|
|
Oxidation Processes of N-methylguanines
Trnková, L. ; Třísková, I. ; Liška, Alan ; Ludvík, Jiří
The oxidation processes of N-methylguanines were investigated in both experimental and\ntheoretical way. Voltammetric oxidation potentials of guanine and its methyl analogues,\nacquired on polymer pencil graphite electrode (pPeGE), were compared with the HOMO\n(SOMO) energies calculated by density functional (DFT) methods. Our study contributes to\nunderstanding not only the oxidation processes of methylated guanines but also their role in\nepigenetics.
|
|
|
Differences in Electrochemical Reduction of Mono- and Polynuclear Acylgermanes
Šimková, Ludmila ; Dunlop, David ; Liška, Alan ; Ludvík, Jiří
Recently, titanocene derivatives have been investigated in term of their potential use as\ncytostatics in the treatment of oncological diseases. The potentials for reduction or oxidation of\nindividual substances are one of the key properties which fundamentally affect the cytostatic\nefficiency. Our previous results led us to investigate the redox properties of series of titanocene\ndifluoride and dichloride derivatives. This study is mainly focused on the effect of the\nsubstitution of cyclopentadienyl ring and the halide anion on the redox properties of the\nderivative.
|
|
|
Differences in Electrochemical Reduction of Mono- and Polynuclear Acylgermanes
Liška, Alan ; Frühwirt, P. ; Haas, M. ; Ludvík, Jiří ; Gescheidt-Demmer, G.
Ail the studied compounds accept first electron under formation a stable anion radical. The\ncorresponding reduction potentials in aprotic media depend on electronic (inductive,\nmesomeric) properties of the substituents, their number, and position. Here, aromatic acyl group\n(benzoyl group with various substitution on aromatic ring) is the principal substituent. The\nredox properties of presented organoelement compounds with central heteroatom Ge (Si, Sn)\nare controlled by peripheral carbonyl groups (in role of redox centers), their number, and\naromatic ring substitution. The measured first reduction potentials E1 values are found in wide\nrange (> 900 mV) due to the fact that the redox centers are carbony 1 groups connected through\nheteroatom in case of acylgermanes, while for di- and trinuclear derivatives (which are\nmolecules with multiple redox centers) the easiest reducible center is the bridging aromatic unit\ninfluenced by the closest carbonyl groups. Thus, it is possible to distinguish both groups ofnonequivalent\ncarbonyl substituents.
|
|
|
Electrochemistry of Phospholes
Koláčná, Lucie ; Liška, Alan ; Ludvík, Jiří
Seventeen pentasubstituted phospholes with expected application in organic electronics were\nsynthesized and characterized electrochemically and by UV-vis spectra. Quantum chemical\ncalculations ofredox potentials and HOMO-LUMO energies were performed and experimental\nand theoretical data were successfully correlated. Tuning of redox properties can be achieved\nby combination of induction and resonance effects of substituents, extension / diminution of\nthe pi- delocalized system and by steric changes which affect intramolecular electron\ncommunication.
|
|
|
Electrochemistry of macrocyclic complexes
Kaďorková, Veronika ; Liška, Alan (advisor) ; Kotek, Jan (referee)
The present thesis summarizes fundamental electrochemical properties of copper(II) complexes derived from three cyclame-like macrocyclic ligands. Target application of the studied complexes is radioimaging in medicine. The complexes were studied by means of DC-polarography and cyclic voltammery on mercury hanging drop electrode in buffered media (0.1M sodium acetate, pH 5) upon mixing of the ligand and copper(II) sulfate stock solutions. All three complexes undergo a single two-electron irreversible reduction process yielding free ligand and copper amalgam. The apparent thermodynamic stability of the investigated complexes (expressed as negative shift of the observed reduction potentials relatively to copper(II) sulfate) correlates to structural motifs employed in the individual ligand molecules. Presence of the bridged moiety as well as the carboxylate group seems to enhance the overall stability whereas the phenolic oxygen atoms in role of donor atoms seem to be less efficient.
|
|
|
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
|
|
|
Electrochemistry of Calixarenes
Liška, Alan ; Ludvík, Jiří (advisor) ; Zima, Jiří (referee) ; Cibulka, Radek (referee)
In the present thesis, both the published and the "ready-to-be-submitted" results concerning electrochemistry of calixarenes are summarized. The main focus is given to the detailed interpretation of experimental data, acquired during a systematic study of electroactive calixarene derivatives. The experiments were conducted under aprotic conditions (DMF) on mercury electrodes (mainly cyclic voltammetry and DC-polarography). It is demonstrated that electrochemistry should not serve only for redox characterization of studied compounds, but it offers a great number of other valuable information. The subject matter of the study are the calix[4]arenes (prevalently in the cone-conformation) which bear one to four reducible or oxidizable substituents ("redox probes") at various positions in order to be electrochemically investigable. Nitro- and nitroso compounds together with aldehydes, ketones, nitriles, aldoximes, carboxylic acids and corresponding esters, sulphones and esters of sulphonic acids are the most discussed compound series. Their relationship between structure and electrochemical response is presented in new connections ("stereoelectrochemistry"), in other words, how the redox probe position on the benzene ring (para-/meta-), bridging groups, or adjacent vs. opposite aromatic units...
|
|
|
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.
|
|
|
Electrochemistry of Calixarenes
Liška, Alan
In the present thesis, both the published and the "ready-to-be-submitted" results concerning electrochemistry of calixarenes are summarized. The main focus is given to the detailed interpretation of experimental data, acquired during a systematic study of electroactive calixarene derivatives. The experiments were conducted under aprotic conditions (DMF) on mercury electrodes (mainly cyclic voltammetry and DC-polarography). It is demonstrated that electrochemistry should not serve only for redox characterization of studied compounds, but it offers a great number of other valuable information. The subject matter of the study are the calix[4]arenes (prevalently in the cone-conformation) which bear one to four reducible or oxidizable substituents ("redox probes") at various positions in order to be electrochemically investigable. Nitro- and nitroso compounds together with aldehydes, ketones, nitriles, aldoximes, carboxylic acids and corresponding esters, sulphones and esters of sulphonic acids are the most discussed compound series. Their relationship between structure and electrochemical response is presented in new connections ("stereoelectrochemistry"), in other words, how the redox probe position on the benzene ring (para-/meta-), bridging groups, or adjacent vs. opposite aromatic units...
|
|
|
Electrochemistry of Calixarenes
Liška, Alan
In the present thesis, both the published and the "ready-to-be-submitted" results concerning electrochemistry of calixarenes are summarized. The main focus is given to the detailed interpretation of experimental data, acquired during a systematic study of electroactive calixarene derivatives. The experiments were conducted under aprotic conditions (DMF) on mercury electrodes (mainly cyclic voltammetry and DC-polarography). It is demonstrated that electrochemistry should not serve only for redox characterization of studied compounds, but it offers a great number of other valuable information. The subject matter of the study are the calix[4]arenes (prevalently in the cone-conformation) which bear one to four reducible or oxidizable substituents ("redox probes") at various positions in order to be electrochemically investigable. Nitro- and nitroso compounds together with aldehydes, ketones, nitriles, aldoximes, carboxylic acids and corresponding esters, sulphones and esters of sulphonic acids are the most discussed compound series. Their relationship between structure and electrochemical response is presented in new connections ("stereoelectrochemistry"), in other words, how the redox probe position on the benzene ring (para-/meta-), bridging groups, or adjacent vs. opposite aromatic units...
|
guest ::
RSS feed.