Os polímeros com propriedades luminescentes, e mais especificamente, os eletroluminescentes, tem atraído muita atenção devido a sua possível aplicação em dispositivos ópticos e eletrônicos do tipo LEDs (light-emitting diodes). Grande parte das pesquisas realizadas no campo da eletroluminescência se baseia em estudos sobre poli (arilenos-vinilenos), como o poli-(p-fenileno vinileno), PPV, e seus derivados. No processo de polimerização de tais polímeros, a influência de algumas variáveis são importantes em suas propriedades finais. Este trabalho descreve a exploração da influência de diversas variáveis no processo de polimerização do derivado do PPV, o poli-(2-metoxi-5-hexiloxi-p-fenileno-vinileno) MH-PPV. Além disso, com o intuito de verificar a influência da presença de aditivos na massa molar dos polímeros foram realizadas polimerizações utilizando-se os aditivos 4-metoxifenol, cloreto de tercbutila e cloreto de benzila durante o processo de polimerização. Também foram realizados estudos sobre o modo de adição e temperatura de polimerização utilizando o aditivo cloreto de benziIa. Todos os produtos foram caracterizados por HPSEC (Cromatografia de Exclusão por Tamanho) para determinação das massas molares dos polímeros. Observou-se que a temperatura e a velocidade de adição da base no meio reacional são variáveis que influenciam significativamente no processo de polimerização e, conseqüentemente, na distribuição na massa molar dos polímeros. Foi constatado que o uso de aditivos no processo de polimerização previne a formação de géis; fornece polímeros com baixa massa molar, aumentando a solubilidade dos polímeros em solventes orgânicos como clorofórmio e THF. A análise térmica dos polímeros revelou que além da Tg em tomo de 160oC, todos os polímeros apresentaram uma transição em tomo de 75oC. Os espectros de absorção e emissão não foram afetados de forma significativa dentro dos valores de massas molares médias obtidas. Foi possível também obter uma relação entre os valores de massa molar obtidos por HPSEC e valores de viscosidade relativa, que pode ser utilizada para estimar valores de Mw através de medidas de tempo de escoamento / Electroluminescent polymers have been widely investigated due to its potential applications in optoelectronic devices such as polymer light-emitting diodes (PLEDs). Most of the polymers suitable for application in PLEDs are related to the poly(arylenes-vinylene) polymers, including the poly(p-phenylene-vinylene) (PPV) and its derivatives, which are of special interest. Such materials can exhibit significant differences on their final properties upon changes on specific synthesis parameters. In this work it is described the influence of three different additives, viz. 4-methoxyphenol, terc-butyl chloride and benzyl chloride, on the polymerization process of the derivative poly(2-methoxy-5-hexyloxy-p-phenylenevinylene) MHPPV. Size Exclusion Chromatography analyses revealed that the type and rate of incorporation of the additives to the polymerization reaction largely affects the molecular weight of the polymers. In addition, it was observed that the use of additives leads to the synthesis of low molecular weight polymers, increasing their solubilities in common organic solvents, eg. chloroform and tetrahydrofuran. The glass transition temperature (Tg) of the polymers was determined by differential scanning calorimetry (DSC) to be ca. 160oC. Interestingly, all the polymers presented an additional transition point at ca. 75oC. Neither the electronic absorption nor the emission spectra were affected by the differences on the molecular weight of the polymers. Finally, it was possible to establish correlations between the molecular weight analyses (from HPSEC) and viscosity experiments, which can be useful for Mw determination

This work deals with investigation of intercalation of alkaline metals in electrochromic devices by the help of the quartz crystal microbalance method. The general aim is to investigate the influence of molar mass and resistance on properties of vanadium pentoxide and tungsten trioxide electrochromic films. The main measuring method used for investigating of interacalation of sodium and lithium ions into these films is the cyclic voltammetry. Drawn graphs reveals that sodium and lithium ions shows different qualities during intercalation, particularly in participation of solvent, therefore, in the influence of molar mass and in structural changes in the films.

Two series of aliphatic hyperbranched (HB) polyesters have been synthesized from 2,2-bis(hydroxymethyl)propionic acid and di-trimethylolpropane using pseudo-one-step or one-step procedure. The structure and properties of these HB polyesters, investigated with different characterization techniques in solution, melt and solid state, were compared between each other, with commercial Boltorn HB polyesters and samples obtained by modification of the end -OH groups with ß-alanine or stearic acid. Seven HB polyesters were fractionated in order to obtain three fractions of each sample. The experimental results obtained from NMR spectroscopy, acid and hydroxyl number titration, GPC, vapour pressure osmometry, MALDI TOF and ESI mass spectrometry indicate that during the synthesis reactivity of terminal and linear -OH groups was not the same and that side reactions occurred in significant amount, which led to the lowering of the number average molar mass and broadening of the molar mass distribution. According to the results obtained from viscosimetry of diluted solutions and dynamic light scattering the best solvents for these HB polyesters are 0.7 mass % solution of LiCl in N,N-dimethylacetamide and N-methyl-2-pyrrolidinon (NMP). The limiting viscosity number and the hydrodynamic radius of the samples increase up to the sixth pseudo generation in these two solvents. Investigated HB polyesters behave as Newtonian liquids in concentrated solutions (c < 50 mass % in NMP) at T < 55 °C. The same was observed for the samples from fourth till sixth pseudo generation in melt at T > 70 °C. At all other experimental conditions used in this work these polymers show shear-thinning behaviour due to the high ability for the aggregation. Thermal stability of investigated HB polyesters increases with increasing number of the pseudo generation. The influence of the procedure for the synthesis and type of end groups on the properties of these polymers is discussed.

L’objectif de cette thèse est de proposer une stratégie simplifiée et précise pour caractériser et modéliser le comportement mécanique des polymères amorphes de l'état quasi-fluide à l'état solide.L'étude a été réalisée sur des PMMA de masses molaires et de degré de réticulations différentes.D’abord, le comportement mécanique dans le domaine viscoélastique linéaire est étudié à l'aide de tests DMTA et rhéologiques. Il ressort de l’étude que l'augmentation de la masse molaire et du degré de réticulation augmentait les modules de stockage et de perte en tant que la transition α. En parallèle, l'utilisation du principe de superposition temps-température a permis de déterminer «des vitesses de déformation équivalentes à la température de référence».Ensuite, le comportement mécanique à grande déformation est étudié par essais cycliques en traction uni-axial et de cisaillement à haute température et couplés à la DIC. De plus, les effets de la vitesse de déformation et de la température ont été couplés grâce à "vitesse de déformation équivalent à la température de référence" extrait des observations dans le domaine linéaire. Les résultats ont montré que cibler la même vitesse de déformation équivalente conduira aux mêmes courbes contrainte-déformation, c'est-à-dire la même réponse mécanique. Ceci permet de réduire le nombre de tests expérimentaux nécessaires pour caractériser le comportement mécanique des polymères amorphes.Enfin, un modèle basée dans un cadre thermodynamique a été utilisée pour reproduire la réponse mécanique des PMMAs à grande déformation. Le modèle présentait un bon accord avec les données expérimentales, étant capable de reproduire des comportements visco-élasto-plastiques, viscoélastiques, hyperélastiques et visco-hyperelastiques pour la traction cyclique. / The present PhD thesis proposes a simplified and accurate strategy for characterising and modelling the mechanical behaviour of amorphous polymers from the quasi-fluid state up to the solid state.The study was carried out on PMMAs with different molar masses and crosslinking degree.First, we addressed the mechanical behaviour in the linear viscoelastic domain using DMTA and rheological tests. Results showed that increasing the molar mas and crosslinking degree increased the elastic and loss moduli as the α-transition. In parallel, using the time-temperature superposition principle allowed determining “equivalent strain rates at reference temperature”.Then, we performed uniaxial tensile and shear uploading-unloading tests at high temperature and coupled with DIC, to characterise the mechanical behaviour at large strain. Additionally, strain rate and temperature effects were coupled by means of the “equivalent strain rate at reference temperature” extracted from observations in the linear domain. Results showed that targeting the same equivalent strain rate lead to the same stress-strain curves, i.e. same mechanical response. This allows reducing the number of experimental tests needed to characterise the mechanical behaviour of amorphous polymers.Finally, a constitutive modelling based in a thermodynamics framework, was used to reproduce the mechanical response of the PMMAs at large deformation. The model presented a good agreement with the experimental data, being able to reproduce viscoelastoplastic, viscoelastic, hyperelastic and viscohyperelastic behaviours for cyclic loading tensile.

No description available.

Casein is the major protein fraction in milk, and its cross-linking has been a topic of scientific interest for many years. Enzymatic cross-linking has huge potential to modify relevant techno-functional properties of casein, whereas non-enzymatic cross-linking occurs naturally during the storage and processing of milk and dairy products. Two size separation techniques were applied for characterisation of these reactions: gel electrophoresis and size exclusion chromatography. This review summarises their separation principles and discusses the outcome of studies on cross-linked casein from the last ~20 years. Both methods, however, show limitations concerning separation range and are applied mainly under denaturing and reducing conditions. In contrast, field flow fractionation has a broad separation range and can be easily applied under native conditions. Although this method has become a powerful tool in polymer and nanoparticle analysis and was used in few studies on casein micelles, it has not yet been applied to investigate cross-linked casein. Finally, the principles and requirements for absolute molar mass determination are reviewed, which will be of increased interest in the future since suitable calibration substances for casein polymers are scarce.

Předkládaná disertační práce se zabývá charakterizací, zpracováním a gelací rozpustného kolagenu. Literární rešerše shrnuje postavení kolagenu na trhu s transplantáty, jeho aplikace a jednotlivé typy kolagenu. Detailně jsou rozebrány jednotlivé metody charakterizace rozpustného kolagenu a způsoby jeho gelace. Experimentální část je rozdělena na dvě podkapitoly. První podkapitola experimentální části se zabývá rozpouštěním a gelací rozpustného kolagenu v natlakované CO2 atmosféře. Proti jiným podobným metodám, metoda pracuje na poměrně nízkém tlaku (do 0.9MPa) a je bezpečná z pohledu denaturace kolagenu neboť funguje za nízké teploty blízké 0°C. Tímto způsobem mohou být průhledné gely, obsahující velmi tenká vlákna kolagenu, vytvořeny mnohem rychleji než za použití konvenčních metod. Rychlost gelace a transparentnost dává konceptu potenciál v oblasti oftalmologie a měla by přinést podstatné výhody pro injektovatelné produkty, vytváření mikro kuliček a 3D tisk. Druhá část popisuje unikátní charakterizaci rozpustného kolagenu v nativním stavu pomocí metody průtokové frakcionace s víceúhlovým rozptylem světla (AF4-MALS). Získaná molekulová hmotnost (při nejvyšší detekované koncentraci) odpovídá předpovězené hmotnosti a nativní i denaturovaný kolagen lze snadno rozeznat v konformačním grafu. Tato nová metoda poskytuje konzistentní a stabilní výsledky ve srovnání s ostatními zavedenými metodami. Metoda může být použita pro optimalizaci kvality výtěžků během výroby rozpustného kolagenu, nebo pro citlivou detekci denaturace během zpracování kolagenu.

This thesis, which is a continuation of the previous Bachelor thesis, is dedicated to the study of polyelectrolyte complexes between hyaluronan (HA) and bovine serum albumin (BSA). Interactions between HA and BSA and a formation of complexes were studied by SEC-MALLS method, where a molar mass, a root mean square (rms) radius, a hydronamic radius and an intrinsic viscosity of particles of the system were defined. Furthermore the interactions were studied by calorimetric measurement ITC, where thermodynamic character of complex formation was determined. Additionally, dynamic and electrophoretic light scattering methods (DLS and ELS) were applied, where hydrodynamic radius and a value of the zeta potential were defined. Also the effect of higher temperature on the character and complex formation was examined by SEC-MALLS and ITC measurements. The interactions were confirmed at any of the used media, but with different efficiency. It was also proved that complexes become smaller in their radii and viscosity with growing BSA concentration. Furthermore it was proved, that the high ionic strength hinders surface charges of HA and BSA molecules and minimizes their mutual interactions. At the higher ionic strength the radii of the complexes, their intrinsic viscosity and zeta potential are increased. The higher temperature has only minimal effect on the formation of the complexes.

No description available.

CHARLES UNIVERSITY FACULTY OF PHARMACY IN HRADEC KRÁLOVÉ DEPARTMENT OF PHARMACEUTICAL TECHNOLOGY Author: Tereza Pokorná Title of Diploma thesis Terbinafine-loaded biodegradable polymeric systems for topical administration Supervisor: PharmDr. Eva Šnejdrová, Ph.D. In the diploma thesis the released properties of solid dispersions with terbinafine, based on polyesters of D,L-lactic acid and glycol acid, branched with pentaerythritol and tripentaerythritol are studied. The theoretical part deals with solid dispersions, their classification and methods of preparation, methods of drug dissolution testing, properties, effect, use of terbinafine and preparations containing terbinafine. In the experimental part, solid dispersions were prepared by the melting method. The drug was incorporated into the polyester in the form of a hydrochloride or a base in a concentration of 10 % or 20 %. Some systems were plasticized with 30% triethyl citrate. Thin layers were formulated from solid dispersions, and drug dissolution tests were performed on phosphate buffer pH 7.4 at 37 řC. Assay of terbinafine released was performed spectrophotometrically at 223 nm and ultra-high performance liquid chromatography. Based on the results of this diploma thesis, it can be clearly stated that the suitable carrier of terbinafine...