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Ternary macrocyclic complexes of metals with fluoride anions
Kuncová, Lucie ; Kubíček, Vojtěch (advisor) ; Schulz, Jiří (referee)
The aim of this thesis was to synthesize three ligands derived from mackrocycle TACN, which were previously investigated in our laboratory group, and subsequently prepare gallium and aluminum complexes with these ligands for the study of coordination properties. The complexes were characterized by NMR, HPLC-MS and EA. For the complexes that were prepared, data on the ability to bind fluoride anions (i.e. the formation of ternary macrocyclic complexes) were measured using fluoride ion-selective electrode. Dissociation equilibria at pH = 8-10 were also studied for the complex [Ga(L1)] that had the highest percentage of bound fluorine anions (~ 95%).
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Synthesis and properties of supramolecular polymers
Vitvarová, Tereza ; Vohlídal, Jiří (advisor) ; Jindřich, Jindřich (referee) ; Royal, Guy (referee)
New π-conjugated building blocks (unimers) for metallo-supramolecular polymers (MSPs), whose comprise: (i) substituted phosphole ring surrounded by two thiophene rings as the central block, (ii) 2,2':6',2''-terpyridine-4'-yl (tpy) end-groups as ion-selectors, and (iii) different linkers inserted between the central block and tpy end-groups, are described. Chemical and physical properties of those unimers were studied with attention on correlation between properties and structure of unimers. For example the unimer without linkers shows the UV/vis absorption maximum red shifted about 60 to 100 nm compared to bis(tpy)terthiophenes, which proves that replacing of the thiophene with phosphole unit significantly enhances the delocalization of electrons within the unimer molecule and significant area of absorption spectra can be covered. Introduction of linkers (ethynediyl, ethynediyl-thiophene-2,5-diyl, ethynediyl-1,4-phenylene) has a minor effect on the bandgap energy. All prepared unimers underwent self-assembling process with various metal ions (Co2+ , Cu2+ , Fe2+ , Ni2+ and Zn2+ ) resulting into metallo-supramolecular polymers. Three stages of the assembly of unimers into related MSPs were observed and characterized by absorption, fluorescence spectroscopy and size exclusion chromatography: 1)...
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Gallium complexes for molecular imaging of bone tissue
Holub, Jan ; Kubíček, Vojtěch (advisor) ; Vojtíšek, Pavel (referee)
Title: Gallium Complexes for Molecular Imaging of Bone Tissue Author: Bc. Jan Holub Department of Inorganic Chemistry, Faculty of Science, Charles University Supervisor: RNDr. Vojtěch Kubíček, PhD. Supervisor's Email address: kubicek@natur.cuni.cz ABSTRACT This thesis is focused on preparing new ligands for selective complexation of gallium, which might serve as potential radiopharmaceuticals for 68 Ga-PET bone imaging. Two new ligands were prepared, combining 1,4,7-triazacyclonone-1,4-diacetic acid macrocyclic skeleton and bis(phosphonate) pendant arm, bound to the remaining free nitrogen atom on the macrocycle. Macrocyclic skeleton is responsible for high kinetic and thermodynamic stability of the Ga3+ complex and the bis(phosphonate) pendant arm insures selective delivery of the complex to the bone tissue. Both new ligands were fully characterized by NMR and mass spectroscopy. Complexation of Ga3+ was studied by 31 P and 71 Ga NMR spectroscopy. Binding to bone tissue was simulated by adsorption of the complexes to hydroxoapatite. Radiochemical experiments including study of 68 Ga complexation kinetics and basic in-vivo experiments including biodistribution studies and PET examination were done in cooperation with Johannes-Gutenberg Universität Mainz in Germany. Data obtained from these experiments were...
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Synthesis and properties of supramolecular polymers
Vitvarová, Tereza
New π-conjugated building blocks (unimers) for metallo-supramolecular polymers (MSPs), whose comprise: (i) substituted phosphole ring surrounded by two thiophene rings as the central block, (ii) 2,2':6',2''-terpyridine-4'-yl (tpy) end-groups as ion-selectors, and (iii) different linkers inserted between the central block and tpy end-groups, are described. Chemical and physical properties of those unimers were studied with attention on correlation between properties and structure of unimers. For example the unimer without linkers shows the UV/vis absorption maximum red shifted about 60 to 100 nm compared to bis(tpy)terthiophenes, which proves that replacing of the thiophene with phosphole unit significantly enhances the delocalization of electrons within the unimer molecule and significant area of absorption spectra can be covered. Introduction of linkers (ethynediyl, ethynediyl-thiophene-2,5-diyl, ethynediyl-1,4-phenylene) has a minor effect on the bandgap energy. All prepared unimers underwent self-assembling process with various metal ions (Co2+ , Cu2+ , Fe2+ , Ni2+ and Zn2+ ) resulting into metallo-supramolecular polymers. Three stages of the assembly of unimers into related MSPs were observed and characterized by absorption, fluorescence spectroscopy and size exclusion chromatography: 1)...
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Synthesis and properties of supramolecular polymers
Vitvarová, Tereza
New π-conjugated building blocks (unimers) for metallo-supramolecular polymers (MSPs), whose comprise: (i) substituted phosphole ring surrounded by two thiophene rings as the central block, (ii) 2,2':6',2''-terpyridine-4'-yl (tpy) end-groups as ion-selectors, and (iii) different linkers inserted between the central block and tpy end-groups, are described. Chemical and physical properties of those unimers were studied with attention on correlation between properties and structure of unimers. For example the unimer without linkers shows the UV/vis absorption maximum red shifted about 60 to 100 nm compared to bis(tpy)terthiophenes, which proves that replacing of the thiophene with phosphole unit significantly enhances the delocalization of electrons within the unimer molecule and significant area of absorption spectra can be covered. Introduction of linkers (ethynediyl, ethynediyl-thiophene-2,5-diyl, ethynediyl-1,4-phenylene) has a minor effect on the bandgap energy. All prepared unimers underwent self-assembling process with various metal ions (Co2+ , Cu2+ , Fe2+ , Ni2+ and Zn2+ ) resulting into metallo-supramolecular polymers. Three stages of the assembly of unimers into related MSPs were observed and characterized by absorption, fluorescence spectroscopy and size exclusion chromatography: 1)...
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Synthesis and properties of supramolecular polymers
Vitvarová, Tereza ; Vohlídal, Jiří (advisor) ; Jindřich, Jindřich (referee) ; Royal, Guy (referee)
New π-conjugated building blocks (unimers) for metallo-supramolecular polymers (MSPs), whose comprise: (i) substituted phosphole ring surrounded by two thiophene rings as the central block, (ii) 2,2':6',2''-terpyridine-4'-yl (tpy) end-groups as ion-selectors, and (iii) different linkers inserted between the central block and tpy end-groups, are described. Chemical and physical properties of those unimers were studied with attention on correlation between properties and structure of unimers. For example the unimer without linkers shows the UV/vis absorption maximum red shifted about 60 to 100 nm compared to bis(tpy)terthiophenes, which proves that replacing of the thiophene with phosphole unit significantly enhances the delocalization of electrons within the unimer molecule and significant area of absorption spectra can be covered. Introduction of linkers (ethynediyl, ethynediyl-thiophene-2,5-diyl, ethynediyl-1,4-phenylene) has a minor effect on the bandgap energy. All prepared unimers underwent self-assembling process with various metal ions (Co2+ , Cu2+ , Fe2+ , Ni2+ and Zn2+ ) resulting into metallo-supramolecular polymers. Three stages of the assembly of unimers into related MSPs were observed and characterized by absorption, fluorescence spectroscopy and size exclusion chromatography: 1)...
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Geminal bis(phosphinates)
David, Tomáš ; Lukeš, Ivan (advisor) ; Grüner, Bohumír (referee) ; Růžička, Aleš (referee)
Slow complexation is one of the major limitations of current macrocyclic chela- tors utilized in nuclear medicine for complexation of metal radionuclides. This property can be improved by ligand design. Among metal radioisotopes, the copper ones (e.g. 60Cu, 61Cu, 62Cu, 64Cu and 67Cu) have become commonly available in recent years and cyclam-derived ligands are the most suitable ligands for Cu2+ complexation. To alter the complexation rate, bis(phosphinic acid) group is promising unit as it is able to complex metal ions in acidic solu- tions. However, geminal bis(phosphinates) represent poorly studied group of compounds and, thus, it is challenging to uncover their properties. Several simple amino-bis(phosphinates) were synthesized and its acid-base and coordi- nation properties were studied. Unlike structurally similar geminal bis(phosphonates), the title compounds showed negligible adsorption onto hydroxyapatite (commonly used model of bone tissue). The obtained knowledge dealing with geminal bis(phosphinates) was utilized in synthe- sis of two novel cyclam derivatives. The ligands (bearing either one geminal bis(phosphinate) or one geminal phosphino-phosphonate pendant arm) were synthesized by highly efficient procedure. The corresponding Cu2+ complexes are formed with very high rates and show...
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Gallium complexes for molecular imaging of bone tissue
Holub, Jan ; Kubíček, Vojtěch (advisor) ; Vojtíšek, Pavel (referee)
Title: Gallium Complexes for Molecular Imaging of Bone Tissue Author: Bc. Jan Holub Department of Inorganic Chemistry, Faculty of Science, Charles University Supervisor: RNDr. Vojtěch Kubíček, PhD. Supervisor's Email address: kubicek@natur.cuni.cz ABSTRACT This thesis is focused on preparing new ligands for selective complexation of gallium, which might serve as potential radiopharmaceuticals for 68 Ga-PET bone imaging. Two new ligands were prepared, combining 1,4,7-triazacyclonone-1,4-diacetic acid macrocyclic skeleton and bis(phosphonate) pendant arm, bound to the remaining free nitrogen atom on the macrocycle. Macrocyclic skeleton is responsible for high kinetic and thermodynamic stability of the Ga3+ complex and the bis(phosphonate) pendant arm insures selective delivery of the complex to the bone tissue. Both new ligands were fully characterized by NMR and mass spectroscopy. Complexation of Ga3+ was studied by 31 P and 71 Ga NMR spectroscopy. Binding to bone tissue was simulated by adsorption of the complexes to hydroxoapatite. Radiochemical experiments including study of 68 Ga complexation kinetics and basic in-vivo experiments including biodistribution studies and PET examination were done in cooperation with Johannes-Gutenberg Universität Mainz in Germany. Data obtained from these experiments were...
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