASY results presented a good agreement with the conventional methods.

Comparison of Disposable Pipette Extraction and Dispersive Solid-Phase Extraction in the QuEChERS Method for Analysis of Pesticides in Strawberries

In this study, we sought to assess the applicability of GC–MS/MS for the identification and quantification of 36 pesticides in strawberry from integrated pest management (IPM) and organic farming (OF). Citrate versions of QuEChERS (quick, easy, cheap, effective, rugged and safe) using dispersive solid-phase extraction (d-SPE) and disposable pipette extraction (DPX) for cleanup were compared for pesticide extraction. For cleanup, a combination of MgSO4, primary secondary amine and C18 was used for both the versions. Significant differences were observed in recovery results between the two sample preparation versions (DPX and d-SPE). Overall, 86% of the pesticides achieved recoveries (three spiking levels 10, 50 and 200 µg/kg) in the range of 70–120%, with <13% RSD. The matrix effects were also evaluated in both the versions and in strawberries from different crop types. Although not evidencing significant differences between the two methodologies were observed, however, the DPX cleanup proved to be a faster technique and easy to execute. The results indicate that QuEChERS with d-SPE and DPX and GC–MS/MS analysis achieved reliable quantification and identification of 36 pesticide residues in strawberries from OF and IPM.

QuEChERS: a sample preparation for extraction of carbaryl from rat feces

Carbamate compounds are an important group of cholinesterase inhibitors. There is a need for creating awareness regarding the risks of the inadequate carbamate use in the residential areas due to potential adverse human effects. Carbaryl is a commonly used pesticide worldwide. A simple, fast, and high throughput method was developed employing liquid chromatography with fluorescence detector to determine carbaryl residues in rat feces. The extraction was performed by using a rapid, easy, cheap, effective, reliable, and safe (QuEChERS) method, using acetonitrile as the extracting solvent. The parameters for the performance of the extraction method were optimized, such as ratio of mass of sample per volume of extraction solvent, QuEChERS content, and cleanup columns. Linear response was obtained for all calibration curves (solven and matrix-matched) over the established concentration range (5 500 mg/L) with a correlation coefficients higher than 0.999. The achieved recovery was 97.9% with relative standard deviation values of 1.1% (n D 4) at 167 mg/kg fortified concentration level and the limits of detection and quantification were 27.7 and 92.3 mg/kg respectively.

Estudo da norma contabilística e de relato financeiro nº 13 – interesses em empreendimentos conjuntos e investimentos em associadas e suas implicações fiscais e de auditoria

Dissertação apresentada ao Instituto Superior de Contabilidade e Administração do Porto para a obtenção do Grau de Mestre em Auditoria Orientada pelo Dr. José da Silva Fernandes

A novel framework for modeling value for the customer, an essay on negotiation

This paper proposes a novel framework for modelling the Value for the Customer, the so-called the Conceptual Model for Decomposing Value for the Customer (CMDVC). This conceptual model is first validated through an exploratory case study where the authors validate both the proposed constructs of the model and their relations. In a second step the authors propose a mathematical formulation for the CMDVC as well as a computational method. This has enabled the final quantitative discussion of how the CMDVC can be applied and used in the enterprise environment, and the final validation by the people in the enterprise. Along this research, we were able to confirm that the results of this novel quantitative approach to model the Value for the Customer is consistent with the company's empirical experience. The paper further discusses the merits and limitations of this approach, proposing that the model is likely to bring value to support not only the contract preparation at an Ex-Ante Negotiation Phase, as demonstrated, but also along the actual negotiation process, as finally confirmed by an enterprise testimonial.

Peer Instruction method in introductory math courses

Learning is not a spectator’s sport. Students do not learn much by just sitting in class listening their teachers, memorizing pre-packaged assignments and spitting out answers. The teaching-learning process has been a constant target of studies, particularly in Higher Education, in consequence of the annual increase of new students. The concern with maintaining a desired quality level in the training of these students, conjugated with the will to widen the access to all of those who finish Secondary School Education, has triggered a greater intervention from the education specialists, in partnership with the teachers of all Higher Education areas, in the analysis of this problem. Considering the particular case of Engineering, it has been witnessed a rising concern with the active learning strategies and forms of assessment. Research has demonstrated that students learn more if they are actively engaged with the material they are studying. In this presentation we describe, present and discuss the techniques and the results of Peer Instruction method in an introductory Calculus courses of an Engineering Bach

Scheduling maintenance activities of electric power transmission networks using an hybrid constraint method

In this paper we present a Constraint Logic Programming (CLP) based model, and hybrid solving method for the Scheduling of Maintenance Activities in the Power Transmission Network. The model distinguishes from others not only because of its completeness but also by the way it models and solves the Electric Constraints. Specifically we present a efficient filtering algorithm for the Electrical Constraints. Furthermore, the solving method improves the pure CLP methods efficiency by integrating a type of Local Search technique with CLP. To test the approach we compare the method results with another method using a 24 bus network, which considerers 42 tasks and 24 maintenance periods.

An efficient method for optimal location and sizing of fixed and switched shunt capacitors in large distribution systems

This paper proposes a computationally efficient methodology for the optimal location and sizing of static and switched shunt capacitors in large distribution systems. The problem is formulated as the maximization of the savings produced by the reduction in energy losses and the avoided costs due to investment deferral in the expansion of the network. The proposed method selects the nodes to be compensated, as well as the optimal capacitor ratings and their operational characteristics, i.e. fixed or switched. After an appropriate linearization, the optimization problem was formulated as a large-scale mixed-integer linear problem, suitable for being solved by means of a widespread commercial package. Results of the proposed optimizing method are compared with another recent methodology reported in the literature using two test cases: a 15-bus and a 33-bus distribution network. For the both cases tested, the proposed methodology delivers better solutions indicated by higher loss savings, which are achieved with lower amounts of capacitive compensation. The proposed method has also been applied for compensating to an actual large distribution network served by AES-Venezuela in the metropolitan area of Caracas. A convergence time of about 4 seconds after 22298 iterations demonstrates the ability of the proposed methodology for efficiently handling large-scale compensation problems.

Research on using the decision tree method in order to select the best alternative for the pharmacies supply

Introduction / Aims: Adopting the important decisions represents a specific task of the manager. An efficient manager takes these decisions during a sistematic process with well-defined elements, each with a precise order. In the pharmaceutical practice and business, in the supply process of the pharmacies, there are situations when the medicine distributors offer a certain discount, but require payment in a shorter period of time. In these cases, the analysis of the offer can be made with the help of the decision tree method, which permits identifying the decision offering the best possible result in a given situation. The aims of the research have been the analysis of the product offers of many different suppliers and the establishing of the most advantageous ways of pharmacy supplying. Material / Methods: There have been studied the general product offers of the following medical stores: A&G Med, Farmanord, Farmexim, Mediplus, Montero and Relad. In the case of medicine offers including a discount, the decision tree method has been applied in order to select the most advantageous offers. The Decision Tree is a management method used in taking the right decisions and it is generally used when one needs to evaluate the decisions that involve a series of stages. The tree diagram is used in order to look for the most efficient means to attain a specific goal. The decision trees are the most probabilistic methods, useful when adopting risk taking decisions. Results: The results of the analysis on the tree diagrams have indicated the fact that purchasing medicines with discount (1%, 10%, 15%) and payment in a shorter time interval (120 days) is more profitable than purchasing without a discount and payment in a longer time interval (160 days). Discussion / Conclusion: Depending on the results of the tree diagram analysis, the pharmacies would purchase from the selected suppliers. The research has shown that the decision tree method represents a valuable work instrument in choosing the best ways for supplying pharmacies and it is very useful to the specialists from the pharmaceutical field, pharmaceutical management, to medicine suppliers, pharmacy practitioners from the community pharmacies and especially to pharmacy managers, chief – pharmacists.