This thesis first briefly mentions the characteristics of the skin and contains a review of current knowledge on the in vitro permeation testing of drugs through the skin. It describes the basic data about nerve agents and the possibilities of prophylaxis poisoning warfare agents focusing on preventive transdermal administration. The experimental work is focused on in vitro testing abilities oxime HI-6 and posibly other reactivators enzyme acetylcholinesterase penetrate through pig skin. Experiments were conducted in static diffusion cells Franz type. The amount of test substance leaked through the skin is determined in the sample of receptor fluid by HPLC. Keywords permeation in vitro; transdermal; pig skin; Franz cell; substance HI-6; antidota; nerve agents; acetylcholinesterase

Os minerais são de extrema importância no metabolismo geral e no desempenho produtivo e reprodutivo dos bovinos. Atualmente, no Brasil, existem poucos estudos sobre o diagnóstico de deficiências minerais em bovinos, através de análise de macroelementos e elementos traço em fluidos biológicos. A maior parte das informações disponíveis limitam-se ao diagnóstico clínico de deficiências isoladas e à análise de elementos nas pastagens e no solo, que podem sugerir deficiências sub clínicas de alguns minerais, mas apresentam várias limitações e interferências. O objetivo deste trabalho foi desenvolver um método de análise simples, com introdução direta da amostra, utilizando a técnica de q-ICP-MS e DRC-ICP-MS, para determinação de Ca, Cu, Fe, Mg, Zn, I, Mo, As, Se, Ni, Co, Ba, Cs, Mn e Pb em sêmen bovino. Para realização das análises, foi utilizada calibração em meio aquoso e as amostras foram diluídas na proporção 1:50 em solução contendo 0,01% v/v Triton® X-100 e 0,5% v/v de ácido nítrico. Também foram avaliadas a calibração por ajuste de matriz e a análise das amostras após digestão por microondas, para confirmação dos resultados obtidos por introdução direta e calibração em meio aquoso. O DRC foi essencial para determinação de níquel. O gás de reação utilizado foi H2 e os parâmetros RPq e vazão do gás foram estudados para otimização do método. Os limites de detecção para determinação de 44Ca, 63Cu, 57Fe, 24Mg, 64Zn, 127I, 98Mo, 75As, 82Se, 59Co, 138Ba, 133Cs, 55Mn e 208Pb foram: 0,262; 0,003; 0,168; 0,004; 0,004; 0,026; 0,007; 0,007; 0,033; 0,002; 0,005; 0,002; 0,003; 0,002 µg L-1 respectivamente, e para determinação de 60Ni por DRC-ICP-MS o LD foi 0,020 µgL-1. O método desenvolvido foi aplicado para determinação de 15 elementos em amostras de sêmen de bovinos de diferentes raças usadas em programas de reprodução e inseminação artificial. / The minerals are of extreme importance in the general metabolism and in the productive and reproductive performance of the bovines. Nowadays, in Brazil, few studies exist on the diagnosis of mineral deficiencies in bovine, through macroelementos analysis and trace elements in biological fluids. Most of the available information is limited to the clinical diagnosis of isolated deficiencies and the analysis of elements in the pastures and in the soil, that can suggest sub clinical deficiencies of some minerals, but present several limitations and interferences. The objective of this work was to develop a method of simple analysis, with direct introduction of the sample, using the technique of q-ICP-MS and DRC-ICP-MS, for determination of Ca, Cu, Fe, Mg, Zn, I, Mo, As, Se, Ni, Co, Ba, Cs, Mn and Pb in bovine semen. Aqueous medium calibration was used in the analysis and the samples were diluted in the proportion 1:50 in solution containing 0,01% v/v Triton® X-100 and 0,5% v/v of nitric acid. They were also evaluated the matrix matching and the analysis of samples after digestion for microwave, for confirmation of the results obtained by direct introduction and calibration in aqueous medium. DRC went essential for nickel determination. The reaction gas used it was H2 and the parameters RPq and gas flow rate were studied for optimization of the method. The detection limits for determination of 44Ca, 63Cu, 57Fe, 24Mg, 64Zn, 127I, 98Mo, 75As, 82Se, 59Co, 138Ba, 133Cs, 55Mn and 208Pb were: 0,262; 0,003; 0,168; 0,004; 0,004; 0,026; 0,007; 0,007; 0,033; 0,002; 0,005; 0,002; 0,003; 0,002 µg L-1 respectively, and for determination of 60Ni for DRC-ICP-MS the LOD was 0,020 µgL-1. The developed method was applied for determination of 15 elements in bovine semen samples of different breed used in reproduction programs and artificial insemination.

Os minerais são de extrema importância no metabolismo geral e no desempenho produtivo e reprodutivo dos bovinos. Atualmente, no Brasil, existem poucos estudos sobre o diagnóstico de deficiências minerais em bovinos, através de análise de macroelementos e elementos traço em fluidos biológicos. A maior parte das informações disponíveis limitam-se ao diagnóstico clínico de deficiências isoladas e à análise de elementos nas pastagens e no solo, que podem sugerir deficiências sub clínicas de alguns minerais, mas apresentam várias limitações e interferências. O objetivo deste trabalho foi desenvolver um método de análise simples, com introdução direta da amostra, utilizando a técnica de q-ICP-MS e DRC-ICP-MS, para determinação de Ca, Cu, Fe, Mg, Zn, I, Mo, As, Se, Ni, Co, Ba, Cs, Mn e Pb em sêmen bovino. Para realização das análises, foi utilizada calibração em meio aquoso e as amostras foram diluídas na proporção 1:50 em solução contendo 0,01% v/v Triton® X-100 e 0,5% v/v de ácido nítrico. Também foram avaliadas a calibração por ajuste de matriz e a análise das amostras após digestão por microondas, para confirmação dos resultados obtidos por introdução direta e calibração em meio aquoso. O DRC foi essencial para determinação de níquel. O gás de reação utilizado foi H2 e os parâmetros RPq e vazão do gás foram estudados para otimização do método. Os limites de detecção para determinação de 44Ca, 63Cu, 57Fe, 24Mg, 64Zn, 127I, 98Mo, 75As, 82Se, 59Co, 138Ba, 133Cs, 55Mn e 208Pb foram: 0,262; 0,003; 0,168; 0,004; 0,004; 0,026; 0,007; 0,007; 0,033; 0,002; 0,005; 0,002; 0,003; 0,002 µg L-1 respectivamente, e para determinação de 60Ni por DRC-ICP-MS o LD foi 0,020 µgL-1. O método desenvolvido foi aplicado para determinação de 15 elementos em amostras de sêmen de bovinos de diferentes raças usadas em programas de reprodução e inseminação artificial. / The minerals are of extreme importance in the general metabolism and in the productive and reproductive performance of the bovines. Nowadays, in Brazil, few studies exist on the diagnosis of mineral deficiencies in bovine, through macroelementos analysis and trace elements in biological fluids. Most of the available information is limited to the clinical diagnosis of isolated deficiencies and the analysis of elements in the pastures and in the soil, that can suggest sub clinical deficiencies of some minerals, but present several limitations and interferences. The objective of this work was to develop a method of simple analysis, with direct introduction of the sample, using the technique of q-ICP-MS and DRC-ICP-MS, for determination of Ca, Cu, Fe, Mg, Zn, I, Mo, As, Se, Ni, Co, Ba, Cs, Mn and Pb in bovine semen. Aqueous medium calibration was used in the analysis and the samples were diluted in the proportion 1:50 in solution containing 0,01% v/v Triton® X-100 and 0,5% v/v of nitric acid. They were also evaluated the matrix matching and the analysis of samples after digestion for microwave, for confirmation of the results obtained by direct introduction and calibration in aqueous medium. DRC went essential for nickel determination. The reaction gas used it was H2 and the parameters RPq and gas flow rate were studied for optimization of the method. The detection limits for determination of 44Ca, 63Cu, 57Fe, 24Mg, 64Zn, 127I, 98Mo, 75As, 82Se, 59Co, 138Ba, 133Cs, 55Mn and 208Pb were: 0,262; 0,003; 0,168; 0,004; 0,004; 0,026; 0,007; 0,007; 0,033; 0,002; 0,005; 0,002; 0,003; 0,002 µg L-1 respectively, and for determination of 60Ni for DRC-ICP-MS the LOD was 0,020 µgL-1. The developed method was applied for determination of 15 elements in bovine semen samples of different breed used in reproduction programs and artificial insemination.

El presente trabajo tiene el objetivo de analizar los rasgos humorísticos y figuras retóricas en La Colmena de Camilo José Cela. La tesina se basa en las teorías de la superioridad, de la descarga, de la incongruencia y las teorías sociológicas y antropológicas según el estudio de José Antonio Llera. Nuestra investigación ha examinado particularmente el humor negro, grotesco y la ironía presente en la obra de Cela. Hemos podido concluir y afirmar que Cela usa el humor y la ironía a través de descripciones grotescas las cuales forman parte de su critica social y como mecanismo de defensa. Hemos establecido que el autor usa el humor para reflejar su propia elección subjetiva de la realidad de la posguerra. Finalmente hemos constatado que el humor es algo añadido lo cual se muestra a través de sus comentarios omniscientes.

The presented thesis focuses on designing a cryogenic cell for the study of water ice in an environmental scanning electron microscope (ESEM). This cell allows the study ice in the temperature range 80 K – 300 K in a nitrogen gas environment with a pressure of up to 400 Pa. The cell is cooled by a flow cooling system, where liquid or gaseous nitrogen is used as a refrigerant. The cell consists of a double-walled vessel with vacuum insulation, a flow-through heat exchanger, a sample well, and a cooled cell lid. The heat exchanger was designed to be able to dissipate the heat load at the level of 1 W. The exchanger is equipped with an electric resistance heater with an output of approximately 60 W, enabling heating of the sample at speeds of up to 100 K·min-1. The design also includes an LN2 gateway located on the door of the vacuum chamber of the microscope, to which the capillaries of the heat exchanger for the intake and outlet of refrigerant are connected. During the experimental verification of the cryogenic cell in the test vacuum chamber with a pressure of GN2 ~ 400 Pa, the limit temperature of 77.5 K on the sample well was reached.

The essence of this diploma thesis is the design and implementation of software for laser ablation control. The paper describes laser ablation, hardware specifications of device and application requirements. The second part provides description of design and implementation of the actual application in NI LabView.

In this master's thesis, a numerical model of groundwater flow in a contaminated area of Hradec Králové was created. After that, a circulation well was introduced. Two circulation well variants, which differ in the amount of pumped water, were examined. All simulations were performed with the aid of a finite element solver Feflow 5.2. The values of hydraulic head resulting from the mathematical model are in a good agreement with those obtained from the field measurement. The groundwater flow present in the area of interest exhibits south to southwest direction. After introducing the circulation well, I focused on the influence of the amount of pumped water on the groundwater flow. The outcome of this observation was that during the higher volume pumping, the circulation cell is larger and therefore has a higher influence on the groundwater flow. I evaluated that it is more efficient to pump a higher amount of water in the investigated area.

This thesis is focused on increasing the senstitivity of gold determination by electrochemical volatile species generation using two different types of electrolytic cells in continuous flow setting. Externally heated quartz tube atomizer was used as means of atomization and detection of gold with atomic absorption spectrometer. Generation parameters were optimized for electrolytic cell with an ion exchange (nafion) membrane. After selection of new cathode material (Cu) the carrier gas (Ar) flow rate was optimized, where an additional inlet of carrier gas was found to have possitive effect on increasing the sensitivity of determination of gold and efficiency of volatile specie transport to the atomizer. Experiments with Antifoam B showed possitive effect on generation, thus calibration was carried out for optimized experimetal conditions reaching detection limit of 0,53 mg.dm−3 . The efficiency of volatile specie transfer from liquid to gaseous phase was determined between 60 - 65 % by measuring the residual gold content in liquid waste by F-AAS method. Subsequently the effieciency of electrolytic generation of volatile gold specie with radioactive tracer isotopes and autoradigraphy was determined to 0,6 %. These methods confirmed adsorption of generated species on apparatus surface. Using ICP-MS as...

The first aim of this work was to develop copper modified carbon felt electrode for detection of amino acids, which are not electrochemically active on ordinary carbon electrodes. Phenylalanine solution at a concentration 1.0 mmol dm-3 was chosen as the testing solution. Electrode modified with electrochemical deposition of copper from mixture of copper(II) sulphate and sodium sulphate provided very low responses which were decreasing during first measurements, apparently because of insufficient amount of copper. Therefore, further experiments were performed using copper microparticles as a modifier. Copper microparticles activated in nitric acid at a concentration 80 mmol dm-3 were applied at carbon felt by several techniques and in different parts of the felt, i.e. by stirring the felt in microparticles suspension, by dripping of the suspension to the part of the felt in contact with capillary (proximal), between two parts of the carbon felt (sandwich) and at a part of the carbon felt in contact with electrolyte in a measuring cell (distal). Electrodes modified in the distal and in the sandwich arrangement were chosen as the best ones. In the last part, calibration dependences for phenylalanine in concentration range from 0.025 mmol dm-3 to 1.0 mmol dm-3 were measured on the last two electrodes....

Esta tese tem como foco o desenvolvimento de procedimentos analíticos automáticos, visando as determinações fotométricas de vanádio e de estanho em águas e em alimentos empregando o processo de multicomutação em fluxo. Um microcontrolador da família PIC e um programa escrito em linguagem Visual Basic 6.0 foram empregados para controle dos dispositivos e aquisição de dados. A unidade de detecção foi construída empregando LED de alto brilho e celas de fluxo com longo caminho óptico (50-200 mm) para ganho em sensibilidade. O módulo de análises, empregando bombas solenoide como propulsores de fluido e o fotômetro foram integrados, formando uma unidade compacta. A determinação de vanádio em águas, mineral e de rio, foi baseada na redução do V(V) à V(IV) com ácido ascórbico e posterior complexação com Eriocromo Cianina R (ECR). Empregando uma cela de 150 mm, o sistema apresentou resposta linear de 0,02 a 1,00 mg L-1, limite de detecção estimado em 13 ?g L-1, coeficiente de variação de 0,87% (n=10) e frequência analítica de 47 determinações por hora. Recuperações entre 89 e 109% foram obtidas para adição de V(V) nas amostras de águas. O procedimento para a determinação de estanho em alimentos foi desenvolvido empregando bomba de multi-seringa como unidade de propulsão de fluidos, cela de fluxo com caminho óptico de 200 mm e parada de fluxo de 50 s. Baseado na reação do Sn(IV) com o violeta de pirocatecol (PCV) na presença de surfactantes, o sistema apresentou resposta linear de 0,10 a 1,25 mg L-1, limite de detecção estimado em 0,04 mg L-1, coeficiente de variação de 1,30% (n=10) e frequência analítica de 49 determinações por hora. Recuperações entre 95 e 115% foram obtidas com a adição de Sn(IV) às amostras de alimentos. / Automatic analytical procedures for photometric determinations of vanadium in water and tin in foods were developed using the multicommutation flow analysis process. A microcontroller of the PIC family and a software written in Visual Basic 6.0 language were used for devices control and data acquisition. Detection unit was designed to use high brightness LED and long optical pathlength flow cells (50-200 mm) to improve sensitivity. The flow analysis module using solenoid mini-pumps as fluid propelling devices and the photometer were integrated in order to form a compact unit. The determination of vanadium in mineral and river waters was based on the reduction of V(V) to V(IV) with ascorbic acid and subsequent complexation with Eriochrome Cyanine R (ECR). Employing flow cell of 150 mm, the system presented linear response between 0.02 and 1.00 mg L-1, detection limit of 13 ?g L-1, variation coefficient of 0.87% (n=10) and sampling throughput of 47 determinations per hour. Recoveries between 89 and 109% were attained for vanadium spiked to mineral and river water. The procedure for determination of tin in foods was development employing a multi-syringe pump as fluid propelling device, a flow cell with optical pathlength of 200 mm and stop flow of 50 s. The procedure was based on the reaction of Sn(IV) with pyrocatechol violet (PCV) in the presence of surfactants, presented linear response between 0.10 and 1.25 mg L-1, detection limit of 0.04 mg L-1, variation coefficient of 1.30% (n=10) and sampling throughput of 49 determination per hour. Recoveries between 95 and 115% were attained for tin spiked samples