Diploma thesis deals with the grafting of vinyltrimethoxysilane (VTMOS) onto poly(3–hydroxybutyrate)PHB. Subsequent characterization of the amount of grafted VTMOS and changes in the thermal properties associated with the rate of crystallization. The theoretical part deals with mechanism and the influences of grafting. In the experimental part VTMOS was grafted onto PHB without subjecting VTMOS to hydrolysis and subsequent crosslinking. By differential scanning calorimetry (DSC) and Avrami equation, the effect of grafted silane group on pure was studied. The MVR was used to compare the rheological properties of initial PHB, grafted PHB and crosslinked PHB by siloxane linkages.

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.

Reversible adsorption of nucleid acids on magnetic carriers was studied in this diploma thesis. Magnetic P(HEMA-co­-GMA) microspheres and magnetic glass particles were used. The aim of the study was to isolate DNA in suitable quality for polymerase chain reaction (PCR). Adsorption of DNA on magnetic carriers was achieved after DNA condensation by PEG and NaCl in separation mixture. PEGs of various molecular weight (600 and 6000 g/mol) and different concentrations of PEG in separation mixture (4, 8, 12, 16%) were used. Quantity of eluted DNA incerased with molecular weight and concentration of PEG in separation mixtures. Optimized experimental conditions were applied for the separation of DNA from chicken erythrocytes, purified DNA, DNA in crude lysates of bacterial cells of Lactobacillus paracasei ssp. paracasei CCDM 211/06 and from real samples (liquid dairy products, hard cheese). The presence of target DNA in eluates was tested using genus specific PCR (genus Lactobacillus) or species specific PCR (species Bifidobacterium longum) Aqueous two-phase system (liquid-liquid) was used for separation of DNA from real symplex, too. At first the condiotions aqueous two-phase systém creation were studied. It was created by 16% PEG of various molecular weight (600, 6000 g/mol) and by various concentration of ammonium sulphate. Reversible DNA adsorption on carboxyl group-containing magnetic nonporous P(HEMA-co-EDMA) microspheres for the isolation PCR-ready DNA from liquid dairy products containing PCR inhibitors was studied, too. The quality of isolated DNA was checked by PCR amplification.The presumption on the elimination of PCR inhibitors from DNA samples was confirmed.

Samples with thin layer of poly[methyl(phenyl)silylene] were prepared for cathodoluminescence measurement. Dependence of cathodoluminescence on temperature was studied on these samples. Spectra of emitted light were measured on the samples when they were gradually heated to 20, 50, 75, 100 and 125°C. Kinetics of the process of poly[methyl(phenyl)silylene] regeneration at higher temperature was observed. Samples of polysilylene were displayed by scanning electron microscopy.

The isolation of deoxyribonucleic acid (DNA) was studied in the diploma thesis by using three different methods: phenol extraction, salting with sodium chloride and magnetic separation with reversible adsorption of nucleic acids on different magnetic carriers. There were used five different properly functionalized carriers for the isolation of DNA: magnetic silicagel, P(HEMA-co-GMA) ox. I, P(HEMA-co-GMA) ox. II, Dynal DNA Direct and Perovskit 439. The reversible imobilization of DNA on the magnetic carrier was proceeded under the conditions of high concentration of NaCl and poly(ethyleneglycol) (PEG). There was induced the condensation of DNA by 2 M NaCl and PEG with molecular mass 6000 for binding of the DNA to the magnetic carriers and the final concentration of PEG in the separation mixture was 8 and 16 %. The aim was to gain the DNA of quality suitable for polymerase chain reaction (PCR). The DNA was isolated from the bacterial cultures of three probiotic strains, L. amylovorus CCM 4380T, L. zeae CCM 7069 T, L. plantarum CCM 7039T, which were cultivated in MRS medium. The DNA was also isolated from the fermented dairy products: Jihočeský zákys s ovocem jahoda (the fermented dairy product with the probiotic culture of Lactobacillus acidophilus, Bifidobacterium lactis and Streptococcus thermophilus), Revital active (the yogurt with inulin and the probiotic culture of Lactobacillus rhamnosus, Lactobacillus acidophilus and Bifidobacterium sp.) and Actimel višeň (the dairy product with the probiotic culture of Lactobacillus casei). When the PCR with the isolated DNA was passed off, the PCR products were detected by the gel electrophoresis with agarose. The success of the DNA isolation of the probiotic bacteria by phenol extraction, salting with NaCl and by magnetic separation, was verified by the PCR method. The method of magnetic separation using magnetic carriers was also verified for the isolation of DNA of quality suitable for PCR from the probiotic fermented dairy products.

The diploma thesis is focused on the study of the influence of cultivation conditions and arrangement for the production of extracellular polymeric substances by using yeast-like microorganism Aureobasidium pullulans. In the theoretical part a brief description of A. pullulans, its use in biotechnology and produced exobiopolymers, especially pullulan and poly-L-malic acid are presented. The first aim of the experimental part was to set the most appropriate cultivation conditions for A. pullulans CCM 8182. Growth and production properties in optimum conditions were compared with cultivation on waste substrates - oat bran, buckwheat husks, apple fiber and others. Waste substrates can be used as cheap nutrient sources which enable reducing cost of potential biotechnological production. As a further part of this work, optimization of HPLC/RI method for analysis of exobiopolymers has been done. Optimal mobile phase composition and chromatography conditions were proposed. Column Roa organic acid H+ was the most suitable for simultaneous separartion of glucose and malic acid. Before HPLC analysis hydrolysis of polymers was done. Sulphuric acid (5 mmol/L) was used as a mobile phase at flow rate 0.5 mL/min and temperature 60 °C. The highest production of pullulan occurred using oat bran as a substarate (13.03 g/L) at an initial pH 7.5. Maximum production of poly-L-malic acid was observed during the cultivation on apple peels (2.89 g/L) at pH 6. It was found that the higher production of poly-L-malic acid occurred at pH 6, while higher production of pullulan was at pH 7.5.

Dans le contexte des cellules photovoltaïques (PV) à base de silicium cristallin (c-Si), le développement de structures de contacts dits « passivants », qui permettent de limiter les pertes par recombinaisons des porteurs de charge à l’interface entre le métal et le c-Si, est un des principaux leviers vers l’obtention de plus hauts rendements. Une approche de contacts passivés consiste à intégrer entre le métal et le c-Si une jonction composée d’une couche de silicium poly-cristallin (poly-Si) fortement dopée sur une mince couche d’oxyde de silicium (SiOx < 2 nm).Les objectifs de ce travail sont d’une part de développer une jonction poly-Si/SiOx compatible avec la fabrication industrielle des cellules PV, et d’autre part d’améliorer la compréhension des mécanismes de passivation et de transport des charges au niveau de la fine couche de SiOx située à l’interface entre le poly-Si et le c-Si.Dans ce travail, une jonction de poly-Si/SiOx dopée au bore a été développée, le dopage de la couche étant dans un premier temps réalisé in-situ pendant l’étape de dépôt chimique en phase vapeur assisté par plasma (PECVD) de la couche poly-Si. La méthode de dépôt PECVD est répandue dans l’industrie PV et permet la fabrication de la couche poly-Si d’un seul côté du substrat c-Si. Cependant, elle induit une forte concentration d’hydrogène dans la couche déposée, ce qui entraine la formation de cloques à l’interface avec le c-Si et tend à dégrader les propriétés de passivation de surface de la jonction après recuit de cristallisation. L’optimisation des conditions de dépôt (température de dépôt et ratio de gaz H2/SiH4) a permis d’obtenir des couches de poly-Si dopées in-situ intègres. Par la suite, une méthode de dopage alternative, par le biais du dépôt d’une couche diélectrique riche en bore sur le poly-Si, a été appliquée afin de réduire l’apport en hydrogène pendant le dépôt et d’obtenir des couches de poly-Si intègres plus épaisses. L’ajout d’une étape d’hydrogénation a permis d’obtenir des propriétés de passivation de surface au niveau de l’état de l’art pour les deux types de jonctions poly-Si/SiOx développées.A la suite du développement de la jonction poly-Si/SiOx, la caractérisation physico-chimique de la couche SiOx a été réalisée et a démontré une possible amélioration de la stœchiométrie de la couche vers SiO2 ainsi qu’une dégradation de son homogénéité en épaisseur sous l’effet du recuit de cristallisation à haute température. Ces phénomènes pourraient s’expliquer par une diffusion des atomes d’oxygène à l’interface. D’autre part, l’étude du transport des charges à travers le SiOx par C-AFM a mis en évidence les limites de cette technique quant à la détermination de nano-ouvertures au sein de la couche SiOx (qui favoriseraient le transport des charges). Enfin, une méthode de caractérisation des défauts recombinants à l’interface entre une jonction de poly-Si intrinsèque et le c-Si a été mise en œuvre. Cette méthode a permis de modéliser les recombinaisons à l’interface poly-Si/c-Si via deux défauts discrets apparents dont les niveaux d’énergie dans la bande interdite et les ratios de sections efficaces de capture des électrons et des trous ont été déterminés. / In the context of high efficiency solar cells (SCs) based on crystalline silicon (c-Si), the development of "passivating" contact structures to limit the recombination of charge carriers at the interface between the metal electrode and the c-Si has been identified as the next step to further improve the photovoltaic (PV) conversion efficiency. Passivating contacts consisting of a highly doped poly-crystalline silicon layer (poly-Si) on top of a thin layer of silicon oxide (SiOx ≤ 2 nm) are particularly sparking interest as they already demonstrated promising conversion efficiency when integrated in SCs.The objectives of this work are to develop a poly-Si/SiOx passivating contact compatible with the industrial production of c-Si SCs, and to investigate the passivation and charge transport mechanisms in the region of the thin SiOx layer located at the interface between the poly-Si and the c-Si.In this work, a boron-doped poly-Si/SiOx contact was fabricated. The doping of the layer was first performed in-situ during the deposition of a hydrogen-rich amorphous silicon (a-Si:H) layer by plasma-enhanced chemical vapor deposition (PECVD). The PECVD step was followed by an annealing step for crystallization of the poly-Si layer. The PECVD presents the advantages of being widespread in the PV industry and enabling the fabrication of the poly-Si contact on a single side of the c-Si substrate. However, it induces a high concentration of hydrogen in the deposited layer, which causes the formation of blisters at the interface with the c-Si and tends to degrade the surface passivation properties of the contact after annealing for crystallization. The optimization of the deposition conditions (temperature and H2/SiH4 gas ratio) enabled to obtain blister-free in-situ doped poly Si layers. An alternative doping method consisting of the deposition of a boron-rich dielectric layer on top of the poly-Si layer was applied to reduce the hydrogen content of the deposited layer. This approach enabled to obtain thicker blister-free poly-Si layers. The diffusion of hydrogen in the contact after annealing is known to provide a further chemical passivation of the poly-Si/c-Si interface. In this work, the addition of a hydrogenation step enabled to obtain state-of-the-art surface passivation properties for the two types of poly Si/SiOx contact fabricated.After developing the poly-Si/SiOx contact, a study of the effect of the annealing step on the chemical and structural properties of the SiOx layer was performed. Results indicated a possible improvement of the stoichiometry of the layer towards SiO2 as well as a degradation of its homogeneity at the poly-Si/c-Si interface after annealing at high temperature. These phenomena could be explained by a diffusion of the oxygen atoms content in the interfacial SiOx layer. The transport mechanism of charge carriers through the SiOx layer was conducted by C-AFM. This study revealed the limits of this technique to determine the presence of pinholes within the SiOx layer (that would help the transport of charge carriers). Finally, a method for characterizing recombinant defects at the interface between an intrinsic poly-Si junction and the c-Si has been developed. This method enabled to model the recombination phenomena at the poly-Si/c-Si interface via two apparent discrete defects. Their associated energy levels in the bandgap and ratios of electron and hole capture cross sections were estimated.

Poly (2-ethyl-2-oxazoline)-based amphiphilic diblock copolymer has the potential to form promising membrane materials for water purification due to the thermal stability and good solubility in aqueous solution and also for gas separation because of the presence of polar amide group along the polymer backbone. Moreover, their self-assembly into micelles renders them candidate materials as nanocarriers for drug delivery applications. In this study, a novel well-defined linear PEtOx-based amphiphilic diblock copolymer with a hydrophobic fluoropolymer, i.e., PVDF, have been successfully synthesized by implementing a synthesis methodology that involves the following four steps. In the first step, poly (2-ethyl-2-oxazoline) (PEtOx) was synthesized via living cationic ring-opening polymerization (LCROP) of 2-ethyl-2-oxazoline (EtOx) monomer. The “living” nature of LCROP allows the desirable termination to occur by using the proper termination agent, namely, water, to achieve the polymer with a terminal hydroxyl group, i.e., PEtOx-OH. The hydroxyl end group in PEtOx-OH was converted to PEtOx-Br using 2-bromopropionyl bromide via an esterification reaction. In the third step, the PEtOx-Br macro-CTA was subsequently reacted with potassium ethyl xanthate to insert the necessary RAFT agent via nucleophilic substitution reaction to obtain PEtOx-Xanthate. It s worth mentioning that this step is vital for the sequential addition of the second block via the RAFT polymerization reaction of fluorinated monomer, i.e., VDF, to finally obtain the well-defined amphiphilic diblock copolymer with variable controlled chain lengths. Proton Nuclear Magnetic Resonance Spectroscopy (1H-NMR) and Fourier Transform Infrared Spectroscopy (FT-IR) confirmed the structure of the macroinitiator and final copolymer, respectively. Size Exclusion Chromatography (SEC) determined the number-average molecular weight (Mn) and the polydispersity index (PDI) of the obtained copolymer. Furthermore, the polymorphism of the diblock copolymer characterized by X-Ray Diffraction (XRD) indicated that the copolymer displays the electroactive α-phase. The resultant amphiphilic diblock copolymer exhibits spherical micelles morphology, as confirmed by Dynamic Light Scattering (DLS) and Atomic Force Microscopy (AFM). Moreover, Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) investigated the thermal decomposition behavior of the copolymer and determined the glass transition temperature (Tg ≈ 70 °C), melting temperature (Tm ≈ 160-170 °C), and crystallization temperature (Tc ≈ 135-143 °C) of the diblock copolymer, respectively.

Novel poly(ethylene isophthalate) (PEI) and poly(ethylene terephthalate) (PET) polymers containing terminal units derived from sodio 3-sulfobenzoic acid (SSBA) were synthesized using catalyzed melt polymerization techniques. Various concentrations of the ionic end group, SSBA, were successfully incorporated in a telechelic fashion. For comparison, polyesters containing telechelic alkyl groups with controllable molecular weights were also synthesized. Furthermore, ionic copolymers of dimethyl isophthalate and trans-cyclohexane dicarboxylate, dimethyl isophthalate and dimethyl terephthalate were synthesized to study the influences of polarity and rigidity of the polymer chain backbone on material properties. Novel branched polyester ionomers using trimellitic anhydride were also prepared. In addition to modifying the polymer compositions, PET ionomers were blended with zinc stearate to investigate the effect of plasticizer on the melt processibilty of the ionomers. FTIR spectroscopy, which was used to quantify the sulfonate end groups for all of the ionomers, indicated an absorbance peak for the S-O stretching mode between 600-700 cm⁻¹. ¹H NMR spectroscopy was used to confirm the structure of the ionic and non-ionic polyesters, as well as to verify the presence of the terminal groups. By systematically varying the chemical structure of these ionomer model systems (i.e., altering the contents of ionic functional groups), detailed characterizations were carried out, wherein the ionic interactions/aggregations in the ionomers were found to play an important role in the resulting material properties. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) measurements were performed to study the effects of ionic groups and oligomer composition on the thermal properties of the polyesters. The glass transition temperatures of the ionomers revealed that the ionic interaction helped to maintain the structural integrity of the polymer chains, thus limiting their mobility. The dilute solution viscosity behavior of the ionomers exhibited upward curvature, which is a key characteristic of an ionomer. In PEI ionomers, the ionic aggregates formed at lower temperatures (<150 °C), while at higher temperatures (>150 °C), the ionic aggregations dissociated and behaved similarly to oligomers with lower molecular weights. Dodecanol was used as an effective end-capper to control the molecular weight of the non-ionic polyesters. In addition to telechelic ionic PEI and PET homopolymers, copolymers of poly(ethylene isophthalate-co-trans-1,4-cyclohexane dicarboxylate) (PEI-co-trans-CHDC) and poly(ethylene isophthalate-co-terephthalate) (PEIT) telechelic ionomers were also synthesized and characterized. Introducing trans-1,4-cyclohexane dicarboxylate into PEI ionomers decreased the polarity and packing regularity of the polymer chains. Also, the kinked-structure of dimethyl isophthalate reduced the regularity of the polymer chains in PET ionomers, thus reducing their propensity for rapid crystallization. Crystallization kinetics were studied for both ionic and alkyl telechelic polyesters, and resulting data revealed that the nature of the endgroup had a dramatic effect on crystallization from the melt state. The catalyst residue in the polymers also affected the crystallization rate for both ionic and non-ionic polyesters. With regard to the ionomers, antimony catalyst interacted with ionic aggregates, further increasing the crystallization rate. Branched PEI and PET ionomers showed an increase in melt strength. After blending with zinc stearate, the melt viscosity of the PET ionomers dropped dramatically. / Master of Science

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