O uso de pesticidas levou ao aumento da produtividade e qualidade dos produtos agrícolas, porém o seu uso acarreta na intoxicação dos seres vivos pela ingestão gradativa de seus resíduos que contaminam o solo, a água e os alimentos. Dessa forma, há a necessidade do monitoramento constante de suas concentrações nos compartimentos ambientais. Para isto, busca-se o desenvolvimento de métodos de extração e enriquecimento de forma rápida, com baixo custo, gerando um baixo volume de resíduos, contribuindo com a química verde. Dentre estes métodos destacam-se a extração por banho de ultrassom e a extração por ponto nuvem. Após o procedimento de extração, o extrato obtido pode ser analisado por técnicas de Cromatografia a Líquido de Alta Eficiência (HPLC) e a Cromatografia por Injeção Sequencial (SIC), empregando fases estacionárias modernas, tais como as monolíticas e as partículas superficialmente porosas. O emprego de SIC com coluna monolítica (C18, 50 x 4,6 mm) e empacotada com partículas superficialmente porosas (C18, 30 x 4,6 mm, tamanho de partícula 2,7 µm) foi estudado para separação de simazina (SIM) e atrazina (ATR), e seus metabólitos, desetilatrazina (DEA), desisopropilatrazina (DIA) e hidroxiatrazina (HAT). A separação foi obtida por eluição passo-a-passo, com fases móveis compostas de acetonitrila (ACN) e tampão Acetato de Amônio/Ácido acético (NH4Ac/HAc) 2,5 mM pH 4,2. A separação na coluna monolítica foi realizada com duas fases móveis: MP1= 15:85 (v v-1) ACN:NH4Ac/HAc e MP2= 35:65 (v v-1) ACN:NH4Ac/HAc a uma vazão de 35 µL s-1. A separação na coluna com partículas superficialmente porosas foi efetivada com as fases móveis MP1= 13:87 (v v-1) ACN: NH4Ac/HAc e MP2= 35:65 (v v-1) ACN:NH4Ac/HAc à vazão de 8 µL s-1. A extração por banho de ultrassom em solo fortificado com os herbicidas (100 e 1000 µg kg-1) resultou em recuperações entre 42 e 160%. A separação de DEA, DIA, HAT, SIM e ATR empregando HPLC foi obtida por um gradiente linear de 13 a 35% para a coluna monolítica e de 10 a 35% ACN na coluna com partículas superficialmente porosas, sendo a fase aquosa constituída por tampão NH4Ac/HAc 2,5 mM pH 4,2. Em ambas as colunas a vazão foi de 1,5 mL min-1 e o tempo de análise 15 min. A extração por banho de ultrassom das amostras de solo com presença de ATR, fortificadas com concentrações de 250 a 1000 µg kg-1, proporcionou recuperações entre 40 e 86%. A presença de ATR foi confirmada por espectrometria de massas. Foram realizados estudos de fortificação com ATR e SIM em amostras de água empregando a extração por ponto nuvem com o surfactante Triton-X114. A separação empregando HPLC foi obtida por um gradiente linear de 13 a 90% de ACN para a coluna monolítica e de 10 a 90% de ACN para a coluna empacotada, sempre em tampão NH4Ac/HAc 2,5 mM pH 4,2. Em ambas as colunas a vazão foi de 1,5 mL min-1 e o tempo de análise 16 min. Fortificações entre 1 e 50 µg L-1 resultaram em recuperações entre 65 e 132%. / The use of pesticides has led to increased productivity and quality of agricultural products, but its use brings the intoxication of living beings by the gradual intake of their residues that contaminate soil, water and food. Thus, there is the need for constant monitoring of their concentrations in environmental compartments. For this, there is a quest for development of fast extraction and enrichment methods, at low cost, generating a low volume of waste, contributing to green chemistry. These methods include the extraction assisted by ultrasound bath and the cloud point extraction. After the extraction, the extract obtained can be analyzed by techniques such as High Performance Liquid Chromatography (HPLC) and Sequential Injection Chromatography (SIC) employing modern stationary phases, such as monolithic and superficially porous particles. The use of SIC with either monolithic column (C18, 50 x 4.6 mm) or column packed with superficially porous particles (C18, 30 x 4.6 mm, 2.7 µM particle size) was studied for separating simazine (SIM) and atrazine (ATR), and metabolites, deethylatrazine (DEA), deisopropylatrazine (DIA) and hydroxyatrazine (HAT). Separation was obtained by stepwise elution, with a mobile phase consisting of acetonitrile (ACN) and 2.5 mM ammonium acetate / acetic acid (NH4Ac / HAc) pH 4.2 buffer. The separation was performed with two mobile phases: MP1 = 15:85 (v v -1) ACN: NH4Ac / HAc and MP2 = 35:65 (v v-1) ACN: NH4Ac / HAc at a flow rate of 35 µL s-1. The separation in the column with superficially porous particles was carried out with the mobile phases MP1 = 13:87 (v v-1) ACN: NH4Ac / HAc and MP2 = 35:65 (v v-1) ACN: NH4Ac / HAc at 8 µL s-1. The ultrasound bath extraction from a soil fortified with herbicides (100 and 1000 µg kg-1) resulted in recoveries between 42 and 160 %. Separation of DEA, DIA, HAT SIM and ATR was obtained by HPLC employing a linear gradient from 13 to 35% for the monolithic column and from 10 to 35% ACN in the column packed with superficially porous particles, with the aqueous phases consisting of 2.5 mM NH4Ac / HAc buffer pH 4.2. In both columns the flow rate was 1.5 mL min-1 and the analysis time was15 min. Ultrasonic extraction from a soil sample containing ATR, fortified with concentrations from 250 to 1000 µg kg-1, provided recoveries between 40 and 86%. The presence of ATR was confirmed by mass spectrometry. Fortification studies with ATR and SIM were carried out in water samples employing cloud point extraction using Triton-X114 surfactant. The separation was accomplished by HPLC using a linear gradient from 13 to 90 % of ACN for the monolithic column and from 10 to 90 % ACN for the packed column, always in 2.5 mM NH4Ac / HAc pH 4.2 buffer. In both columns the flow rate was 1.5 mL min -1 and the analysis time 16 min. Fortifications between 1 and 50 µg L-1 resulted in recoveries between 65 and 132%.

This diploma thesis deals with the development of an HPLC method for the determination of selected compounds participating in enzymatic reaction leading to the formation of gallic acid. The analysed reaction mixture contains the following reagents: shikimic acid, NADP+ and shikimatedehydrogenase (SDH) extracted from parsley; the presumed product of the reaction is gallic acid. Two chromatographic methods for the determination of the above mentioned compounds were developed using C18 HPLC column and porous graphitic carbon Hypercarb column. Molecular absorption spectrometric detection in the UV range was used in all measurements. Separation on the C18 column was found particularly suitable for analysing the composition of the end products of the reaction. Because of the NADP+ and shikimic acid peak overlap it is necessary to observe absorbance at 212 and 260 nm. Shikimic acid and NADP+ can be quantified due to the fact that shikimic acid does not absorb at 260 nm while NADP+ absorb radiation at both wavelengths. Separation via Hypercarb column was found particularly suitable for analysing the process of the reaction; additional products or intermediates can be seen in chromatograms compared to the C18 method. Determination with Hypercarb column is characterized by higher sensitivity and lower limit...

[pt] Esta dissertação estuda modelos e algoritmos para o Problema de Alocação Generalizada (PAG) . A motivação para este estudo foi uma nova aplicação do PAG: o Problema de Carregamento de Caminhões (PCC) . A pesquisa desenvolvida concentra-se no estudo e na proposta de algoritmos aproximados (metaeurísticas) e exatos para a resolução do PAG. Os algoritmos aproximados propostos baseiam-se em um conceito recentemente criado por Fischetti e Lodi (2003), que utiliza programação matemática inteira para a exploração eficiente de vizinhanças mais abrangentes. Os resultados obtidos foram comparáveis aos melhores conhecidos, com a vantagem de exigir um esforço pequeno de implementação e um menor tempo de processamento. O algoritmo exato proposto é um algoritmo de branch-and-cut- and-price, que tem como ponto de partida o algoritmo de branch-and-price de Savelsbergh (1997). Técnicas de estabilização da geração de colunas similares às propostas por Du Merle, Villeneuve, Desrosiers e Hansen (1999), foram estudadas no âmbito desta dissertação, que experimenta com diferentes implementações deste mecanismo. O algoritmo de branch-andcut-and-price estabilizado demonstrou sua eficiência ao resolver à otimalidade instâncias que se encontravam em aberto na literatura. Finalmente, experiências com PCC permitiram que os códigos desenvolvidos pudessem ser avaliados em problemas reais. / [en] This dissertation tackles the Generalized Assignment Problem (PAG), models and algorithms are studied and proposed. This work was motivated by a real world application: the Truck Loading Problem (PCC). Research was done on approximated (metaheuristics) and exact algorithm for solving the PAG. The approximated algorithms proposed were based on a recent idea from Fischetti and Lodi (2003). It uses integer programming to explore wider neighborhoods. The results were compared to the best known, while demanding much less implementation effort and using less cpu time. The exact algorithm proposed is a branch-and-cut- and-price developed from the branch-and-price algorithm of Savelsbergh (1997). We used stabilized column generation techniques similar to the one by Du Merle, Villeneuve, Desrosiers and Hansen (1999), and devised experiments with different implementations of this mechanism. The resulting algorithm proved its efficiency by solving to optimality open instances from the literature. Finally, experiments with the PCC turned possible the evaluation of the codes developed on real problems.

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The diploma thesis deals with the design and assessment of the steel supporting structure of the production hall. The transverse dimension of the hall is 21,00 m, the longitudinal dimension is 70,00 m, the height of the hall is 17,56 m. S355 steel is used as the main supporting material. The supporting part of the hall consists of columns on which is placed a truss and two crane tracks at two height levels. Three different types of purlins and pillars are considered in the design of the steel structure. For the selected variant, a static calculation of the main bearing elements, including selected details, is drawn up and drawings are drawn up.

Denna rapport ämnar undersöka de vanligast förekommande typerna av teknologier för vågkraftverk (eng. Wave Energy Converter, WEC) teknologier för att jämföra de olika konceptens förmåga att absorbera vågenergi. Koncept som undersöks är punktabsorbatorer och oscillerande vattenkolumner. I denna rapport används de vanligt använda engelska översättningarna point absorber och oscillating water column (OWC). Beräkningar görs för de olika koncepten i liknande vågförhållanden för att kunna jämföra den energi som kan utvinnas. I rapporten sker beräkningar under optimala vågförhållanden. Vågorna antas vara linjära och vågkraftverken antas vara i fas med vågens svängningsrörelse. Den vågdata som använts är uppmätt utanför Belmullet i Irland. Beräkningar görs på vågor med en signifikant våghöjd på 1,25 m och en periodtid på 7,5 s. Det görs även beräkningar på den största uppmätta förekommande vågen. I huvudsak används effektberäkningar enligt en modell som Kjell Budal. Syftet är att grafiskt och numeriskt jämföra den teoretiska och faktiska maxeffekt som kan utvinnas ur respektive våg. Resultatet från undersökningen visar att den största bidragande faktorn till en hög energiutvinning beror på bojens volym. Volymen måste anpassas för de vågförhållanden som finns där bojen ska placeras.Vid beräkningar av en OWC med tvärsnittsarea på 19 m2 visar det sig att den effekt som kan utvinnas av en luftkammare med tillhörande turbin är ungefär 10 kW, 1/30 av de 300kW som kan utvinnas av en point absorber. En OWC består dock sällan utav en ensam luftkammare utan ofta i en array med ett flertal luftkammare med separata turbiner för att öka effekten. / This report intends to examine the most common types of wave energy converter technologies to compare the different concepts' ability to absorb wave energy. Concepts being investigated are point absorbers and oscillating water columns (OWC). Calculations are made for the different concepts in the same wave conditions to be able to compare the energy that can be extracted. In the report, calculations are made under optimal wave conditions. The waves are assumed to be linear and the wave energy converter is assumed to be in phase with the oscillating motion of the wave. The wave data used is measured outside Belmullet in Ireland. Calculations are made on waves with a significant wave height of 1.25 m and a period time of 7.5 s. Calculations are also made on the largest measured wave present. In essence, power calculations are used according to a model developed by Kjell Budal and with the help of this be able to graphically and numerically compare the theoretical and actual maximum power that can be extracted from each scale. The results from the survey show that the largest contributing factor to high energy recovery is due to the volume of the buoy. The volume must be adapted to the wave conditions that exist where the buoy is to be placed.When calculating an OWC with a cross sectional area of 19 m2, it turns out that the power that can be extracted from an air chamber with an associated turbine is approximately 10 kW, 1/30 of the 300 kW that can be extracted by one point absorber. However, an OWC rarely consists of a single air chamber but often in a construction with several air chambers with separate turbines to increase the power.

Integer programming can be used to provide solutionsto complex decision and planning problems occurring in a wide varietyof situations. Applying integer programming to a real life problembasically involves a first phase where a mathematical model isconstructed, and a second phase where the problem described by themodel is solved. While the nature of the challenges involved in therespective two phases differ, the strong relationship between theproperties of models, and which methods that are appropriate for theirsolution, links the two phases. This thesis constitutes of threepapers, of which the third one considers the modeling phase, while thefirst and second one consider the solution phase.   Many applications of column generation yield master problems of setpartitioning type, and the first and second papers presentmethodologies for solving such problems. The characteristics of themethodologies presented are that all successively found solutions arefeasible and integral, where the retention of integrality is a majordistinction from other column generation methods presented in theliterature.   The third paper concerns nurse scheduling and describes the results ofa pilot implementation of a scheduling tool at a Swedish nursing ward.This paper focuses on the practical aspects of modeling and thechallenges of providing a solution to a complex real life problem.

Thesis (MScEng (Civil Engineering))--University of Stellenbosch, 2006. / The predominately manual, time-consuming and error-prone procedure currently used in engineering offices for the calculation of preliminary column forces in multi-storey buildings constitutes the motive for the research described in this study. Identifying the current procedure as in need of improvement, techniques and prototype software posing a semi-automated alternative, are developed. Influence areas used for load-assignment are established with the use of a Voronoi diagram calculated for a specific floor geometry. The forces transferred to the columns are based solely on the size of the influence areas thus calculated. The definition of the floor geometry, as well as the definition of loads and other necessary input parameters, are performed in a CAD-system, into which the Voronoi functionality is integrated. The accuracy of the forces obtained with the implemented procedure and, consequently, the accuracy of the forces as they are calculated in current practice, is determined through comparison with the results of finite element analyses. The comparative analysis of a sample of typical floor geometries allows an evaluation of the results and the identification of tendencies observed regarding the errors obtained. It is concluded that calculating column forces based on influence areas, i.e. solving a geometrical problem without taking any stiffness properties into account, is unsafe. The implication hereof is twofold. Firstly, it serves as a warning concerning the technique currently used in practice and secondly, it steers the investigation in the direction of a finite element analysis: using the influence areas as a basis for automatic meshing, a semi-automated analysis can be performed relatively inexpensively, using plate elements.

The need of making arsenic contaminated ground water potable is urgent in parts of Burkina Faso. An implementation of a treatment design using Granular Ferric Hydroxide (GFH) is under development. Water from a tube-well in Lilgomdé, Yatenga province, Burkina Faso, has been treated with the adsorbent GFH through column experiments. The water had an arsenic concentration varying between 99 and 215 μg/L and an average pH of 7.9. The study has shown that arsenic, predominantly in the form of arsenate, can be adsorbed to the material in significant amounts despite a high natural pH and the presence of ions competing with arsenic for adsorption sites on the GFH. When run through the column, the pH of the effluent water drastically decreased in the beginning. However, the low pH was soon followed by a slower readjustment towards the pH of the influent water. The adsorption of phosphates and fluorides was also studied. Both competitors exist in higher molar quantities than arsenic in the ground water. Even though arsenic displays a higher affinity for the GFH, an average 44 % of total phosphate and 64 % of the fluoride were adsorbed, making them a factor affecting the results of the study. Hydrogen carbonate is also believed to affect the adsorption process but this could not be confirmed. The empty bed contact time (EBCT), describing the average time of contact between the adsorbent and the water, has shown to be of importance. Increasing the EBCT resulted in notably more arsenic being adsorbed per volume GFH. When increasing the contact time, the study showed that reducing the speed of the flow was more effective than increasing the volume of the adsorbent. The GFH was also found to have a self-regenerating ability to a certain extent. When interrupting the experiment and leaving the column material in the aqueous solution for several days, the arsenic adsorption capacity after the break was shown to be higher than just before it. A 13 % increased capacity was shown in one experiment. Conclusively, the results of this study suggest no hindrances towards developing larger scale columns and prototypes to be applied at tube-well pump stations. Further investigations on the treatment method with GFH, on arsenic contaminated water, are recommended.

The aim of this work is to study the in-vitro aerodynamic performance of a new inhaled theophylline formulation prepared by supercritical fluids technique. For the analysis of the output from the in-vitro tests (and further in-vivo tests) a new, fast, sensitive high performance liquid chromatographic (HPLC) method was developed and validated for the determination of theophylline and other related derivatives in aqueous and urine samples using new packing materials (monolithic columns). These columns achieve efficient separation under lower backpressure and shorter time comparing to other traditionally or newly introduced C18 columns. Solution enhanced dispersion by supercritical fluid (SEDS) process has been applied for the production of anhydrous theophylline as pure crystals in the range 2-5 μm to be used as new inhaled dry powder formulation for asthma. Fifteen theophylline samples have been prepared under different experimental conditions. The drug produced by this method has been subject to a number of solid-phase analytical procedures designed to establish the crystal structure [X-ray powder diffraction (XRPD)], the structure and conformation [(FTIR), Fourier-transform Raman spectroscopy (FT-Raman)], and the morphology and particle size [scanning electron microscope (SEM)]. While, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC) have been used to monitor any phase transition or polymorphic changes after processing. All these analytical techniques gave a satisfactory indication of the solid-state chemistry of the processed particles and assess the development of new inhalation product. The performance of inhaled SEDS theophylline with or without a carrier was evaluated using the developed HPLC method. Three samples having different particle sizes were selected out of the prepared powders by SEDS technique to be tested. The dose sampling unit and the Anderson Cascade Impactor were used to determine the in-vitro emitted dose and the deposition profiles of SEDS samples, respectively. The effect of different inhalation flows was studied using two different flows 28.3, and 60 L min-1 with 4 L inhalation volume. Different DPI devices were investigated in this study; Easyhaler® and Spinhaler®. The particle size has an important effect on the aerodynamic behaviour and deposition profile of inhaled drug, the smaller the particles the greater the total lung deposition. The presence of a carrier improves the respirable fraction for all the tested formulations.