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Macrocyclic complexes with open coordination sphere
Jaroš, Adam ; Kubíček, Vojtěch (advisor) ; Gyepes, Róbert (referee)
The aim of this work was to synthesize and study acid-base and coordination properties of ligands bearing a neutral or negative charge on their pendant arms. Acid-base properties of two ligands and thermodynamic stability of their complexes with gallium, copper, and zinc ions were studied using potentiometry, UV-Vis and NMR. Solid state structure of one of the ligands and its complex with copper ion was studied using RTG structural analysis. Structure of complexes in solution was studied using methods of computational chemistry.
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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...
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Synthesis and coordination properties of TACN phosphinate derivatives
Kohúteková, Soňa ; Kubíček, Vojtěch (advisor) ; Gyepes, Róbert (referee)
The aim of this work is preparation and characterization of a ligand for a selective complexation of gallium (III). The ligand is a derivative of macrocycle NOTA with bis(phosphinic) pendant arm. Protonation constants and stability constants with copper (II), nickel (II), zinc (II) and gallium (III) cations were determined by potentiometric titrations. The ligand was also used for studying complexation kinetics with gallium (III) ions and might serve as a potential contrast agent for 68 Ga-PET.
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Coordination properties of TACN ethylphosphonic derivative
Poláková, Zuzana ; Kubíček, Vojtěch (advisor) ; Schulz, Jiří (referee)
Ligand NOTPOEt was synthesized. Protonation constants and stability constants of Cu(II), Zn(II), Ni(II) and Ga(III) complexes were determined by potentiometric titrations. Cu(II) complex was characterized by UV-VIS spectroscopy and formation of Ga(III) complex was studied by NMR spectroscopy. The work was aimed at characterisation of the ligand with respect to potential application in biomedical imaging techniques.
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Coordination properties of NOTA monoamide
Kubinec, Jan ; Kubíček, Vojtěch (advisor) ; Matulková, Irena (referee)
The aim of this thesis was to prepare monoamide of macrocycle NOTA, which was successfully prepared and fully characterized. Acid-base properties were investigated by potentiometric titration and four protonation constants were found, which are lower than pKa ` s of NOTA ligand. Coordination properties with selected ions from the first row of transition metals were investigated. Stability constants of studied complexes are also lower than the same complexes with NOTA ligand. Key words: macrocyclic complexes, positron emission tomography, thermodynamic stability, formation kinetic, radiopharmaceuticals
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Bifunctional ligands for copper(II) complexation
Benešová, Martina ; Kotek, Jan (advisor) ; Kozempel, Ján (referee)
Title: Bifunctional ligands for copper(II) complexation Author: Bc. Martina Benešová Supervisor: doc. RNDr. Jan Kotek, Ph.D. Institution: Department of Inorganic Chemistry, Faculty of Science, CU in Prague Author's e-mail: EvaGlaser@seznam.cz ABSTRACT The main aim of this thesis was preparation of macrocyclic ligands based on 1,4,8,11- tetraazacyclotetradecane skeleton, which is suitable for selective complexation of divalent copper, and study of their properties. These ligands are suggested for potential utilization in nuclear medicine. Cyclam macrocycle was modified to bear one coordinating aminobenzylphospinate pendant arm (compound L1) or monophosphinate-bis(phosphonate) pendant arm (compound L2). During the synthesis, the skeleton was protected in positions 1, 4 and 8. In the frame of this work the synthesis of both targeted products was developed. Furthermore, a study of the thermodynamic, kinetic and coordination properties of ligand L2 was investigated by UV/VIS spectrophotometry and potentiometric titrations. A model bioconjugation of ligand L1 with primary amine was also studied. KEYWORDS Cyclam, phosphinates, phosphonates, nuclear medicine, copper(II) complexes, kinetic inertness, thermodynamic stability.
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Symmetrical aminophosphinates
Procházková, Soňa ; Kubíček, Vojtěch (advisor) ; Vojtíšek, Pavel (referee)
Title: Symmetrical aminophosphinates Author: Bc. Soňa Procházková Department of Inorganic Chemistry, Faculty of Science, Charles University Supervisor: RNDr. Vojtěch Kubíček, Ph.D. Supervisor's email address: kubicek@natur.cuni.cz ABSTRACT Two types of α-aminophosphinates were prepared and studied: phosphinate analogues of iminodiacetic acid − aminobis(methyl(hydroxymethyl)phosphinic acid) (IDPhm ) and aminobis(methyl(2-carboxyethyl)phosphinic acid) (IDPce ), and bis(aminomethyl- phosphinates) − (hydroxy(fenyl)methylen)bis(aminomethylphosphinic acid) (PheOHABPin) and (methylen)bis(aminomethylphosphinic acid) (ABPin). All prepared compounds were fully characterized (by NMR, MS, elemental analysis). One crystal structure was determined by X-ray singlecrystal analysis. The diphosphinates were synthesized by Mannich type reaction, whereas the bis(aminomethylphosphinates) were prepared by multistep synthesis including reactive silylesters. Compounds were prepared in moderate or good yields Acid-base and coordination properties of ligands were investigated and compared by potentiometric and NMR titrations. The values of protonation constants of aminogroups, which determine stability of complexes, showed surprising results. An extremely low basicity of nitrogen atom was found in diphosphinates. So, these compounds...
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Bifunctional chelators for selective copper(II) binding
Paúrová, Monika ; Kotek, Jan (advisor) ; Vojtíšek, Pavel (referee)
Title: Bifunctional chelators for selective copper(II) binding Autor: Bc. Monika Paúrová Department: Department of Inorganic Chemistry, Faculty of Science Supervisor: doc. RNDr. Jan Kotek, Ph.D. Supervisor's e-mail: modrej@natur.cuni.cz Abstract: In this Master thesis, cyclam bifunctional derivatives bearing pendant phosphinate groups (4-methyl-11-p-aminobenzyl-1,4,8,11-tetraazacyclotetradecane-1,8- bis(methylenephosphinic acid)) and phosphonate groups (4-methyl-11-p-aminobenzyl- 1,4,8,11-tetraazacyclotetradecane-1,8-bis(methylenephosphonic acid)), were prepared and studied as potential ligands for complexation of divalent copper. These ligands are suitable for binding to a macromolecular carrier. Keywords: radiomedicine, copper, cyclam, chelating agent, phosphinate, phosphonate, kinetic inertness, kinetic lability, thermodynamic stability
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Bifunctional ligands for copper(II) complexation
Blahut, Jan ; Kotek, Jan (advisor) ; Svoboda, Jan (referee)
Because of an indisputable pharmacological advatages of radiometal-labeled compounds, a purpose of this work it to design and synthesize a new chelatation system for copper(II) complexation. The solution properties of the ligand and copper complex are also studied, as well as its ability for binding a targeting molecule.
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