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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.
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Preparation of titanocene complexes with cytostatic properties
Dunlop, David ; Lamač, Martin (advisor) ; Demel, Jan (referee)
Cytotoxicity of titanocene dihalides has been a persistent topic in scientific literature, dating back to the 1970's. The intensively studied titanocene dichloride, which has disappointed in phase II clinical trials on humans, has been substituted by various titanocenes, which bear aryl-substituted cyclopentadienyl ligands. The activity of these complexes can be interestingly further improved via substitution of chloride ligands by fluorides. However, the mechanism of action of these complexes remains somewhat of a mystery, starting with their transport into the cells, stability under physiological conditions, etc. This thesis describes the preparation of several variously substituted titanocene dichlorides and difluorides. These complexes are a part of a larger series, which will help to further the understanding of structural effects on the cytotoxicity of titanocenes. All prepared complexes are characterized via 1 H ,13 C NMR and IR spectroscopy. Complexes containing fluoride ligands have also been characterized via 19 F NMR spectroscopy, melting points, RTG structural analysis (if monocrystals were available) and elemental analysis. Keywords: titanocene dihalides, organometallics, cytotoxicity, cancer cells
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Development of novel photoactive cationic zirconocene complexes
Dunlop, David ; Lamač, Martin (advisor) ; Schulz, Jiří (referee)
Title: Development of novel photoactive cationic zirconocene complexes Author: Bc. David Dunlop Department: Department of inorganic chemistry Supervisor: RNDr. Martin Lamač Ph.D. Advisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Abstract: Environmental concerns have brought about an unprecedented demand for sustainable energy sources among which electromagnetic radiation, light, currently dominates. Development of novel light- harvesting compounds and materials is at the forefront of current science, as it is essential to further our technological progress. This thesis contributes to the field by development of novel photoactive cationic group 4 metallocene complexes stabilized by pendant imine and pyridinyl donor groups, or N,O-donor aromatic ligands, as crystalline [B(C6F5)4]− salts. The complexes are prepared either by protonation of the intramolecularly bound imine moiety by PhNMe2H[B(C6F5)4] or by chloride ligand abstraction, by Li[B(C6F5)4]·2.5Et2O or in situ generated Et3Si[B(C6F5)4]. Prepared compounds were characterized by NMR spectroscopy. Solid state structures of the compounds were determined by X-ray diffraction analysis. The cationic complexes of Zr and Hf exhibited significantly enhanced luminescence which originates from triplet ligand-to-metal (3 LMCT) excited states with lifetimes of up to...
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Preparation of titanocene complexes with cytostatic properties
Dunlop, David ; Lamač, Martin (advisor) ; Demel, Jan (referee)
Cytotoxicity of titanocene dihalides has been a persistent topic in scientific literature, dating back to the 1970's. The intensively studied titanocene dichloride, which has disappointed in phase II clinical trials on humans, has been substituted by various titanocenes, which bear aryl-substituted cyclopentadienyl ligands. The activity of these complexes can be interestingly further improved via substitution of chloride ligands by fluorides. However, the mechanism of action of these complexes remains somewhat of a mystery, starting with their transport into the cells, stability under physiological conditions, etc. This thesis describes the preparation of several variously substituted titanocene dichlorides and difluorides. These complexes are a part of a larger series, which will help to further the understanding of structural effects on the cytotoxicity of titanocenes. All prepared complexes are characterized via 1 H ,13 C NMR and IR spectroscopy. Complexes containing fluoride ligands have also been characterized via 19 F NMR spectroscopy, melting points, RTG structural analysis (if monocrystals were available) and elemental analysis. Keywords: titanocene dihalides, organometallics, cytotoxicity, cancer cells
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