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Macrocycles and complexation of large metal cations
Faltejsek, Jan ; Hermann, Petr (advisor) ; Drahoš, Bohuslav (referee)
In the last years, radioisotopes of heavy elements from the bottom of the Periodic Table have been increasingly used in nuclear medicine with focus on alpha-therapy. These large metal ions demand ligands fulfilling their special requirements. Complexes of polyazamacrocyclic ligands have been used in radiomedicine for a long time as diagnostic and therapeutic agents. This work aims to con- tribute to understanding of coordination chemistry of large macrocycles toward large metal ions. Thus, this work deals with structural studies, formation and decomplexation kinetics of Ln(III)-H4pyta complexes employing X-ray solid-state and solution NMR/UV-Vis spectroscopic data. The H4pyta is a 18-membered hexaazamacrocycle formed by two pyridine units and four amine groups which are modified with four acetate pendant arms. In the solid state, several isomeric complexes were structu- rally characterized. Large Ln(III) ions form decacoordinated species with two and two acetates on each side of the macrocyclic N6-plane. Small Ln(III) binds the ligand in a nonadentate fashion with one pendant non-coordinated. In the middle of lanthanide series, both isomers were characterized for several Ln(III) ions. Formation of the complexes takes place in a three-step mechanism with fast formation of an out-of-cage intermediate...
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Studies of Lanthanide Complexes by a Combination of Spectroscopic Methods
Krupová, Monika ; Bouř, Petr (advisor) ; Kapitán, Josef (referee)
Studies of Lanthanide Complexes by a Combination of Spectroscopic Methods Monika Krupová (Department of Physical and Macromoecular Chemistry, Faculty of Science, Charles University in Prague) Since conventional structural analysis offers rather limited means for the chirality detection, a series of lanthanide tris-(β-diketonates) are investigated as effective receptors for a better chirality sensing in biomolecular substrates. These lanthanide complexes containing β-diketonate ligands are electrically neutral; they can further coordinate with various small organic molecules such as chiral alcohols, amino alcohols or amino acids in organic solvents and produce a strong chiral signal. Previously, a resonance in Raman scattering was observed in the studied systems due to the correspondence of europium electronic transition energy to the laser excitation wavelength, about a 100-fold signal enhancement if compared to non-resonant vibrational ROA was observed. This enabled shorter detection times as well as lower sample concentrations. In the current work, interaction of the Eu(FOD) complex with (R)- and (S)- enantiomer of 1-phenylethanol in n-hexane was studied using IR spectroscopy, Raman spectroscopy and Raman optical activity (ROA), UV-Vis spectroscopy and ultraviolet circular dichroism (UVCD). Only...
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Studies of Lanthanide Complexes by a Combination of Spectroscopic Methods
Krupová, Monika ; Bouř, Petr (advisor) ; Kapitán, Josef (referee)
Studies of Lanthanide Complexes by a Combination of Spectroscopic Methods Monika Krupová (Department of Physical and Macromoecular Chemistry, Faculty of Science, Charles University in Prague) Since conventional structural analysis offers rather limited means for the chirality detection, a series of lanthanide tris-(β-diketonates) are investigated as effective receptors for a better chirality sensing in biomolecular substrates. These lanthanide complexes containing β-diketonate ligands are electrically neutral; they can further coordinate with various small organic molecules such as chiral alcohols, amino alcohols or amino acids in organic solvents and produce a strong chiral signal. Previously, a resonance in Raman scattering was observed in the studied systems due to the correspondence of europium electronic transition energy to the laser excitation wavelength, about a 100-fold signal enhancement if compared to non-resonant vibrational ROA was observed. This enabled shorter detection times as well as lower sample concentrations. In the current work, interaction of the Eu(FOD) complex with (R)- and (S)- enantiomer of 1-phenylethanol in n-hexane was studied using IR spectroscopy, Raman spectroscopy and Raman optical activity (ROA), UV-Vis spectroscopy and ultraviolet circular dichroism (UVCD). Only...
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Titaniun Dioxide - Phosphonate Assemblies as Medical Nanoprobes
Řehoř, Ivan ; Lukeš, Ivan (advisor) ; Lang, Kamil (referee) ; Peters, Joop (referee)
Titanium Dioxide - Phosphonate Assemblies as Medical Nanoprobes Ivan Řehoř PhD. Thesis Abstract: Multimodal imaging-therapeutic nanoprobe TiO2@RhdGd was prepared and successfully used for in- vitro and in-vivo cell tracking as well as for killing of cancer cells in-vitro. TiO2 nanoparticles, 12 nm in diameter, were used as a core for phosphonic acid modified functionalities, responsible for contrast in MRI and optical imaging. The phosphonic acid derivatives, used for surface modification, allows for grafting extraordinarily high loads of irreversibly adsorbed molecules of both types in one step. The prepared probe shows very high 1 H r1 relaxivity value as well as relaxivity density value, both crucial parameters for its use in MRI. The presence of fluorescent dye in its structure allows for its visualization by means of fluorescence microscopy. The applicability of the probe was studied, using three living systems - mesenchymal stem cells, cancer HeLa cells and T-lymphocytes. The probe did not exhibit toxicity in any of these systems and its long time storage in a lysosomal compartment was confirmed. Labeled cells were successfully visualized in-vitro by means of fluorescence microscopy and MRI. Consequent visualization of labeled cells in-vivo by means of fluorescence microscopy was also achieved....
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