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Self-assembled polymer systems responsive to external stimuli for biomedicine
Sincari, Vladimir ; Štěpánek, Petr (advisor) ; Matějíček, Pavel (referee) ; Sedláková, Zdeňka (referee)
The first work in my doctoral thesis described a novel rapid and eco-friendly reversible addition-fragmentation chain transfer (RAFT) polymerization reaction of the N-(2- hydroxypropyl) methacrylamide (HPMA) monomer under microwave irradiation (MWI). Optimal conditions for the polymerization such as reaction time, solvents, monomer stoichiometry and RAFT agents was determined. The polymerization kinetics demonstrated the linear increase in the number-average molecular weight (Mn) with monomer conversion. Good agreement between the theoretical and experimental Mn values was verified with pseudo-first- order kinetic plots, with low dispersities (Đ ≤ 1.04). Furthermore, this publication demonstrated the ability of MWI to facilitate copolymer formation by the preparation of relevant copolymers, such as poly(HPMA-b-bocAPMA), poly(HPMA-b-MABH) and poly(HPMA-b-PDPA) which were used as a base for the following work in the thesis. The second and third study are devoted to delivery of therapeutic molecules by using cargo-delivery self-assemblies in the form of polymersomes (PS). Such drug delivery systems (DDS) potentially minimize the premature degradation of drug, fast clearance from bloodstream and dosing frequency which leads to lower toxicity. The main advantage of DDS is the controlled manner of drug...
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Multicomponental polyurethane systems with targeted properties. Preparation and characterization.
Serkis-Rodzeń, Magdalena ; Špírková, Milena (advisor) ; Uchman, Mariusz Marcin (referee) ; Sedláková, Zdeňka (referee)
Thermoplastic polyurethanes (PU) have been widely used for many applications due to their excellent functional properties, recycling included. PUs prepared in this Thesis are based on polycarbonate macrodiols and other bifunctional components, leading to linear solely aliphatic polymer materials. The main part of this study is focused on synthesis and analysis of polyurethane water dispersions (PUDs) and PUD-based films. The novelty of presented herein research involves ecofriendly method for preparation of thermoplastic PUs based on polycarbonates. The PU nanoparticles dispersed in water were measured by scattering methods, whereas the final films were characterized for their morphology and mechanical, thermal and water resistance. A balance between hydrophilic and hydrophobic parts of PUs for the particles stability and the films properties was investigated as well. The PUDs were blended with two types of colloidal silica for improve of the PUD- based films resistances with simultaneous preserving of their thermoplastic character. More significant enhancement was observed for the organic-inorganic nanocomposites containing silica with smaller particles, due to creation of higher physical crosslinking density between the nanofiller and PU matrix. We modified the acetone process of PUDs preparation...
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The increased diagnostic efficiency of QF-PCR for aneuploidy of amniotic fluid
Sedláková, Zdeňka ; Macek, Milan (advisor) ; Daňková, Pavlína (referee)
Quantitative fluorescence polymerase chain reaction (QF-PCR) is a molecular genetic method based on the amplification of microsatellites (Short tandem repeats, STR) and measurement of the peak heights of amplicons in the electropherogram. Currently, the QF-PCR deemed reliable, fast, and inexpensive method that is gradually replacing conventional cytogenetic analysis of aneuploidy (examination of long-term cultures of amniotic fluid). However, in certain cases it is impossible to determine the parental origin and meiotic aneuploidy by QF-PCR. The aim of this work was to verify the new dinucleotide STR markers on chromozomes 13, 16, 18, 21, and 22 and further increase the diagnostic efficiency of QF-PCR retaining other STR markers on chromozome 15, 16, 22 and to determine the population and the analytical characteristics of these markers. For all dinucleotide STR markers stutter occurred in high frequency and therefore there were found not to be suitable for routine diagnostics. STR markers for chromozomes 15, 16 and 22 were tested on 100 patients. We selected four informative markers for both chromozome 16 and 22, and three markers for chromozome 15. Thus, I expanded set of diagnostic STR markers in this thesis.
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The synthesis of poly(butadiene)diol-based polyurethanes with LC properties
Poláková, Lenka ; Sedláková, Zdeňka (advisor) ; Šňupárek, Jaromír (referee) ; Hamplová, Věra (referee)
8 Summary The PhD thesis is focused on the synthesis and characterization of low-molecular mesogenic thiols and poly(butadiene)diols and polyurethanes with LC side chains. Within the frame of this work, following tasks have been solved: Two groups of low-molecular compounds containing a biphenyl or an azobenzene as a rigid mesogenic part have been synthesized: N YNOSHXO SH Y = -H -OCH3 -O(CH2)3CH3 -O(CH2)7CH3 X = -H -CN Composition and structure of the prepared units were confirmed by elemental analysis and 1 H NMR spectroscopy. Thermal behavior, with the respect to the temperature-dependent mesophase formation, was studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray scattering techniques (SAXS, WAXS). It was found that the presence and the type of the substituent on the mesogenic core play a crucial role in the ordering of the thiol molecules into a LC phase. The thiols synthesized were grafted onto double bonds of the commercially available telechelic poly(butadiene)diol Krasol LBH 3 000 (declared Mn ~ 2 600 Da, Mw/Mn = 1.10). The addition reactions proceeded in the presence of radical initiator (AIBN). Molar ratio of thiol/double bonds varied within the range of 0.15 (resp. 0.2) to 1.0 for each type of the thiol. The structure of the resulted comb-like...
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The increased diagnostic efficiency of QF-PCR for aneuploidy of amniotic fluid
Sedláková, Zdeňka ; Macek, Milan (advisor) ; Šolc, Roman (referee)
Quantitative fluorescence polymerase chain reaction (QF-PCR) is a molecular genetic method based on the amplification of microsatellites (Short tandem repeats, STR) and measurement of the peak heights of amplicons in the electropherogram. Currently, the QF- PCR deemed reliable, fast, and inexpensive method that is gradually replacing conventional cytogenetic analysis of aneuploidy (examination of long-term cultures of amniotic fluid). However, in certain cases it is impossible to determine the parental origin and meiotic aneuploidy by QF-PCR. The aim of this work was to verify the new dinucleotide STR markers on chromosomes 13, 16, 18, 21, and 22 and further increase the diagnostic efficiency of QF-PCR retaining other STR markers on chromosome 15, 16, 22 and to determine the population and the analytical characteristics of these markers. For all dinucleotide STR markers stutter occurred in high frequency and therefore there were found not to be suitable for routine diagnostics. STR markers for chromosomes 15, 16 and 22 were tested on 100 patients. We selected four informative markers for both chromosome 16 and 22, and three markers for chromosome 15. Thus, I expanded set of diagnostic STR markers in this thesis. Key words: QF-PCR, STR markers, prenatal diagnosis, trisomy.
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SYNTHESIS AND CHARACTERIZATION OF NANOMATERIALS CONTAINING BORON COMPOUNDS
Vrbata, David ; Uchman, Mariusz Marcin (advisor) ; Hrubý, Martin (referee) ; Sedláková, Zdeňka (referee)
This thesis is focused on synthesis and polymerization of caprolactone and its derivatives by living ring opening polymerization (LROP), Self-assembly in aqueous solutions produced nanoaggregates comprised of amphiphilic block copolymers or telechelic polymers with incorporated boron compounds (phenyl boronic acids and boron clusters). Incorporation of boron compounds was facilitated either by covalent or non-covalent bonding. Obtained complex nanoparticle structures manifested stimuli-responsive behaviour and were investigated under varying conditions by combination of light scattering, fluorescence spectroscopy and electron microscopy. The obtained results on solution behaviour of polymers in combination with added value of boron compounds, yield general aspects of nano aggregate morphology, responsive character tuning and practical aspects of synthesis and self-assembly overcame in the preparation process. The publications wrote during this thesis are therefore adding valuable information to researchers engaged in biomedical utilization of such nano assemblies.
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Hybrid Nanostructures Containing Boron Compounds
Li, Jianwei ; Matějíček, Pavel (advisor) ; Olejniczak, Agnieszka (referee) ; Sedláková, Zdeňka (referee)
Boron cluster compounds (BCCs) are inorganic polyhedral structures. Their unique properties such as high chemical & thermal stability, three-center two-electron bonds, and three- dimensional aromaticity have drawn great attention. Incorporation of BCCs into polymers via covalent bonds or noncovalent interactions are extensively investigated in the recent decades. BCC-containing polymeric materials have been widely reported in the biological applications such as BNCT and enzyme inhibitors, and energy storage for example Li-ion batteries and solution-based Mg batteries. This dissertation is focused on the preparation and characterization of BCC-containing polymeric materials. The synthesized BCC-containing polymeric materials are also evaluated by in vitro experimental for biomedical applications or Li-ion mobility for Li-ion batteries studies. The ideas are to maximally simplify the preparation steps of BCC-containing polymers and deeply understand the physical chemistry properties of BCCs in these materials. Therefore, the studies can be generally divided into two parts: (i) Design of boron-containing hybrid systems. For biological applications, the corresponding BCC-containing polymeric materials must be water-soluble or form stable nanostructures in aqueous solutions. We performed a feasible...
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Oriented copolymers with liquid crystalline building blocks
Horodecka, Sabina Jolanta ; Strachota, Adam (advisor) ; Uchman, Mariusz Marcin (referee) ; Sedláková, Zdeňka (referee)
Several series of reversible physical networks based on polydimethylsiloxane (PDMS) chains and liquid crystalline (LC) structural units were synthesized and studied, which belong to three different architecture types: (1) LC-grafted PDMS (with LC quartets at the grafting sites), (2) LC-end-capped linear PDMS, (3) and linear 'infinite' LC-PDMS copolymers (with alternating LC and PDMS segments). PDMS spacers of different lengths of were tested, as well as 6 different polyaromatic mesogens of azo type and azo-free type. Hydrosilylation coupling of vinyl-functional mesogens, obtained as part of an international cooperation, with commercial Si-H-functional PDMS was employed to synthesize all the studied materials. The copolymers were physically crosslinked by the nano-aggregation of the LC units contained in their macromolecules. The thermotropic properties of the LC-nano-aggregates lent interesting physical properties to the whole material, making some of the copolymers attractive as potential smart materials. The PDMS spacer segments were selected for the sake of their extreme flexibility, which should provide elastic properties to the physically crosslinked copolymers, and also because of their (desired) incompatibility with the mesogens. This latter effect was highly helpful for achieving the...
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Novel hybrid polysaccharide-based polymers for biomedicine
Loukotová, Lenka ; Hrubý, Martin (advisor) ; Sedláková, Zdeňka (referee) ; Poučková, Pavla (referee)
1 Abstract This doctoral thesis is focused on the synthesis and characterization of novel hybrid polysaccharide-based polymers applicable for biomedicine, specifically for a conceptually new bimodal cancer treatment - immunoradiotherapy. For this purpose, polysaccharides β-glucan from Auricularia auricula-judae and κ-carrageenan from Kappaphycus alvarezii, exhibiting immunostimulatory and anticancer activities, were chosen to be grafted with thermoresponsive poly(2-isopropyl-2-oxazoline-co-2-butyl-2-oxazoline)s (POXs) (with different graft lengths and grafting densities) that induced a lower critical solution temperature of the final polymers. The thermoresponsive behavior of resulting polymers was studied with temperature-dependent light scattering methods, fluorescence measurements and also nuclear magnetic spectroscopy to select a polymer material with the most suitable properties for the intended application, aiming at a polymer depot formation after the injection of a polymer solution into the body. The chosen polymer, β-glucan-graft-POX with graft length of 2500 Da, was then modified to bear 1,4,7,10-tetraazacyclododecane-1,4,7,10- tetraacetic acid and a fluorescent dye Dyomics-615 at the graft ends and tested first in vitro to investigate its immunostimulatory properties and also the cellular uptake....
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