|
|
Preparation of titanium and zirconium metallocene complexes with pendant nitrile groups
Večeřa, Miloš ; Štěpnička, Petr (advisor) ; Vojtíšek, Pavel (referee)
Preparation of metallocene complexes of titanium and zirconium with pendant nitrile groups Miloš Večeřa bachelor thesis Abstract: Two cyclopentadienide salts with pendant nitrile groups were prepared in the form of their corresponding lithium salts and these salts were utilized for the preparation of titanium and zirconium metallocene complexes. One of the ligands was already described in the literature, while the other as well as all the prepared group 4 metallocene complexes are new compounds. Starting materials for these syntheses were 6,6-dimethylfulvene and spiro[2.4]hepta-4,6-diene which, upon a nucleophilic attack by 2-lithio-2-methylpropanenitrile, afforded the corresponding substituted lithium cyclopentadienides, which were characterized by 1 H and 13 C NMR spectroscopy and infrared spectroscopy. Then lithium salts were reacted with Cp*TiCl3 and Cp*ZrCl3 to give the corresponding metallocene dichlorides. Solid-state structures of the prepared titanocene dichlorides were elucidated by means of single crystal X-ray diffraction analysis. The obtained structures allowed a comparison with the known structures of the previously prepared homologous derivative. Unfortunately the corresponding zirconocene dichlorides did not crystallize. Moreover, all the newly prepared metallocenes were characterized by 1...
|
|
|
Salts of 2-aminoethanol and ferrocene-based acids
Zábranský, Martin ; Štěpnička, Petr (advisor) ; Němec, Ivan (referee)
Combination of the compact but sterically flexible ferrocene scaffold with intermolecular binding potential and conformational variability of (2-hydroxyethyl)ammonium structural motif was utilised in the construction of solid crystalline materials. Crystallisation in systems containing ferrocenecarboxylic, 2-ferrocenylacetic, 3-ferrocenylpropionic, 3-ferrocenyl- acrylic, 3-ferrocenylacrylic, 3-ferrocenylpropiolic, ferrocene-1,1'-dicarboxylic or ferrocene- sulfonic acid with 2-aminoethanol afforded crystals of the corresponding salts. The resulting crystalline products were characterised with the usual methods (proton nuclear magnetic resonance, infrared spectroscopy, elemental analysis) and their crystal structures were determined by means of single-crystal X-ray diffraction analysis. The crystal structures of the salts mentioned above usually contain rather complicated two dimensional networks of charge-assisted hydrogen bonds. With the aim of studying potentially more simple hydrogen-bonded structures, additional crystallisation experiments were conducted in systems of ferrocenecarboxylic acid and 2-(methylamino)ethanol or 2-(dimethylamino)ethanol. These experiments yielded simple salt of the former amine and adducts of salts of both bases with ferrocenecarboxylic acid in the ratio of 1:1. The...
|
|
| |
|
|
Mineralogical analysis of historical paintings
Čermáková, Zdeňka ; Hradil, David (advisor) ; Kanický, Viktor (referee) ; Artioli, Gilberto (referee)
Historical painted works of art have a very complex inner structure. The period painting technique led to the execution of a ground layer followed by several layers of underpainting and a top paint layer, over which a layer of glaze has been applied to increase the resistance to external wear. Each of these colour layers is composed of a dye or a pigment (or their mixture) bound by organic binder. Throughout the history, pigments were commonly prepared from minerals, either extracted from natural deposits or created artificially. In these heterogeneous layers containing both inorganic and organic components, undesirable degradation changes either driven by processes taking place directly in the colour layer or influenced by external agents may occur. Mineralogical approach, which focuses primarily on the structure of studied pigments, helps in the clarification of the occurring processes, in the determination of conditions leading to degradation as well as in the identification of original/degradation phases. Furthermore, it can be profitably applied in the micro- analysis of mineral pigments present in tiny micro-samples obtained from works of art, contributes to the artwork's provenance/authorship studies and the determination of regional provenance of the employed mineral pigments. This Ph.D....
|
|
|
Optimisation of Isolation Procedure and Characterization of Amorphous PHB granules
Kratochvíl, Zdeněk ; Obruča, Stanislav (referee) ; Kalina, Michal (advisor)
First artificial PHB granules were prepared under the terms of this thesis. The effect of used PHB solvent, ultrasonic bath temperature and time, solvent evaporation temperature and stabilizing agent nature was investigated using dynamic and electrophoretic light scattering. The most proper parameters were demonstrated at samples which were prepared by dissolving of PHB in chloroform, stabilizing with CTAB or lecithin, ultrasonifying at 35 °C followed by chloroform evaporating at 60 °C. Based on ATR-FTIR and Raman spectroscopy results, it was found out that PHB within the artificial granules were in crystalline form. The native PHB granules were isolated from Cupriavidus necator using either lysosyme, deoxyribonuclease and cell disruption by ultrasonification or digestion with alcalase, SDS and EDTA. Granules obtained by both isolation procedures were characterized by ATR-FTIR, Raman spectroscopy, light scattering techniques and DSC. According to the analyses results, the second mentioned procedure turned out to be more effective for obtaining the polymer in amorphous state. Furthermore, the polymer within granules recovered by using this procedure was thermally more stable. Last but not least, the native PHB granules samples were exposed to effect of acetone, lipase and sodium hypochlorite, assuming that polymer crystallinity should be increased by these chemicals in varying degrees. The highest degree of crystallinity was achieved after their treatment with lipase.
|
|
|
Fourier transform infrared spectroscopy: application in a study of transient species in discharge and ablation plasma
Kubelík, Petr ; Civiš, Svatopluk (advisor) ; Wild, Jan (referee) ; Rohlena, Karel (referee)
The present dissertation consists of two thematically related parts. The first one (includes two publications) deals with the study of chemical pro- cesses and spectroscopy of highly reactive particles produced in the discharge plasma. This part includes the analysis of ro-vibronic CN radical transitions in the infrared region and the study of chemical reactions in pulsed dischar- ges. The discharge was used as a tool for research of decomposition of simple precursors (acetonitrile, formamide and BrCN) and the subsequent formation of intermediates and reaction products in plasma. The obtained experimental results were interpreted using a numerical model developed in context of this work and used to simulate the kinetics of the studied systems. The second part (includes seven works) is aimed at high-resolved spectro- scopy of metals in the ablation plasma. A total of six different metals were studied: Au, Ag, Cu, Cs, K and Na. The main motivation for spectroscopic research on metals in the infrared region is to obtain information on atomic metals transitions, which are particularly important for astronomical identi- fication of lines in the spectra of stars and their spectroscopic assignments. Each publication contains a summary of the analyzed atomic transitions of which a considerable portion had not...
|
|
|
Spectroscopic Investigation of Lattice Dynamics in Multidomain Ferroelectrics
John Vakkechalil, Elizabeth ; Hlinka, Jiří (advisor) ; Hlídek, Pavel (referee) ; Hehlen, Bernard (referee)
Title: Spectroscopic investigations of lattice dynamics in multidomain ferroelectrics Author: Elizabeth Vakkechalil John Department: Department of Condensed Matter Physics Institution: Department of Dielectrics, Institute of Physics, AVČR, Na Slovance 2, Praha 8, 182 21, Czech Republic. Supervisor: Ing. Jiří Hlinka, PhD., Department of Dielectrics, Institute of Physics, AVČR., Na Slovance 2, Praha 8, 182 21, Czech Republic. Consultants: RNDr. Stanislav Kamba CSc., Ing. Ivan Gregora CSc. Fyzikální ústav AVČR, Na Slovance 2, Praha 8, 182 21, Czech Republic. Abstract: Lead based ferroelectric perovskites exhibit attractive physical and structural properties. Ferroelectric domains are known to have a very essential impact on dielectric and piezoelectric properties of ferroelectrics. Tailoring of domain structures allows to change the macroscopic symmetry of the material and to purposely modify its average tensor properties. Ferroelastic domains play also a key role in physics of epitaxial ferroelectric films. Here we studied signature of domain structure in PbTiO3 thin film grown by metalorganic chemical vapor deposition technique on different substrates, namely LaAlO3, MgO, NdGaO3, SrTiO3 (100), SrTiO3 (110), SrTiO3 (111) doped with 0.5% Nb and LSAT. Certain aspects of domain structure can be...
|
|
|
Application of vibrational spectroscopy to analysis of artwork - mortars
Křížová, Iva ; Němec, Ivan (advisor) ; Hynek, Radovan (referee)
The aim of this work was to determine the possibility of identifying the protein and lipid additives, such as blood, gelatin, curd, lard or eggs, in the model samples of lime based mortars using infrared spectroscopy. We have focused on the reflectance techniques of infrared spectroscopy, and we proved that by these methods can be determined the presence of additives, down to tenths percent by weight. Detailed resolution of lipid and protein additives can be achieved only for samples containing at least one weight percent of additive. There were not observed any spectral changes which can be correlated with performed curing and aging of prepared model samples.
|
|
|
Methods for determination of hyaluronan
Černá, Lucie ; Venerová, Tereza (referee) ; Pekař, Miloslav (advisor)
This thesis deals with a summary of individual method for determining of hyaluronan concentration, especially in aqueous solutions. Selected methods were compared to their functionality in university workplace. Any functional methods may be used for many purposes in university workplace in research of materials based on hyaluronan. It has been studied usability to assess residual content of hyaluronan in supernatant of gel formed from hyaluronan and surfuctant, in this thesis. We choosed sptectrophotometric methods, especially with UV spectroscopy and IR spectroscopy. Two precipitation methods using alcian blue were also tested. As the most reliable, the least demanding and specific method seems to be the method using IR spectroscopy, thanks to it we are able to determine the concentration of HA from 0.01 %. With this method, it has been found, that if there will be located some amount of HA in supernatant, it will be below the detection limit of assay. The remanining methods were modified to help determine the concentrations of HA, but works only in aqueous solutions. A possible variation for determination of very low concentrations of HA may be the method using ELISA kits. However their cost is higher than the above-mentioned methods.
|
|
|
Study of Optical Properties of Metallic Structures and Their Applications in Nano-Optics
Neuman, Tomáš ; Munzar,, Dominik (referee) ; Kalousek, Radek (advisor)
Interaction of metallic structures with electromagnetic radiation is a living topic of near-field optics including plasmonics and nanophotonics. The field-matter interaction treated on the subwavelength scale opens the path to a wide range of applications, among others to different variants of the surface enhanced spectroscopy. In this thesis we theoretically describe how the near-field properties of the metallic structures can be accessed by a probe of near-field scanning optical microscope. Formation of the signal in the near-field microscopy utilizing weakly interacting probes is discussed. Further, we elucidate the mechanism of the surface enhanced infrared spectroscopy. We utilize a model example of linear dipole antennas interacting with sample structures. A close connection is found between the spectroscopic signal and signal of the scattering type near-field optical microscopy.
|
guest ::
