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Mechanisms and kinetics of poly(3-hydroxybutyrate) reactions
Melčová, Veronika ; Sedláček,, Tomáš (referee) ; Bakoš, Dušan (referee) ; Přikryl, Radek (advisor)
Tato práce se zabývá reakcemi bakteriálního biopolymeru poly(3-hydroxybutyrátu) s vybranými reaktivními činidly v tavenině. Využity byly sloučeniny různých funkčních skupin; isokyanáty, karbodiimidy, alkoholy a epoxidy; a funkcionality; od dvou po polyfunkční. Cílem je charakterizovat kinetiku termické degradace tohoto polymeru během zpracování samotného a s přídavkem výše uvedených činidel v různých množstvích. Za tímto účelem bylo provedeno reologické měření sestávající ze čtyř po sobě jdoucích frekvenčních testů v rozsahu 0,1–50 Hz a ze získaných dat byl vyhodnocen parametr kvantifikující rychlost poklesu viskozity. Tento kinetický parametr umožnil porovnání účinků jednotlivých činidel. Dále byly připraveny reaktivní vzorky hnětením, při němž byl zaznamenán a diskutován kroutící moment, a také v roztocích, u kterých byla měřena viskozita. U takto připravených vzorků byly studovány tepelné vlastnosti, molekulová hmotnost a infračervená spektra. Z testovaných aditiv vykázaly nejlepší celkové výsledky v provedených experimentech polymerní karbodiimid Raschig 9000, hexamethylen diisokyanát, poly(glycidyl methakrylát) syntetizovaný pro účely této práce a poly(hexamethylen diisokyanát). Pozoruhodné je, že vzorek se 100násobným molárním přebytkem Raschigu měl o 20–30 % nižší rychlost poklesu viskozity v oblasti frekvence 0,1–5 Hz. Kromě toho byl proveden test enzymatické biologické rozložitelnosti s lipázou a v abiotických podmínkách. Nejvyšší rychlost poklesu molekulové hmotnosti vykazoval poly(3-hydroxybutyrát) aditivovaný poly(glycidylmethakrylátem).
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Poly(3-hydroxybutyrate) based materials for 3D printing in medical applications
Krobot, Štěpán ; Vojtová, Lucy (referee) ; Přikryl, Radek (advisor)
Tato diplomová práce se zabývá přípravou a testováním 3D tištěných skafoldů pro kostní tkáňové inženýrství. Cílem práce je laboratorní příprava polymerních směsí na bázi poly(3-hydroxybutyrátu), polymléčné kyseliny a polykaprolaktonu a jejich zpracování do podoby 3D tiskových strun. Byly připraveny tři polymerní směsi, které byly zpracovány do podoby 3D tiskových strun. Pro vyhodnocení termických vlastností byla provedena diferenciální skenovací kalorimetrie, následně teplotní věžový test a test „warpingu“ pro stanovení zpracovatelských podmínek při 3D tisku. Nejnižší naměřený „warping“ koeficient byl 1,26 u směsi poly(3-hydroxybutyrátu) s polykaprolaktonem a změkčovadlem. Ke studiu mechanických vlastností materiálů byla použita tahová zkouška, tříbodová ohybová zkouška a tlaková zkouška. Skafoldy s různými povrchy pro kostní tkáňové inženýrství byly 3D tisknuty z připravených strun s cílem určit nejoptimálnější povrch pro proliferaci buněk. Pro stanovení povrchových vlastností a jejich vlivu na adhezi buněk bylo provedeno měření optického kontaktního úhlu s využitím metody OWRK pro výpočet povrchové energie. 3D vytištěné povrchy byly také podrobeny analýze drsnosti pomocí konfokálního mikroskopu, aby byla určena jejich drsnost a její vliv na kontaktní úhel s vodou a růst buněk. Nakonec v poslední části byly ve spolupráci s Ústavem experimentální medicíny AV ČR provedeny in vitro testy na skafoldech s cílem zjistit, zda jsou připravené materiály necytotoxické, a jak povrch skafoldu ovlivňuje růst a proliferaci buněk. Bylo zjištěno, že dva ze tří materiálů nejsou cytotoxické (obě směsi poly(3-hydroxybutyrátu) s polykaprolaktonem) a že jejich mechanické vlastnosti jsou srovnatelné s lidskou trabekulární kostí. Nejoptimálnějším povrchem pro růst buněk je pravděpodobně mřížka o průměru 50 m s drsností podél perimetru 1,9 m, což odpovídá kontaktnímu úhlu s vodou 74,1°.
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Biocomposites based on polyhydroxybutyrate for 3D printing
Horálek, Matyáš ; Tocháček, Jiří (referee) ; Přikryl, Radek (advisor)
The submitted diploma thesis deals with preparation and characterization of biocomposite based on poly-3-hydroxybutyrate. Biocomposites were fabricated with respect to later use in 3D printing. The methodology for testing different kinds of materials and their suitability for 3D printing as well as evaluation of mechanical and thermal properties was established. The first part of this work was focused on the experiments with print temperature and the material flow rate and its influence on the look of 3D printed object and on the material tendency to warp during 3D printing. The design of the experiment method was used for the analyzing of obtained data. It was proven that the amount of kaolin and tributyl citrate has positive influence in reducing warping. By optimization of the biocomposite recipe it was achieved improvement in tensile modulus of elasticticity, ductility, tensile strength, notched and unnotched toughness.
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Optimization of poly(3-hydroxybutyrate) based biocomposite with respect to its printability and mechanical properties
Chaloupková, Kateřina ; Obruča, Stanislav (referee) ; Přikryl, Radek (advisor)
The presented theses deals with preparation and optimalization of biocompatible material based on poly(3-hydroxybutyrate). Other components of prepared samples are polylactid acid, hydroxyapatite and commercially available plasticizer Syncroflex3114. These components were chosen based on their biocompatibility and properties that can be possibly used in tissue engineering. Theoretical part of this theses contains general overview of bone tissue and review of materials used in bone tissue regeneration. Part of this thesis also deals with the problematics of scaffolds. Aim of the experimental part is a planned experiment, which is used to optimize the mixture with respect to printability and mechanical properties. The first step is the preparation of samples based on the proposed conditions and their subsequent processing into a filament with an exact diameter of 1,75 mm for 3D printing using the fused deposition modeling method. From the prepared filaments, test specimens were printed for the following experiments: temperature tower, warping coefficient measurement, bending and pressure test. Data from these experiments were processed using a mathematical model in the form of graphs and equations which show the effect of material components on the measured quantity. It was found that the amount of plasticizer in the sample affects the properties the most. This effect is negative in all cases and worsens the properties of the material. The result of the planned experiment is also a mixture optimized for the best possible printability and mechanical properties (bending modulus 3,3 GPa and pressure modulus 2,3 GPa). With regard to the potential application of the material in bone tissue engineering, the first accelerated biodegradation screening tests were performed for selected samples. The results of accelerated degradation tests are ambiguous and further optimization is needed. Simultaneously with the diploma thesis, biological testing of scaffolds printed on a 3D printer from prepared samples took place. All tested samples were found to be biocompatible.
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Preparation of Poly(3-hydroxybutyrate) based acrylic monomer
Liška, Marek ; Přikryl, Radek (referee) ; Figalla, Silvestr (advisor)
The main aim of this thesis is to research and prepare acrylic (methacrylic) monomers derived from poly(3-hydroxybutyrate). The monomers were prepared in two-step syntheses. In the first step P3HB was depolymerised with selected alcohols and afterwards, products of those syntheses were used as substrate and mixed with polymethylmethacrylate to produce their methacrylic derivates. The selected alcohols for the alcoholysis were ethanol and ethylene glycol. In total, four substances were prepared. Products of alcoholysis were ethyl-3- hydroxybutyrate, 2-hydroxyethyl-3-hydroxybutyrate and their methacrylic derivates. Significant part of this thesis is aimed towards the analysis of prepared substances and the analysis of reactions. In the process, titrations and instrumental methods, such as gel permeation chromatography (GPC), infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), thermogravimetry (TGA) and differential scanning calorimetry (DSC) were used. This work describes preparation and analysis of polymers prepared from methacrylates from the mentioned syntheses. Cross-linked polymers, because of their low glass-transition temperature are elastomers.
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Microfibers based on polyhydroxybutyrate for medical applications
Gregušková, Zuzana ; Obruča, Stanislav (referee) ; Přikryl, Radek (advisor)
Diplomová práca je zameraná na mikrovlákna na báze biopolyméru poly(3-hydroxybutyrátu) a ich využitie v medicínskych aplikáciách. Teoretická časť práce sa zaoberá štúdiom procesu tvorby vláken pomocou technológie odstredivého zvlákňovania, jeho kinetikou a faktormi ovplyvňujúcimi vznik a vlastnosti vláken. Teoretická časť sa následne orientuje na krátky prehľad biopolymérov používaných v tejto technológii, charakteristiku materiálu poly(3-hydroxybutyrátu) a taktiež prezentuje návrh potenciálnej cieľovej aplikácie daných mikrovláken. Praktická časť sa koncentruje sa prípravu mikrovláken zo spomínaného poly(3-hydroxybutyrátu). Sledované a optimalizované sú viaceré parametre vedúce k lepšej zvlákniteľnosti materiálu. Praktická časť je rozšírená o modifikáciu polymérneho roztoku prídavkom iných biopolymérov a zmäkčovadiel a prípravu mikrovláken z takto modifikovanej polymérnej zmesi. Pozornosť je venovaná taktiež optimalizácii procesných parametrov. Pripravené mikrovlákna sú následne analyzované a charakterizované viacerými metódami a vzájomne porovnávané s cieľom vyvinúť alternatívu k súčasne používaným substrátom pre rast buniek v 3D.
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Effect of chemical structure of plasticizer on material properties based on polyhydroxybutyrate
Stehnová, Ivana ; Alexy, Pavol (referee) ; Přikryl, Radek (advisor)
This master’s thesis deals with plasticization of poly(3-hydroxybutyrate), polylactid acid and their blend. It explores effect of chemical structure of plasticizer on mechanical properties of this polymer blend and on its diffusion from the polymer blend. Syntheses of plasticizers based on oligomeric polyadipates, citrates, lactate and esters of 2 ethylhexanoic acid with poly(ethyleneglycol) were carried out. Molecular weight distribution of synthesized plasticizers was determined using gel permeation chromatography. Poly(3-hydroxybutyrate), polylactid acid and their blend were plasticized with synthesized and commercial plasticizers. From commercial, chosed plasticizers were based on citrates and ester of 2-ethylhexanoic acid with poly(ethyleneglycol). Thermal stability of selected commercial plasticizers in polylactid acid was studied using thermogravimetry. Diffusion of plasticizers from poly(3-hydroxybutyrate), polylactid acid and their blend during exposure to 110 °C was also investigated. Mechanical properties of prepared blends were tested by tensile test. Almost all used plasticizers showed positive softening effect in blend. The highest elongation at break was detected for the blend with commercial acetyltributylcitrate, where elongation at break reached 328 % relative to 21 % for neat non-plasticized blend.
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Study of microplastic sorption properties
Hlaváčková, Hana ; Kučerík, Jiří (referee) ; Řezáčová, Veronika (advisor)
There is currently an effort to replace conventional plastics with biodegradable products that will have the ability to replace these substances. One of the possible biodegradable felt, which is currently being studied in detail, is also poly (3-hydroxybutyrate), which is produced by bacteria. This bachelor thesis deals with the sorption of selected substances on poly(3-hydroxybutyrate) microparticles. Substances whose contamination of water sources is a significant problem today have been selected for this work. Specifically, the sorption of the nonsteroidal anti-inflammatory substance ibuprofen, the triazole fungicide tebuconazole and the most common drug caffeine on PHB particles, which fall in the size of the microplastic group, were studied. The method of liquid chromatography with mass detection was used for analyzes.
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Biocomposite material for 3D print in the field of regenerative medicine
Chaloupková, Kateřina ; Obruča, Stanislav (referee) ; Přikryl, Radek (advisor)
The presented thesis deals with preparation of material for use in regenerative medicine based on poly(3-hydroxybutyrate) and its characterization. In addition to poly (3-hydroxybutyrate), there were used other materials lactic acid (PLA), tricalcium phosphate (TCP) and two types of plasticizers Citroflex®B-6 (CB6) and Syncroflex3114 (S3114). These materials were selected based on their biocompatibility and, in the case of TCP, also bioactivity. TCP allows new bone to grow on the surface of the scaffold. PLA was used to improve the mechanical properties of the material. Both plasticizers have been used to improve the processability of the material. Theoretical part of this work contains a literature review describing basic information about used materials. Aim of the experimental part is to prepare the material, characterization of properties and determination of printability on a 3D printer. The material is examined for thermal properties by thermogravimetric analysis and differential scanning calorimetry. This work also deals with the matter of 3D printing, especially FDM technology. It has been found that materials containing the syncroflex plasticizer are better processed and therefore printed on a 3D printer. The printability tests performed are temperature towers and filling studies. Printed samples were subjected to mechanical tests of tensile and bending tests. Experiments of cytotoxicity and biocompatibility of the material were also performed. Within the work, TCP particles were characterized using a particle size analyzer. The average TCP particle size is 10,76 µm. Using SEM-EDX, the distribution of TCP in sample filaments was subsequently observed, where it was found that by mixing TCP particles with the remaining components of materials, TCP particles agglomerate into formations up to 20 µm in size. Roughness of materials was determined by confocal microscopy. Cytotoxicity was also tested in the extracts of samples on mouse fibroblasts. Cytotoxicity was determined by metabolic activity assay and light microscopy. The metabolic activity test proved the biocompatibility of the observed materials; therefore, it was possible to perform cell proliferation and biocompatibility tests directly on the samples. Assays were performed using human mesenchymal stem cells. DNA quantification was used to determine cell proliferation. Shape of cells was subsequently observed by confocal microscopy. Tests confirmed growth of cells and their appropriate shape. Stem cell differentiation into bone was performed by measuring alkaline phosphatase activity.
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Isolation of lignin from grape seeds and its application as filler for polyhydroxyalkanoates (PHA)
Vostrejš, Pavel ; Vítová, Eva (referee) ; Kovalčík, Adriána (advisor)
This diploma thesis deals with 1) the preparation of biodegradable polymer films based on polyhydroxyalkanoates (PHA) and 2) their modification by lignin as an active additive. The motivation for this work was to prepare active packaging material for food packaging. Polymer films were prepared by blending of neat crystalline poly(3hydroxybutyrate) (P3HB) and amorphous polyhydroxyalkanoate (PHA). The lignin was isolated from grape seeds derived from grape pomace. The solubility of lignin in chloroform was improved by acetylation. The properties of the isolated lignin were determined by elemental analysis, ash content, and infrared spectroscopy (FTIR). Lignin was used as an active additive for the modification of polymeric films prepared by solution casting of P3HB or P3HB blended with amorphous polyhydroxyalkanoate. The effect of different concentrations of lignin in the range of 1 to 10 % was tested. The lignin type and concentration had a different influence on the final thermal and mechanical behaviour of polymeric films. Lignin increased the values of the Young modulus and tensile strength of the prepared films. Differential scanning calorimetry data confirmed that lignin positively modified crystallization kinetics of P3HB. Thermogravimetry was used to analyse the thermal stability of PHA films. Lignin markedly increased the thermal stability of PHA films. However, acetylated lignin harms the mechanical properties of films. Moreover, this work showed that lignin isolated from grape seeds and added into PHA films proved its high antioxidant capacity. PHA films with lignin displayed much better gas barrier properties compared with PHA films without lignin. The prepared bioactive PHA films fulfil the requirements for sustainable food packaging with high antioxidant capacity and excellent gas barrier properties.
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