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The thermodynamic stability of etringite
Magrla, Radek ; Durica,, Tibor (referee) ; Bílek,, Vlastimil (referee) ; Brauner,, Josef (referee) ; Fridrichová, Marcela (advisor)
The theoretical part of this doctoral thesis summarizes the current knowledge of portland cement and its manufacturing technology, information of FBC ash, Aft phases, AFm phases and the current knowledge of thermodynamic stability of ettringite. The practical part of the doctoral thesis focuses on manufacturing of ettringite based on yeelimite clinker, studying the influence of environment on thermodynamic stability of ettringite and manufacturing of ettringite by direct addition of calcium hydroxide and aluminum sulfate.
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Zirconium ternary complexes with fluoride anions
Zach, Kamil - Lukáš ; Kubíček, Vojtěch (advisor) ; Schulz, Jiří (referee)
Modern medicine uses non-invasive imaging methods for diagnostic purposes. Positron emission tomography is one of them. During the examination, the patient is injected with a radiopharmaceutical that is accumulated in tissue abnormalities and emits detectable radiation during its nuclear decay. The world's most commonly used radionuclide for these purposes is the radioisotope 18 F. The biodistribution of the fluoride ion itself is not very specific, so the radioisotope is usually bound to the structure of bioactive molecules. The actual preparation of these molecules is very challenging, so new labeling methods are currently being sought. One of the new possibilities is the preparation of labeled ternary complexes. In this work, the preparation of two polyazamacrocyclic ligands, H3NOTA and H3PCTA, which have acetate arms attached to their skeleton via aliphatic nitrogen atoms, is described. Zirconium complexes were prepared with these ligands. Subsequently, coordination and dissociation studies of fluoride ions to the prepared complexes were carried out. The measurements were monitored with a fluoride ion selective electrode. Both kinetic and thermodynamic aspects of coordination and decoordination were investigated in the measurements. Furthermore, characterization of the prepared ternary...
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The thermodynamic stability of etringite
Magrla, Radek ; Durica,, Tibor (referee) ; Bílek,, Vlastimil (referee) ; Brauner,, Josef (referee) ; Fridrichová, Marcela (advisor)
The theoretical part of this doctoral thesis summarizes the current knowledge of portland cement and its manufacturing technology, information of FBC ash, Aft phases, AFm phases and the current knowledge of thermodynamic stability of ettringite. The practical part of the doctoral thesis focuses on manufacturing of ettringite based on yeelimite clinker, studying the influence of environment on thermodynamic stability of ettringite and manufacturing of ettringite by direct addition of calcium hydroxide and aluminum sulfate.
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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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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 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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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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Complexes of 1,4,7-triazacyclononane derivatives
Kubinec, Jan ; Kubíček, Vojtěch (advisor) ; Vojtíšek, Pavel (referee)
The aim of this thesis was to prepare monoamide of macrocycle H3NOTA, which was prepared by multiple step synthesis. Ligand was characterized by NMR, MS and X-ray difraction analysis. Acid-base properties were studied by potentiometric titrations. Four protonation constants pKa`s were found and these protonation constants are lower than pKa`s of H3NOTA. Coordination properties with selected metal ions from the first row of transition metal, metal ions of biological interest and with lithium ions were investigated by potentiometric titration. Stability constants show that monoethylamide derivative of macrocycle H3NOTA forms complexes with lower stability than diethylamide derivative of macrocycle H3NOTA. Stability constants for complexes which contains amide group are lower than for H3NOTA complexes. Kinetics of Ga3+ complexation was investigated at different pH by 71 Ga NMR. The rate constants of and half-lives of complexation were determined at pH = 1. The rate constant was higher and the half-life of complexation was shorter than for H3NOTA ligand. Key words: macrocyclic complexes, thermodynamic stability, formation kinetics, radiopharmaceutical
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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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