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Electrochemistry of Nitrocalixarenes
Liška, Alan ; Vojtíšek, Pavel (advisor) ; Cibulka, Radek (referee)
In this diploma thesis a detailed investigation of the step-by-step reduction mechanism of cone-mono-, di-, tri and tetranitrocalix[4]arenes (in non-aqueous DMF) is presented. The intramolecular interaction of reducible (and reduced) centers and its consequences for the geometry of the starting molecule was discussed including the character of radicalic intermediates and their spin state. It was found, that the electrochemically generated radical anions of nitrogroups (unlike their starting electroneutral state) can act as ligands. Therefore, a study of complex formation equilibria of cone-tetranitrocalix[4]arenes with alkali metal cations followed. The possible use of a "stereoelectrochemical" approach (the relationship between geometry or conformation of the molecule and its electrochemical data) was demonstrated in describing and explaining conformational and electrochemical differences between two isomeric dinitrocalix[4]arenes. Finally, a new series of 1,3-alt-tetranitrothiacalix[4]arenes was electrochemically characterized and compared with the "classic" calixarene derivatives. Key words: electrochemistry, calixarenes, stereochemistry
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Exectrochemical methods as tools for study complex macrocyclic moleculs
Liška, Alan ; Vojtíšek, Pavel (advisor) ; Liška, František (referee)
By means of electrochemical techniques, the electroreduction of polynitrocalix[4]arenes - molecules with multiple redox centers - was investigated and described. Based on interpretation of experimental data and on their correlation with quantum chemical calculations the relationship between structure and redox properties of the title molecules was revealed and discussed. It was shown that the tetranitrocalix[4]arenes involve two different couples of equivalent nitrogroups, what confirms experimentally the pinched shape of the molecule even in solution. The sequence of reduction steps was determined and the corresponding mechanism described. In the first part of the thesis different reduction mechanisms of p-substituted nitroaromates were found in dependence on substitution. It points to an important influence of lower ring substitution on the redox properties of the whole tetranitrocalix[4]arene.
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Electrochemistry of Nitrocalixarenes
Liška, Alan ; Vojtíšek, Pavel (advisor) ; Cibulka, Radek (referee)
In this diploma thesis a detailed investigation of the step-by-step reduction mechanism of cone-mono-, di-, tri and tetranitrocalix[4]arenes (in non-aqueous DMF) is presented. The intramolecular interaction of reducible (and reduced) centers and its consequences for the geometry of the starting molecule was discussed including the character of radicalic intermediates and their spin state. It was found, that the electrochemically generated radical anions of nitrogroups (unlike their starting electroneutral state) can act as ligands. Therefore, a study of complex formation equilibria of cone-tetranitrocalix[4]arenes with alkali metal cations followed. The possible use of a "stereoelectrochemical" approach (the relationship between geometry or conformation of the molecule and its electrochemical data) was demonstrated in describing and explaining conformational and electrochemical differences between two isomeric dinitrocalix[4]arenes. Finally, a new series of 1,3-alt-tetranitrothiacalix[4]arenes was electrochemically characterized and compared with the "classic" calixarene derivatives. Key words: electrochemistry, calixarenes, stereochemistry
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Exectrochemical methods as tools for study complex macrocyclic moleculs
Liška, Alan ; Vojtíšek, Pavel (advisor) ; Liška, František (referee)
By means of electrochemical techniques, the electroreduction of polynitrocalix[4]arenes - molecules with multiple redox centers - was investigated and described. Based on interpretation of experimental data and on their correlation with quantum chemical calculations the relationship between structure and redox properties of the title molecules was revealed and discussed. It was shown that the tetranitrocalix[4]arenes involve two different couples of equivalent nitrogroups, what confirms experimentally the pinched shape of the molecule even in solution. The sequence of reduction steps was determined and the corresponding mechanism described. In the first part of the thesis different reduction mechanisms of p-substituted nitroaromates were found in dependence on substitution. It points to an important influence of lower ring substitution on the redox properties of the whole tetranitrocalix[4]arene.
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Validation of macromolecular crystal structures
Řezáčová, Pavlína
X-ray crystallography is the main technique of macromolecular structure determination. Typical problems of protein crystallography diffraction data measured at limited resolution and inaccurate phase informacion adversely affect the quality of electron density maps and consequently the quality of the final model. Currently, there are many methods of protein quality validation. These can be subdivided into two main groups The first group assesses the model quality by evaluating the agreement of the model with the diffraction data. The second group of structure validation methods is based on comparison of the macromolecular model geometrical parameters with standards values derived from the crystal structures of small molecules or high-resolution macromolecular structures. This work is focused on introduction to widely used macromolecular structure-validation software. The main global quality criteria and reliable indicators for detecting local errors are summarized.
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