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Complexes of macrocyclic ligands with phosphonate and phosphinate penant arms for molecular imaging
Pazderová, Lucia ; Kubíček, Vojtěch (advisor) ; Pinkas, Jiří (referee) ; Polášek, Miloslav (referee)
In an effort to increase the thermodynamic stability and the kinetic inertness of the complexes, the five new azamacrobicyclic ligands derived from TACN, cyclen, and cyclam have been prepared. The ligands were decorated with phosphinate or phosphonate pendant arms to maintain fast complexation. Since the ascending importance of targeted diagnostic and therapy, the bone-targeted non-bridged cyclam derivative with phosphinate-bis(phosphonate) pendant arm (H5TE1PBP) has also been synthesized. The ligands were studied with respect to their application. The bridged TACN (H2bpbtacn) and cyclen (H4bpbcen) ligands show high macrocyclic basicity (logK1 = 12.25 and 12.70, respectively). The thermodynamic stability of H2bpbtacn with Cu(II) ion is more than ten orders of magnitude lower than that of the NOTA ligand. The stability constants of H4bpbcen with Cu(II) and Zn(II) ions are comparable to those given for the DOTA. The stability of Ln(III)-bpbcen complexes is 7-10 orders of magnitude lower compared to DOTA complexes. For both ligands, the lower thermodynamic stability of the complexes is attributed to the high rigidity of the ligand structure. The bridged cyclam derivatives with phosphonate (H4TE2P), bis(phosphinate) (H4TE2bpin), or phosphinate (H2TE2PH) pendants are characterized by high stability of...
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Complexes of cyclen-based macrocyclic ligands with a phosphinate pendant arm
Urbanovský, Peter ; Hermann, Petr (advisor) ; Lyčka, Antonín (referee) ; Pinkas, Jiří (referee)
Lanthanide(III) complexes of DOTA derivatives are utilized in the medical imaging techniques such as magnetic resonance imaging (MRI), magnetic resonance angiography (MRA), and magnetic resonance spectroscopy (MRS), nuclear imaging (PET and SPECT), or optical methods (luminescence). It has been shown that relaxometric parameters of the Gd(III) complexes of DOTA derivatives with a phosphinic acid pendant arm (Gd-DO3APR ) can reach optimal values (e.g. water residence time, τM, being close to ~10 ns). The relaxometric parameters can be further modified through the phosphorus substituents. It is also known that the complexes possess a high thermodynamic stability and they are kinetically inert. The main goal of this Thesis is an investigation of the effect of pendant amino group protonation in substituents bound to the phosphorus atom on properties of the complexes. Thus in this Thesis, DOTA derivatives with the phosphinic acid pendant arm with an amino group and their complexes were prepared and characterized. The complexes are intended as contrast agents for molecular imaging techniques (mainly for MRI and 31 P MRS). The first part of the Thesis introduces two new versatile "phospha-Mannich" protocols performed under mild conditions. Amino-H-phosphinic acids (AHPAs) were synthesized with excess of...
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Processing of aerogel coatings on bulk materials substrates
Torres Rodríguez, Jorge Alberto ; Torre, Sebastián Díaz de la (referee) ; Pinkas, Jiří (referee) ; Kaiser, Jozef (advisor)
Tato práce se zabývá systematickou studií syntézy a zpracováním pokročilých tepelně stabilních aerogelů pro potenciální vysokoteplotní aplikace. V první části dizertační práce jsou podrobně popsány syntetické implikace pro přípravu aerogelů a jejich aplikace spolu s popisem depozičních metod povlaků vytvořených pomocí sol-gel procesu. Experimentální postup je rozdělen do tří částí. První z nich představuje syntetické protokoly k přípravě ZrO2, YSZ, Ln2Zr2O7 (Ln = La3+, Nd3+, Gd3+, and Dy3+) aerogelů, Ln2Zr2O7 prášků a xerogelů. Dále je popsána depoziční metoda, která byla použita pro přípravu povlaků z aerogelů na kovových substrátech. Poté jsou následně specifikovány techniky, jež byly použity pro charakterizaci. Bylo zjištěno, že množství vody a kyseliny dusičné hraje rozhodující roli v přípravě gelů vhodných pro transformaci na aerogely. Po kalcinaci při 500 °C mají ZrO2 a YSZ aerogely velký povrch, a to až do 114 m2 g-1, avšak při 1000 °C dochází k úplnému zhuštění a ztrácí se tak veškerá jejich porézní struktura. Naopak ve srovnání s ZrO2 and YSZ jsou aerogely Ln2Zr2O7 tepelně stabilnější, protože si zachovávají svou porozitu při vyšší kalcinační teplotě (1000 °C), při které dosahují hodnot > 160 m2 g-1. Experimentálně bylo dále zjištěno, že ve studovaném teplotním rozsahu ZrO2 aerogel tvoří tetragonální komplex monoklinický fázový přechod řízený velikostí krystalitů, zatímco YSZ je tvořena jedinou tetragonální fází. Fázové složení zirkoničitanů vzácných zemin je vysoce závislé na způsobu syntézy; všechny Ln2Zr2O7 materiály jsou pyrochlorické nebo fluoritové krystalické fáze. Přímým odléváním aerogelu na kovový substrát dochází k úplnému rozpraskání povlaku z důvodu smršťování, zatímco máčením kovového substrátu v suspenzi je možné vyrobit homogenní, silné a hrubé povlaky z aerogelu. Tyto povlaky neobsahují fázové změny a zůstávají vysoce porézní i po různých tepelných úpravách.
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Homogeneous and heterogeneous titanium complexes and their use for selective ethylene trimerization to 1-hexene
Hodík, Tomáš ; Pinkas, Jiří (advisor) ; Merna, Jan (referee)
This diploma thesis is focused on the design and synthesis of new half-sandwich titanium complexes for anchoring to selected supports (SiO2, SBA-15) and the study of their catalytic activity and selectivity in ethylene trimerization to 1-hexene. The synthetic strategy of half-sandwich titanium complexes with a suitable leaving group for direct anchoring through Ti−O bond was carried out (Cl, Oi-Pr). In addition, the titanium complexes with pendant alkenyl group were prepared and utilised for anchoring to a SiMe2H modified support by Pt-catalysed hydrosilylation reaction. Prepared compounds were characterised by standard spectroscopic methods (IR, NMR, MS). The heterogeneous systems were characterised by MAS NMR and IR spectroscopy, powder XRD, ICP-OES, TGA and the textural parameters were determined from nitrogen adsorption/desorption isotherms. For all prepared materials was studied the catalytic activity for ethylene trimerization and the selectivity to 1-hexene.
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Porphyrin-layered double hydroxide hybrids as novel photofunctional materials
Káfuňková, Eva ; Lang, Kamil (advisor) ; Pinkas, Jiří (referee) ; Bujdák, Juraj (referee)
This Ph.D. Thesis is based on publications to which the author contributed considerably. The list of the publications is attached at the end of this text. This work describes preparation and photophysical properties of hybrid materials derived from layered double hydroxides (LDH) containing Zn2+ /Al3+ or Mg2+ /Al3+ cations. The materials were prepared in the form of powders or thin films. In the first part of my work, photosensitizing porphyrins have been intercalated into ZnRAl and MgRAl LDH (R = 2, 3, 4) using anion-exchange, rehydration, and coprecipitation procedures. According to the obtained results of X-ray analysis, the orientation of the equatorial plain of the porphyrin molecules is nearly perpendicular to LDH layers and fosters the photosensitizing properties of the hybrid materials. Furthermore, the porphyrin-LDH hybrids were used as nanofillers and nanocontainers in eco-friendly polymers, polyurethane (PU) and poly(butylene succinate) (PBS). The porphyrin-LDH material is well dispersed in PU polymer (nanofiller function) to form transparent colored films while porphyrins remain intercalated between LDH layers (nanocontainer function). The polymers allow oxygen diffusion. The second part has been dedicated to investigation of photophysical properties of the porphyrin-LDH powders and the...
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Sol-gel synthesis of ternary ZnxTiyOz nanostructures for applications in solar cell technologies and photonics
Mrázek, Jan ; Nižňanský, Daniel (advisor) ; Pinkas, Jiří (referee) ; Pollert, Emil (referee)
The presented study deals with the sol-gel synthesis of nanocrystalline ternary phases of the general formula ZnxTiyOz, their characterization and potential application in photonics. Achieved results brings new fundamental knowledge about the processes leading to the formation of ZnxTiyOz nanocrystals from amorphous xerogels and gives novel information about structural and opto-electrical properties of prepared materials. Based on the presented results, most of all up-to-date reported ZnxTiyOz compounds with tailored nanocrystalline size and structure can be prepared as powders or thin films. Two sol-gel approaches based on the cluster process and direct heteronucleation were employed to prepare initial sol. Sols were optionally doped by Eu3+ ions to evaluate the effects of rare earth element to crystallization properties of formed compounds. In the first part of our study crystallization properties and structural evolution of thermally treated xerogels were analyzed. As a result a versatile method allowing the preparation of inverse spinel Zn2TiO4, cubic defect spinel ZnTiO3 and rhombohedral ZnTiO3 with tailored nanocrystal sizes was established. Initial composition and thermal annealing allow us to prepare selected ternary phase with tailored nanocrystal size ranging from tens of nanometers up to...
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THE APPLICATION OF NANOMATERIALS FOR LEAD FREE SOLDERS DEVELOPMENT
Pešina, Zbyněk ; Pinkas, Jiří (referee) ; Spousta, Jiří (referee) ; Sopoušek, Jiří (advisor)
The present dissertation is motivated by the search for alternatives of lead-free soldering by nanoparticles of metals and their alloys. The research focuses on the possibility of replacing lead-free solders by nanoparticles. This issue is currently being addressed by the use of lead-free solders but their properties are not entirely equivalent to properties of lead-tin based alloys. The theoretical part of the dissertation first summarizes up-to date knowledge on the development of lead-free alloys currently used for soldering in the electronics. The work compares these lead-free solder candidates with previously used Pb-Sn alloys. The second section of the theoretical part is devoted to nanotechnology that offers possible solutions of problems associated with the use of lead-free solders. The text contains a description of the properties of nanocrystalline materials in comparison with those of compact alloys having the same chemical composition. The possibility of preparation of nanoparticles and potential problems associated with small particle sizes are also presented. Introduction of the experimental part focuses on the preparation of nanoparticles of pure metals and alloys by chemical and physical ways as well as on an instrumentation for characterisation and analysis. Attention is focused on the silver in nanoparticle form that exhibits the low temperature sintering effect, which is thermally activated by decomposition of oxide envelope covering the Ag nanoparticles. This factor is critical for low-temperature sintering and thus also for possible future applications. The thermal effects of the low sintering process were studied by methods of thermal analysis. The preparation of the Cu / Ag nano / Cu joints was carried out in-situ in inert atmosphere and under the action of atmospheric oxygen. In both cases varying conditions of thermal treatment were used. The cross sections of the prepared joints were then used for the metallographic analysis of the local mechanical properties of the resulting silver layer, for the chemical composition evaluation of the resulting layers of the joint, and for the microstructure study. Strength characteristics are represented by testing shear strength of individual joints.
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LC-NMR Analysis of Phenylsilane Polymers
Pinkas, Jiří ; Merna, J. ; Sýkora, Jan
We report the analysis of dehydrocoupling polymerization reactions of phenylsilane via on-flow LC-NMR experiment. The successful separation was achieved by isocratic elution of acetonitrile and aceton (80:20). The separation was solely monitored by 1H NMR detection. The properties of the polymeric product depend on the catalytical system. The products can differ in the molar weight distribution, degree of branching and amount of cyclic and rearranged products. In our particular cases, the weight average molar mass (Mw) varies from several silane units up to 4100 g.mol-1. The branching of polysilanes is monitored by 29Si{1H} INEPT experiment with the polarization transfer from the ortho hydrogen (J~7 Hz). The connectivity within branched unit was established via 1H à 29Si-29Si INEPT-INADEQUATE experiment.
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