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Application of a dielectric barrier discharge plasma atomizer to hydride generation atomic absorption spectrometry (HG-DBD-AAS)
Albrecht, Michal ; Kratzer, Jan (advisor) ; Červený, Václav (referee)
Atomization of plumbane in a novel dielectric barrier discharge (DBD) plasma atomizer has been optimized employing detection by atomic absorption spectrometry. The performance of the DBD atomizer was subsequently compared to that of a conventional externally heated quartz tube atomizer (QTA). Lead from a standard solution was converted to plumbane by chemical reduction with sodium borohydride using an identical hydride generator for both atomizers. Argon at a flow rate of 175 cm3 min-1 was found as the best discharge gas while the DBD power supply rate was optimized to 22 W. The inner surface of the DBD atomizer was passivated by dimethyldichlorosilane (DMDCS) resulting in a twofold increase of sensitivity. Sensitivity of 0.10 s ng-1 Pb and a limit of detection of 0.82 ng cm-3 Pb were reached in the DBD atomizer with DMDCS-modified surface under the optimum atomization conditions. Better performance was achieved in a QTA atomizer, in which detection limit of 0.59 ng cm-3 Pb was reached and sensitivity was doubled (0.22 s ng-1 Pb) in comparison with DMDCS- modified DBD.
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Using of chemical mercury cold vapor generation for speciation analysis of selected mercury compounds employing HPLC and AAS
Králová, Pavlína ; Červený, Václav (advisor) ; Kratzer, Jan (referee)
The aim of this diploma thesis was to verify the usability of the chemical generation of mercury cold vapor for speciation analysis of selected mercury compounds using high - performance liquid chromatography coupled within atomic absorption spectrometry in the determination of mercury in real tap water samples. In this work, mercuric chloride, methylmercury, ethylmercury and phenylmercury were selected as model analytes. In the first part, the working conditions of chemical generation of mercury cold vapor for each of the selected specie of mercury were optimized. Optimized equipment was used to measure the calibration dependence for each specie and the basic characteristics of the method were established. After optimization of the chemical generation, HPLC column was connected prior this derivatization step and in resulted combined apparatus HPLC - CVG - QTAAS, the separation step was optimized . At optimized conditions, the calibration dependence was measured for each specie and the basic characteristics of the developed method including HPLC separation were established. In conclusion, the proposed analytical method was tested on real flowing tap water samples. Because of low content of mercury species in these samples, the recovery of the method was established when comparing the signal of...
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The Comparison of Methods for Determination of Procaine in Medical Formulations
Baptistová, Adéla ; Nesměrák, Karel (advisor) ; Červený, Václav (referee)
The aim of this bachelor thesis was to compare four analytical methods for determination of procaine hydrochloride in medical formulations in terms of precision and measurement trueness, and its time, and financial cost. The selected methods are: titration with potassium bromate, titration with sodium nitrite, UV spectrophotometry, VIS spectrophotometry. Three injection solutions of different concentrations (0.2%, 0.5%, and 1.0% of procaine) were analysed. VIS spectrophotometry provides the most precise results, whereas determination by UV spectrophotometry is the least precise. Measurement trueness is found for UV spectrophotometry and both titrations. UV spectrophotometry is the cheapest method, while titration with sodium nitrite is the most expensive method. Titration with potassium bromate is the least time-consuming method, while VIS spectrophotometry is the most time- consuming method. Keywords: procaine, bromatometric titration, titration with sodium nitrite, UV and VIS spectrophotometry
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Interference study by arsenic determination using UV-photochemical generation of its volatile species with AAS detection
Smolejová, Jana ; Červený, Václav (advisor) ; Nesměrák, Karel (referee)
This thesis deals with the interference study of the UV-photochemical generation of arsenic volatile species with AAS detection and it searches for a suitable reaction modifier, which would improve sensitivity of the As determination. Interferences were classified into 3 groups according to their influence on the As UV-photochemical volatile species generation. Ni2+ , Cu2+ , Cl− and merkaptoethanol belong among the negative interferents. HNO3, Fe3+ , ethanol, SO4 2− , TiO2 and L-cysteine belong among the low-level interferents. Co2+ , acetonitrile, triethanolamine, selenite and Bi3+ belong to a group, which increases the absorbance of arsenic and could, therefore, be called positive interferents. Concentration of 10 mg l−1 of Bi3+ significantly increases the level of absorbance of arsenic. This effect was utilized during measurement of calibration dependence and Bi3+ ions were used as the reaction modifier. The figures of merit of this method with reaction modifier were obtained. Limit of detection was 18 µg l−1 , limit of quantification was 60 µg l−1 , sensitivity was 1.144·10−3 l µg−1 , repeatability was 4.5 % (relative standard deviation) a linear range was 60 - 500 µg l−1 . We achieved eleven times better absorbance by using this reaction modifier compared to UV-photochemical volatile species...
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Determination of Arsenic Using UV-photochemical Generation of the Volatile Species in Formic Acid Medium with AAS Detection
Vlčková, Anna ; Červený, Václav (advisor) ; Hraníček, Jakub (referee)
V této bakalářské práci byla nejprve sestavena aparatura pro stanovení arsenu pomocí UV-fotochemického generování jeho těkavé sloučeniny s AAS detekcí a byly optimalizovány experimentální podmínky navrhované metody. Klíčovými parametry byly: délka reakční cívky ozařované UV světlem; místo zavádění reakčního plynu (vodíku) před UV-fotoreaktor a nosného plynu (argonu) před UV-fotoreaktor a do separátoru fází a jejich průtoky; koncentrace kyseliny mravenčí v nosném roztoku a jeho průtoková rychlost a velikost dávkovaného objemu vzorku. Za optimálních podmínek navrhované metody byla naměřena kalibrační závislost. Pro porovnání výsledků bylo použito stanovení arsenu pomocí chemického generování jeho hydridu. Z porovnání těchto metod vychází chemické generování jednoznačně jako metoda citlivější, protože lze stanovovat koncentrace již od 5,7 ppb As, zatímco metodou UV-fotochemického generování lze stanovovat koncentrace až od 150 ppb As. Za stávajících podmínek je UV-fotochemické generování těkavých sloučenin z důvodu velmi nízké citlivosti (přibližně 16,5 % oproti chemickému generování) pro stanovení arsenu nevhodné.
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Development of post-column hydride generation for analysis of glutathione complexes of arsenic by HPLC-(HG)-ICP-MS
Bradyová, Michaela ; Matoušek, Tomáš (advisor) ; Červený, Václav (referee)
This thesis develops high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-HG-ICP-MS) method used for the analysis of glutathione arsenic complexes in biological samples. The aim of the thesis was to verify the suitability of this methods and to perform pilot studies on analysis of the enzymatic methylation assay containing glutathione and urine. Inclusion of post-column hydride generation step resolves the problem of changing sensitivity of ICP-MS with gradient elution. Using the standards of glutathione complexes, it was verified that the HPLC-HG-ICP-MS method can provide both qualitative and quantitative analysis of these complexes. The limit of detection was found at 5 pg/ml. Analysis of the methylation assay of arsenic with glutathione showed that only DMAsGS complex occurs in the assay during methylation. It was verified that the presence of the enzyme is required for the complex formation. In the samples of urine from unexposed people analyzed by HPLC- HG-ICP-MS and hydride generation-cryotrapping-inductively coupled plasma mass spectrometry (HG-CT-ICP-MS), only the presence of free pentavalent arsenic species was found, whereas neither glutathione complexes nor trivalent species could be observed.
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Analysis of Historical Pharmaceutical Preparations of Naloxone, Adrenaline and Ephedrine.
Nováková, Lucie ; Nesměrák, Karel (advisor) ; Červený, Václav (referee)
The aim of the thesis was to analyze the historical pharmaceutical preparations, including the determination of the active substance and identify theirs possible degradation products. A historical pharmaceutical preparation of naloxone was analyzed by mass spectrometry. Historical pharmaceutical preparations of adrenaline and ephedrine were analyzed by UHPLC-MS and were quantified using a calibration curve. In the historical injection solution of naloxone, "NARCAN", dated around 1980, there were no significant degradation products and the measured mass and UV spectrum was consistent with the spectrum of naloxone. The analyzed sample of naloxone was stable even after 35 years of storage. In the analyzed historical injection solution of adrenaline, "Adrenalin Hydrochlor., Dr. Heisler" (dated between 1917 and 1938) was determined 5.26 ± 0.11 % of the declared amount of adrenaline. In the measured spectras were noticeable degradation products, which have not been described in the literature yet and their identification was beyond the scope of this paper. The analyzed sample of adrenaline was almost completely degraded during about ninety years. The stability test carried out with four standard solutions of adrenaline proved influence of oxygen, light, temperature and time on the degradation of adrenaline. In...
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Extraction of Selected Mercury Compounds from Real Samples for Speciation Analysis Employing RP-HPLC-UV-CVG-QTAAS
Kolorosová, Alžběta ; Červený, Václav (advisor) ; Kratzer, Jan (referee)
The extraction of mercury species (methylmercury, ethylmercury, phenylmercury and inorganic mercury(II)) from fish tissue, its determination by reverse phase HPLC, UV-photochemical generation of cold vapour, and detection by atomic absorption spectrometry is described in this work. Various extraction agents and digestion methods were compared in order to find the best alternative. The mixture of 6.25% tetramethylammonium hydroxide and 0.05 mol·l-1 hydrochloride acid was chosen as the best extraction agent. In addition to the high extraction efficiency, the solution involved positively not only UV-photochemical generation, but also separation of observed species. On the contrary, the poor repeatability was achieved with the microwave-assisted digestion due to the proved sorption of mercury species on the Teflon vessels. Therefore, the extraction by high temperature (50-60 řC) in glass bottles was preferred. The results of the determination of the mercury species after the extraction from the real samples were compared to the outcomes obtained by AMA 254. The proposed extraction technique together with the RP-HPLC-UV-CVG-QTAAS is suitable for the speciation analysis of mercury.
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Speciation analysis of arsenic-glutathione complexes by ion-pairing HPLC-ICP-MS
Zušťáková, Veronika ; Matoušek, Tomáš (advisor) ; Červený, Václav (referee)
The thesis has focused on the separation of arsenic-glutathione species using ion-pairing high performance liquid chromatography with detection by inductively coupled plasma mass spectrometry. Species were separated on chromatographic column Prodigy ODS (3) using an aqueous mobile phase containing 4.7mM tetrabutylammonium hydroxide (TBAH), 2mM malonic acid and 4% methanol at pH 5.85 in the isocratic mode. Simple arsenic species - arsenite (iAsIII), arsenate (iAsV) monomethylarsenic acid (MAsIII), monomethylarsenous acid (MAsV), dimethylarsenic acid (DMAsIII) and dimethylarsenous acid (DMAsV), which served as arsenic standards to determine retention times, were successfully separated under these conditions. Arsenic-glutathione complexes As(GS)3, MAs(GS)2 and DMAs (GS) were not successfully separated. These complexes provided peaks of simple arsenic species. Peak broadening was observed in the first analysis of As(GS)3 and MAs(GS)2 complexes, which disappeared in subsequent analyses. This broadening probably represents a residual of glutathion complex which disintegrated to single species. Powered by TCPDF (www.tcpdf.org)
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Determination of acetylsalicylic acid by sequential injection analysis with spectrophotometric detection
Vrtalová, Martina ; Hraníček, Jakub (advisor) ; Červený, Václav (referee)
This diploma thesis is focused on the determination of acetylsalicylic acid using two methods of flow analysis; Flow Injection Analysis (FIA) and Sequential Injection Analysis (SIA) with spectrophotometric detection. The principle of determination is based on the acetylsalicylic acid decomposition to give salicylic ion. This ion reacts subsequently with Fe3+ ion in acidic solution leading to colored chelating complex Fe(SAL)+ . The increase of absorbance of this complex in its absorption maximum was used for analytical determination. Sodium salicylate (sodium salt of acetylsalicylic acid) was used as a standard substance. In the first part of this work, experimental arrangement for flow injection analysis was setup. Continuously the optimization of experimental conditions of acetylsalicylic acid determination was performed to obtain the higher sensitivity. Under the optimal conditions the basic characteristics of determination was measured. In the second part of this work, the commercial experimental instrument FIA Lab 3500 was used for determination. Optimization of experimental conditions and basic characteristic of determination by sequential injection analysis was performed as well. Developed methods for determination of acetylsalicylic acid with selected technique were verified by analyzing...
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