|
| |
|
|
Ligand design for medicinal applications
Paúrová, Monika ; Kotek, Jan (advisor) ; Trávníček, Zdeněk (referee) ; Řezanka, Pavel (referee)
In recent years, copper radioisotopes have been extensively studied for their suitable coordination and physical properties. Nuclides 61 Cu, 64 Cu and 67 Cu are used in nuclear medicine - in diagnostic as well as in therapeutic applications. The aim of the Thesis is a study of the coordination properties of divalent copper as a stepping stone for the next potential applications. The presented Thesis consists of two thematic parts. The first part deals with the synthesis of cyclam derivatives. Sixteen new macrocyclic ligands with different phosphorus acid coordinating pendant arms (phosphinate, phosphonate, germinal P-C-P) were prepared; an analogous ligand endowed by carboxylic acid pendant arm as well as tetramethylcyclam without coordinating arm were prepared for comparison. The influence of the nature of coordinating acid pendant arms on selectivity and on the rate of copper(II) complexation was studied in detail. The protonation constants of the free ligands and the stability constants of the complexes with selected transition metal ions were determined by potentiometric titrations and by 1 H and 31 P NMR spectroscopy. Kinetic properties - i.e. studies of the formation rate and kinetic inertness of the copper(II) complexes - were performed by UV-Vis spectroscopy. The formation kinetics of the selected...
|
|
|
Lanthanide macrocyclic complexes with phosphonate/phosphinate pendant arms
Procházková, Soňa ; Kubíček, Vojtěch (advisor) ; Cígler, Petr (referee) ; Řezanka, Pavel (referee)
Imaging methods have become an integral part of diagnostic and therapeutic procedures in current medicine. Contrast agents based on metal complexes are often used to improve the final image. Complexes contain radioisotopes in nuclear medicine and gadolinium(III) ion in MRI. These complexes have to show high kinetic and thermodynamic stability and their preparation must not be time consuming. H4DOTA and its derivatives are convenient type of ligand for the formation of stable complexes. This work has focused on phosphonate and phosphinate derivatives of the ligand H4DOTA. The studied compounds can be divided into ligands containing only methylphosphinate/phosphonate (H4DO3APH, H5DO3APOH) and ligands with a second coordination center (H6DO3APIDA, H5DO3APPIN, H4DO3APAM, H8DO3APBP a H7DOTAMBP). The work has examined the possibilities of influencing the way and rate of complexation under different conditions. In order to approach the preparation conditions of radio complexes, kinetics measurements were performed not only under the metal ions excess, but also under the ligand excess. The aim was to compare the results of both types of measurements, which often showed to be different. A mechanism for the formation of various types of intermediates formed during complexation has been proposed. The...
|
|
| |
|
|
Novel approaches to chemical modification of diamond surface
Bartoň, Jan ; Cígler, Petr (advisor) ; Řezanka, Pavel (referee) ; Stehlík, Štěpán (referee)
1 Abstract Diamond is a unique material for its physical and chemical stability. However, many advance applications rely on surface functionalisation. Here, two types of diamond were modified on the surface - thin layer of chemical vapor deposition (CVD) and nanodiamond particles (NDs) high pressure and high temperature (HPHT). The aim of CVD surface modification was to prepare photosensitised, conductive, diamond electrodes for dye sensitized solar cells (DSSC). For this purpose, a thin diamond layer doped with boron was deposited on the silicon wafer. Boron doping provided p-type (semi)conductivity to diamonds. The surface of the diamond was hydrogenated with H-plasma, and a short carbon linker with a protected amino group was UV-photografted to the surface. In another study, a photoconverting dye (P1) was covalently attached to the amine-linker. Furthermore, a dye designed based on donor-π-acceptor (D-π-A) concepts was attached to the surface. Finally, a systematic study was done for differently conductive diamond layer and the underlying silicon wafer These experiments gradually lead to the highest ever reported photocurrents of 6.6 µA cm2 for a flat photosensitised boron-doped-diamond (BDD) electrode. Monomolecular layer surface functionalizations on CVD diamond are difficult to detect or even quantify...
|
|
| |
|
| |
|
|
Ligand design for medicinal applications
Paúrová, Monika ; Kotek, Jan (advisor) ; Trávníček, Zdeněk (referee) ; Řezanka, Pavel (referee)
In recent years, copper radioisotopes have been extensively studied for their suitable coordination and physical properties. Nuclides 61 Cu, 64 Cu and 67 Cu are used in nuclear medicine - in diagnostic as well as in therapeutic applications. The aim of the Thesis is a study of the coordination properties of divalent copper as a stepping stone for the next potential applications. The presented Thesis consists of two thematic parts. The first part deals with the synthesis of cyclam derivatives. Sixteen new macrocyclic ligands with different phosphorus acid coordinating pendant arms (phosphinate, phosphonate, germinal P-C-P) were prepared; an analogous ligand endowed by carboxylic acid pendant arm as well as tetramethylcyclam without coordinating arm were prepared for comparison. The influence of the nature of coordinating acid pendant arms on selectivity and on the rate of copper(II) complexation was studied in detail. The protonation constants of the free ligands and the stability constants of the complexes with selected transition metal ions were determined by potentiometric titrations and by 1 H and 31 P NMR spectroscopy. Kinetic properties - i.e. studies of the formation rate and kinetic inertness of the copper(II) complexes - were performed by UV-Vis spectroscopy. The formation kinetics of the selected...
|
guest ::
