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Biodegradable Nanogels from Biocompatible Polymer Precursors
Oleshchuk, Diana ; Proks, Vladimír (advisor) ; Uchman, Mariusz Marcin (referee) ; Trachtová, Štěpánka (referee)
This doctoral thesis focuses on the development and application of hydrophilic, biocompatible, and biodegradable poly(amino acids)-based nanogels as a new type of delivery system. Within this Ph.D. thesis, nanogelation via horseradish peroxidase (HRP)/H2O2-mediated crosslinking in an inverse miniemulsion was investigated and optimized. The effect of three different surfactants (SPAN 80, TWEEN 85, and AOT) with various concentrations (5 wt% - 25 wt% relative to the dispersed phase with step 5 wt%) on the nanogelation of polyglutamine-based polymer precursor modified with tyramine units (PHEG-Tyr) was investigated. The results indicated that the stabilization of nanogel was most effectively achieved using 20 wt% of the nonionic surfactant SPAN 80. The hydrodynamic diameter (Dh) determined by dynamic light scattering (DLS) was 230 nm, and this size range was further confirmed to be between 200 and 300 nm using (nanoparticle tracking analysis) NTA. Analysis using transmission (TEM) and cryogenic transmission electron microscopy (cryo-TEM) techniques revealed that the nanogel in its dry state exhibited almost spherical shape with a number-average diameter (Dn) of 26 nm and dispersity (Ɖ) of 1.91, and in the frozen hydrate state, the nanogel displayed a larger size with Dn = 182 nm and Ɖ = 1.52,...
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Synthesis of triblock terpolymers as a tool for preparation of smart drug delivery nanosystems
Orságh, Martin ; Uchman, Mariusz Marcin (advisor) ; Fernandez Alvarez, Roberto (referee)
In this thesis, we describe the synthesis and self-assembly of new photo-responsive triblock terpolymers by RAFT polymerization. These triblock terpolymers were characterized by GPC, NMR and IR spectroscopy. The resulting nanoparticles were characterized by DLS, SAXS and Cryo-EM. To avoid problems with RAFT polymerization of the photo-responsive monomer o- nitrobenzyl acrylate, we used naphthacyl methacrylate, a new RAFT-polymerizable photo- responsive monomer. In addition, we used phenylboronic acid moieties to conjugate model drugs with our triblock terpolymers via dynamic covalent bonding and studied stimuli-triggered release of a model drug-like compound, Alizarin Red S. Our results showed that naphthacyl methacrylate is indeed polymerizable by RAFT and that such polymers retain photo-responsive properties. We were also able to bind Alizarin Red S to the polymer via boronate ester linkage and trigger its release by dopamine or fructose addition, both of which are biologically relevant compounds. Therefore, our photo- and diol-responsive nanoparticles open up opportunities for developing new drug-delivery systems.
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Post-polymerization modification of block copolymers as a tool for preparation of new drug delivery nanosystems
Marková, Pavlína ; Uchman, Mariusz Marcin (advisor) ; Košovan, Peter (referee)
Amphiphilic block copolymers self-assemble into clinically efficacious nanostructures, whose size, stability, and surface chemistry can be easily adjusted for each purpose. This versatility has prompted the vast scope of their biomedical applications, especially in the field of drug delivery. In particular, polyester-based nanoparticles have been used in gene, nucleic acid, therapeutic protein and drug delivery for their in vivo biocompatibility and biodegradability. However, most studies have only focused on amphiphilic copolymers with either short hydrophobic segments, no modification or a single preparation pathway. This diploma thesis focuses on the synthesis of poly(ethylene oxide)-b-poly(caprolactone) copolymers containing propargyl groups using two parallel approaches, namely a copolymerization with a modified monomer and a post-polymerization modification. A subsequent thiol-yne click reaction with 1-thioglycerol yielded copolymers with vicinal diols, which can reversibly bind to benzoxaborole- and boronic acid-derived compounds. Both synthetic pathways were evaluated based on macromolecular characteristics afforded by nuclear magnetic resonance spectroscopy and by size exclusion chromatography. Furthermore, we characterized the self-assembled nanoparticles by static and dynamic light...
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Synthesis of block copolymers by ring-opening polymerization and post polymerization modification with phenylboronic acid
Dudičová, Dorota ; Uchman, Mariusz Marcin (advisor) ; Strachota, Adam (referee)
This thesis deals with the synthesis of propargyl-functionalized amphiphilic diblock copolymers, poly(ε-caprolactone)-b-poly(ethylene oxide), PgCL-PEO via Ring Opening Polymerization (ROP) using monohydroxyl-terminated PEO block as the macroinitiator and its post polymerization modification via Copper-Catalyzed Azide-Alkyne Click reaction (CuAAC) to introduce phenylboronic acid functionality into block copolymers. A reproducible synthetic protocol was developed for preparation of well-defined functional diblock copolymers. The amphiphilic block copolymers were characterized in terms of molecular weight and dispersity by various techniques: Nuclear Magnetic Resonance (NMR) spectroscopy, Gel Permeation Chromatography (GPC) and Matrix-Assisted Laser Desorption/Ionization Time-of-Flight (MALDI ToF) Mass Spectrometry. Keywords: Amphiphilic block copolymers, CuAAC click, phenylboronic acid, poly-ε- caprolactone, ring-opening polymerization
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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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Nanoparticles based on complexes of hydrophilic block polyelectrolytes and new gemini ionic surfactants
Šomšáková, Katarína ; Uchman, Mariusz Marcin (advisor) ; Trhlíková, Olga (referee)
This bachelor thesis deals with preparation and study of the aqueous solutions of block polyelectrolyte poly(2-vinylpyridine)-b-poly(ethylen oxide), P2VP-PEO with gemini surfactants 6,6'-(ethan-1,2-diylbis(oxy)) bis(3-dodecylbenzenesulfonate acid), 6,6'- (buthan-1,4-diylbis(oxy)) bis(3- dodecylbenzenesulfonate acid) and 6,6'-(hexane-1,6- diylbis(oxy)) bis(3- dodecylbenzenesulfonate acid) complexes and with P2VP-PEO and sodium dodecylsulfate, SDS, complexes, and compares their physico-chemical properties. Formed particles were characterized by static and dynamic light scattering, zeta potential, isothermal titration calorimetry and transmission cryo-electron microscopy. Even small amount of surfactant leads to coassembly of P2VP-PEO with surfactants, formed by PEO shell and P2VP/surfactant core. The nanoparticles of block polyelectrolyte and gemini surfactants in 0.1M HCl are stable and their size depends on the spacer lenght and the surfactant/polymer ratio.
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Synthesis and characterization of ABA triblock copolymers modified with glucose via thiol - ene click reaction
Hašpl, Adam ; Uchman, Mariusz Marcin (advisor) ; Štěpánek, Miroslav (referee)
The bachelor thesis is focused on method of postpolymerisation modification of two poly(ethylene oxid-b-1,2-butadiene-b-ethylene oxide) amphiphilic block copolymer samples with high content of 1,2-isomer units in inner polybutadiene block by thiolene click. The implemented modification agent was 1-thio-β-D-glucose tetraacetate. The thesis is further focused on methods of copolymer sample characterization before and after modification reaction. Structure and degree of functionalization of vinylic units in polybutadiene block after modification was determined by nuclear magnetic resonance spectroscopy. The dimensions of prepared polymeric particles were studied by static and dynamic light scattering methods. Keywords: ABA triblock copolymers, self-assembly, click reaction, NMR spectroscopy, light scattering
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HIGHT-RATE SUPERCAPACITORS BASED ON CONDUCTING POLY(3,4 ETHYLENEDIOXYTHIOPHENE)
Ivanko, Iryna ; Tomšík, Elena (advisor) ; Uchman, Mariusz Marcin (referee) ; Perrin, François-Xavier (referee)
An understanding of the effect of molecular structure on physicochemical properties of organic semiconducting polymers requires a proper method of preparation during which it is possible to obtain a polymer with a well-defined chemical structure. Therefore, in this work three methods of preparation of poly(3,4-ethylenedioxythiophene) (PEDOT), such as chemical oxidation, electrochemical polymerization, and a new method, namely acid-assisted polymerization, were utilized. Using chemical oxidation polymerization, it was investigated the effect of ions from Hofmeister series, specifically formate ion, on PEDOT physicochemical properties. In particular, it was shown the formation of hydrated oligomer chains which assemble into semicrystaline structure. Moreover, it was demonstrated that hydrated oligomers undergo rearrangement of its chains during the electrochemical treatment with the formation of anisotropic structure, and unique photoluminescence properties. Next method for PEDOT preparation, which was for the first time introduced by us, is acid-assisted polymerization. It was shown that it is possible to prepare, by using polar Brønsted acid, the PEDOT solution without applying oxidant at room temperature. Moreover, we have shown a way to control the optical properties of PEDOT, by the mean of a...
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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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