Charles Univerzity in Prague Faculty of Pharmacy in Hradec Králové Department of Pharmaceutical Technology Candidate: Dana Svobodová Supervisor: doc. RNDr. Milan Dittrich, CSc. Diploma thesis title: Particles with antimicrobial silver The theoretical part of this diploma thesis outlines a brief overview of recent findings on silver nanoparticles. Further, it concerns the kinetic properties of colloidal systems, methods of evaluating the size and shape of colloidal particles, mechanism of antimicrobial activity of colloidal silver and methods of preparation of nanoparticles. Concise information about the toxicity of silver nanoparticles and their impact on the environment is also included. In the experimental part comprehensive report on the results of measurements of granulometric characteristics of microparticles and nanoparticles by photon correlation spectroscopy (PCS) is included. The influence of various modifications of preparation procedures and processing on stability, size and the polydispersity of the size in terms of the volume and intensity diameter of the particles with elemental silver deposited on the surface was studied. Optimisation of the disperse system, quality control of the content of colloidal particles by subsequent reduction, the possibilities of using centrifuge and...

Title: Efficacy of post - isometric relaxation technique on muscle tissue and its viscoelastic properties after physical activity. Objective: This study is a pilot analytical and comparative study. The first aim of this thesis was evaluation of the effect of post-isometric relaxation technique on properties of muscle tissue after physical activity. The second aim of this thesis is to present a literature review regarding this topic using literature available. Methods: This study took place in the laboratory of kinesiology at UK FTVS. Six participants were measured prior to Wingate test, after Wingate test and after post- isometric relaxation or rest. Experimental lower extremity was applied post-isometric relaxation technique and the control lower extremity was not. Muscle tonus of the soleus muscle was measured with myotonometric device developed by Šifta. The final data were processed in the special software in Matlab and the obtained hysteresis curves were used for results analysis. Results: This study had three hypotheses and none of them was confirmed during the measuremets. The first hypothesis pressumed that muscle tonus will increase after the Wingate test, but it was not confirmed and thus further measurements were strongly influenced in the sense that post-isometric relaxation was not...

Dans le domaine de la construction, le béton constitue le matériau le plus consommé. Afin de favoriser le remplissage des coffrages in situ, les bétons sont liquéfiés ponctuellement suite à l'insertion successive d'une aiguille vibrante. Malgré l'arrivée sur le marché des bétons très fluides à auto-plaçant, les bétons ordinaires représentent plus de 90% des formulations employés sur les chantiers. Cependant, les recommandations traditionnelles actuelles se basent sur des études établies au cours de la première moitié du siècle dernier. Ainsi, nous choisissons de les revisiter afin d'incorporer les progrès actuels sur la rhéologie des matériaux cimentaires. A partir d'une étude de la littérature, nous établissons les liens entre les caractéristiques mécaniques des matériels vibrants et le comportement en écoulement des bétons. Puis, dans le chapitre deux, nous mettons en évidence pour quelles consistances de matériau la vibration est réellement nécessaire. Par la suite, nous développons un modèle analytique simple afin de prédire le diamètre d'action d'un vibreur et nous le comparons à deux configurations de mises en œuvre. Enfin, nous proposons un temps minimal de vibration nécessaire au compactage du matériau et un temps maximal afin d'assurer un parement de qualité / In the field of construction, concrete is the most used material. In order to facilitate the casting process, concretes are liquefied punctually following the successive insertion of an internal vibrating poker. Despite the introduction of very fluid to self-compacting concrete, ordinary concrete represents more than 90% of the mix-design used on building sites. However, international recommendations are based on studies carried out during the first half of last century. Thus, we choose to investigate theses recommendations in order to incorporate the current progress on the rheology of cementitious materials. From a study of the literature, we establish the relationship between the mechanical properties of vibrating poker and the fresh behavior of concrete. Then, in chapter two, we determine, for which consistency, the vibration is really needed. Thereafter, we develop a simple analytical model to predict the diameter of action of internal poker and we compare two configurations of casting. Finally, we propose a minimum time of vibration required for compaction of the material and a maximum time to ensure a surface quality

Title: Influence of crank arm length on change of muscle tone of musculus triceps surae Objectives: The aim of this thesis is to conclude the theoretical knowledge of this issue. The experiment is to uncover via the objective results, if the change of the crank arm length can influence the muscle tone of m.triceps surae and additionaly how much. Methods: The measurement for this thesis was processed at Charles University at the Faculty of Physical Activity and Sports, measuring 8 volunteers. Via myotonometry, the biomechanic properties (stiffness and viscosity) of m.triceps surae were measured before and after the workout on a bicycle ergometer. These steps were repeated twice within a week with different crank arm length (170mm and 175mm). On the basis of the reaction of soft tissues on deformation from the tip of the myotonometer, the graphs are depicted, containing the hysteresis curve. We evaluate there two phenomenons - steepness and the content of the curves. They indicate biomechanic properties of soft tissues, resp. also the muscle tissue. Results: The measurements from the 1st and 2nd week were compared. The results of 8 probands show that cycling as a physical activity changes stiffness and viscosity of m. triceps surae and has therefore an influence on the muscle tone. Considering larger...

In the theoretical section of presented diploma thesis are discussed various nanoparticles such as micelles and liposomes, solid lipid nanoparticles and polymeric nanoparticles. Special attention was focused on copolymer PLGA. There are characterized different procedures in the preparation of nanoparticles. From the approches for nanoparticles evaluation are chosen measuring size of nanoparticles and their zeta potential. The experiment was almost unambiguously focused on study of effect of diffrent factors on nanopartlicles size and distribution from linear PLGA and PLGA used for branching of tripentaerythritol and polyacrylic acid. Keywords: nanoparticles, size, size distribution, zeta potential, interactions of nanoparticles

[pt] A demanda global por energia irá aumentar em até 50 porcento nos próximos 20 anos e o petróleo permanecerá sendo a principal fonte de fornecimento de energia. Entre os diferentes tipos de óleos brutos de petróleo, as atenções têm-se concentrado na recuperação de óleos pesados e extrapesados, porque os recursos convencionais de petróleos leves e médios estão globalmente se reduzindo. Os óleos pesados e extrapesados constituem 70 por cento das reservas mundiais, mas devido a sua viscosidade elevada e composição complexa geram problemas. Portanto, a sua recuperação representa um desafio para a indústria do petróleo. Os métodos convencionais só podem ser recuperados cerca 30 por cento do óleo do reservatório e a recuperação avançada de óleo (EOR) que permite obter valores superiores. O método mais utilizado é a injeção de vapor cujo mecanismo principal é o aquecimento do petróleo. Este trabalho apresenta um estudo da influência da presença de nanopartículas no processo de injeção de vapor (aquatermólise), que pode gerar um efeito catalítico promovendo uma melhora no craqueamento incipiente e a consequente diminuição da viscosidade. Um óleo pesado, com viscosidade de 4730 cP a 25 graus Celsius, foi utilizado em escala de bancada para avaliar os efeitos do tempo, da temperatura, do tipo e concentração de nanopartículas (Al2O3-NiO, TiO2 e (Mg,Ni)O) sobre a viscosidade e composição do óleo cru. Os resultados mostraram que a presença de TiO2 e vapor de água podem melhorar a qualidade do petróleo, pela redução das frações pesadas, e diminuir a sua viscosidade em até 13,4 por cento. A técnica foi favorecida com o aumento de temperatura e tempo de aquatermólise. / [en] The global demand in energy will increase by 50 percent over the next 20 years and oil will remain the main source of energy. Among the different types of crude oils, attention has been focused on the recovery of heavy and extra heavy oils, because the conventional resources as light and medium oils are globally decreasing. Heavy and extra heavy oils constitute 70 percent of world reserves, but lead to problems due to their high viscosity and complex composition. Therefore, the recovery of these oils represents a challenge for the oil industry. Conventional methods recover about 30 percent of oil in the reservoir and enhanced oil recovery (EOR) allows to get higher values. The most used method is the injection of steam whose main mechanism of this process is the heating of oil. Consequently there is a reduction of viscosity followed by an incipient cracking, phenomenon affected by the presence of steam water, which needs further studies. This work presents a study of the influence of nanoparticles in the steam injection (aquathermolysis), which can generate a catalytic effect; it enhances the incipient cracking and decreases the viscosity. A heavy oil with viscosity of 4730 cP at 25 Celsius degrees was used in bench scale to evaluate the effects of time, temperature, type and concentration of nanoparticles (Al2O3-NiO, TiO2 and (Mg,Ni)O) on viscosity and composition of the crude oil. The results showed that the presence of TiO2 nanoparticles with steam water may improve the oil quality, by reducing the heavy fractions, and reducing its viscosity up to 13.4 percent.The technique was improved with increasing either temperature or time of aquathermolysis.

Ce travail de thèse porte sur l'étude des mécanismes de blocage d'un écoulement d'eau dans un milieu granulaire par injection d'un produit de colmatage, et s'inscrit plus généralement dans la problématique de l'érosion interne des sols (Projet National ERINOH). Cette recherche, à dominante expérimentale, s'appuie sur une modélisation physique unidimensionnelle. Pour cela, une conduite d'écoulement de 18 cm de diamètre intérieur et 300 cm de longueur maximale, constituée par plusieurs tronçons de 50 cm de longueur assemblés, a été développée. Celle-ci est tout d'abord remplie du matériau granulaire perméable à étudier ; on établit ensuite un écoulement d'eau permanent à pression imposée à l'amont ; finalement on vient injecter localement un produit de colmatage pour essayer de bloquer l'écoulement. Le dispositif est équipé de plusieurs capteurs de pression, de débitmètres, d'un turbidimètre afin de mettre en évidence les paramètres significatifs qui contrôlent le processus de blocage. Les paramètres expérimentaux sont les caractéristiques du milieu granulaire (type de sol, conductivité hydraulique, état de compacité…), les caractéristiques de l'écoulement (vitesses, gradients hydrauliques, régime de l'écoulement…), les propriétés rhéologiques du coulis d'injection (densité, viscosité, seuil de cisaillement…) et la technique d'injection associée. Sur la base des résultats obtenus, on propose des critères de blocage de l'écoulement combinant ces derniers paramètres sous une forme suffisamment simple, utilisable dans la pratique, pour répondre à la demande des industriels impliqués dans le projet de recherche ERINOH, qui sont confrontés à ces pathologies / The present PhD thesis focuses on the mechanisms of blocking permanent water flow through a granular soil by injection of a grout. This work is part of the more general problem of internal erosion of soils (French National Project ERINOH). This research, mainly experimental, is based on a one-dimensional physical modelling. For this, a new original prototype setup, allowing to generate permanent flow in a 18 cm inner diameter and 3 m long plexiglas pipe, has been developed. It is first filled with a highly permeable granular medium, then permanent flow of water is generated at controlled upstream pressure, and finally the grout is injected locally in order to try to block the water flow. The set-up is equipped with multiple pressure sensors, flowmeters, a turbidimeter to monitor the significant parameters that control the clogging process. The experimental parameters are the characteristics of the granular medium (soil type, hydraulic conductivity, density ...), the flow characteristics (flow rate, hydraulic gradient, flow regime ...), the rheological properties of the grout (density, viscosity, yield stress ...) and the associated injection technique. Based on the results obtained, clogging criteria are proposed, as a function of the parameters involved, in a simple form for use in practice.Key-words: internal erosion, clogging, injection, grout, bentonite, yield stress, viscosity.

Cette thèse est consacrée à l'étude de la dynamique et de la rhéologie des fluides complexes. Nous utilisons une méthode de simulation numérique à trois dimensions. Les systèmes que nous étudions ici sont des suspensions de micro-nageurs actifs, des suspensions de particules sphériques rigides en présence d'un champ externe auquel elles sont sensibles et de la dynamique de suspensions de particules sphériques et confinées en cisaillement. Les Micro-nageurs sont les objets microscopiques qui se propulsent dans un fluide et ils sont omniprésents dans la nature. Un exemple commun de micro-nageurs est la micro-algue textit{Chlamydomonas} . Un des buts principaux de cette thèse est de comprendre l'effet de la motilité de ces micro-organismes sur les propriétés macroscopiques globales de la suspension, telles que la viscosité effective pour expliquer les observations expérimentales. Nous avons élaboré différents modèles de suspensions de textit{Chlamydomonas} et effectué des simulations numériques utilisant la version 3D de la dynamique des particules fluides (FPD) (méthode expliquée dans cette thèse). Les résultats de nos simulations numériques ont été présentés et discutés à la lumière des observations expérimentales. Un des modèles proposés intègre tous les phénomènes observés expérimentalement et sont applicables à d'autres types de suspensions de micro-nageurs. Cette thèse consacre également un chapitre sur les effets du confinement sur la dynamique de cisaillement des suspensions diluées de particules sphériques. Nous avons constaté que dans la géométrie confinée, la vitesse angulaire des particules diminue par rapport à celle imposée par l'écoulement de cisaillement. La vitesse angulaire des particules diminue également lorsque la particule est proche d'une paroi unique et la vitesse de translation de la particule par rapport à la vitesse de la paroi diminue. Un autre objectif de cette thèse est d'étudier les suspensions à viscosité effective ajustable. Nous avons mené une étude numérique sur des suspensions de particules sphériques en présence d'un couple externe. Nous avons montré que le changement de vitesse angulaire des particules due à l'application d'un couple externe est suffisante pour modifier fortement la viscosité de la suspension. Basée sur des simulations numériques, une formule semi-empirique a été proposée pour la viscosité des suspensions de particules sphériques valables jusqu'à 40% de concentration. Nous avons également montré que la 2ème loi de Faxén peut être étendue par une expression empirique pour de grandes concentrations. / This work is dedicated to the study of dynamics and rheology of the complex fluids. We use three dimensional numerical simulations. The systems we study here are: suspensions of biological active micro-swimmers, suspensions of rigid spherical particles in presence of an external field and the dynamics of sheared confined spherical particles. Micro-swimmers are the microscopic objects that propel themselves through a fluid and they are ubiquitous in nature. A common example of micro-swimmers is the textit{Chlamydomonas} . One of the main goal of this thesis is to understand the effect of self-motility of these micro-organisms on the global macroscopic properties of the fluid, such as the effective viscosity to explain experimental observations. We elaborated different models for textit{Chlamydomonas} suspensions and conducted numerical simulations using the 3D version of the Fluid Particle Dynamics method (explained in this thesis). The results of our numerical simulations has been shown and discussed in light of the experimental observations. One of the proposed models incorporates all experimentally observed phenomena and is expendable for other types of micro-swimmer suspensions. This thesis is also dealing with the effects of confinement on the dynamics of sheared spherical particles. We found that in confined geometry, angular velocity of sheared particles decreases compared to the one imposed by the shear flow. The angular velocity of the particles decreases also when the particle are close to a single wall and the translational velocity of the particles changes so that the difference between velocity of the particle and the velocity of the wall decreases. Another objective of this work is to study suspensions with tunable effective viscosity. We conducted a numerical investigation of sheared spherical particle suspensions in presence of an external torque. We showed that the change of particle angular velocity with an external torque is sufficient to strongly change the effective viscosity of the suspension. Based on numerical simulations, a semi-empirical formula has been proposed for the effective viscosity of spherical particles suspensions valid up to 40% concentration. We also showed that a modified second Faxén law can be equivalently established for large concentrations.

A obtenção de dados de viscosidade, é fundamental para o projeto de equipamentos, tubulações e otimização de processos, já que esta propriedade afeta tanto a perda de energia por atrito em fluidos, como os mecanismos de transferência de calor e de massa. O presente trabalho de Mestrado teve como objetivo medir experimentalmente dados de viscosidade para misturas formadas por ácidos graxos comerciais e solventes alcoólicos de diferentes tamanhos de cadeia carbônica (etanol, 2-propanol, 1-butanol, 1-pentanol e 1-hexanol), com ou sem a adição de água, variando-se a temperatura desde o ponto de fusão do composto graxo até o ponto de ebulição de cada solvente. Estes dados foram agrupados aos dados experimentais de viscosidades de misturas de triacilgliceróis (TAG) e ácidos graxos (AG) já disponíveis na literatura, para a obtenção de parâmetros de interação entre os grupos funcionais formadores dos componentes presentes nos sistemas estudados, utilizando-se o modelo de contribuição de grupos UNIFAC-VISCO. Em uma primeira abordagem, apenas os parâmetros inexistentes na literatura foram ajustados, obtendo-se um erro relativo médio igual a 10,21 %. A modelagem também foi realizada ajustando-se todos os parâmetros de interação, incluindo os já publicados, obtendo-se nesta segunda abordagem, um erro relativo médio igual a 7,54 %. A capacidade preditiva dos parâmetros obtidos foi testada em misturas semelhantes, formadas por óleos vegetais ou gordura animal, ácidos graxos e solventes alcoólicos, cujas viscosidades também foram determinadas neste trabalho, porém não fizeram parte do banco de dados utilizado na modelagem. Os resultados obtidos foram comparados aos de outros modelos para o cálculo de viscosidades de misturas conhecidos da literatura, dentre eles, a Regra de Kay, o Modelo de Kendall e Monroe e o Modelo CG-UNIMOD. Para fins comparativos, este conjunto de dados também foi ajustado a equação de Grunberg-Nissan, da qual foram obtidos parâmetros de interação entre os componentes das misturas. Os testes preditivos mostraram que o modelo UNIFAC-VISCO proporcionou os menores erros relativos para a maioria das misturas estudadas, porém ainda bastante elevados em alguns casos. Por outro lado, o Modelo de Grunberg-Nissan proporcionou erros relativos bem menores, o que era esperado, uma vez que as viscosidades de cada sistema foram correlacionadas pelo modelo. / The acquisition of viscosity data is critical for the design of equipments and pipes, as well as for the process optimization, since this property affects both the energy loss by friction in fluids, such as the mechanisms of mass and heat transfer. The present work aimed the measurement of experimental viscosity data for mixtures containing commercial fatty acids and alcoholic solvents of different sizes of carbon chain (ethanol, 2-propanol, 1-butanol, 1-pentanol and 1-hexanol), with or without the addition of water, varying the temperature from the melting point of the fatty compound to the boiling point of each solvent. These data were grouped together to experimental viscosity data of triacylglycerols (TAG) and fatty acids (FA) mixtures that were already available in the literature, to obtain interaction parameters between the forming functional groups of the components present in the systems studied, using the group contribution model UNIFAC-VISCO. In a first approach, only the parameters not available in the literature were adjusted obtaining an average error equal to 10.21%. The modeling was also performed by adjusting all interaction parameters, including those already published, obtaining in this second approach, an average error equal to 7.54%. The predictive ability of parameters obtained was tested in similar mixtures containing vegetable oils or animal fats, fatty acids and alcoholic solvents, whose viscosities were also determined in this work, but were not part of the database used in the modeling. The obtained results were compared to other known models for the calculation of viscosities of mixtures, such as the Kay\'s Rule, the Kendall and Monroe model and the CG-UNIMOD. For comparative purposes, this data set was also adjusted to the Grunberg-Nissan equation, in which interaction parameters between the components of mixtures were obtained. The predictive tests showed that the UNIFAC-VISCO model provided the lowest relative errors for most of the mixtures studied, but still quite high in some cases. On the other hand, the Grunberg-Nissan model provided relative errors much smaller, which was expected, since the viscosities of each system were correlated by the model.

Como intuito de contribuir para a elucidação do mecanismo de quimi-excitação da reação peroxi-oxalato, a transformação quimiluminescente mais eficiente conhecida que envolve a versão intermolecular do mecanismo \"Chemically Initiated Electron Exchange Luminescence\" - CIEEL, foram efetuados estudos cinéticos e determinados os rendimentos quânticos de quimi-excitação desta reação em diferentes solventes e misturas de solventes. A cinética da reação de oxalato de bis-2,4,6-triclorofenila com peróxido de hidrogênio, catalisada por imidazol foi estudada na presença de 9,10-difenilantraceno como ativador (ACT) em diferentes solventes. O comportamento das constantes de velocidade observados em função da polaridade e viscosidade dos solventes indica que o mecanismo dos passos iniciais desta transformação até a formação do intermediário de alta energia (IAE) não sofre modificações drásticas em função das propriedades de solventes, permitindo a escolha de solventes e misturas de solventes adequados para o estudo do mecanismo de quimi-excitação do sistema. A influência da viscosidade sobre os rendimentos quânticos singlete (Φs) e os rendimentos quânticos singlete na concentração infinita do ACT (Φs∞ - obtidos de gráficos duplo recíprocos entre os (Φs) e a [ACT]) foi estudada em misturas entre acetato de etila e ftalato dimetilico (que possuem viscosidades diferentes e parâmetros de polaridade similares, além de levarem a rendimentos quânticos altos), indicando um aumento considerável dos rendimentos quânticos singlete com o aumento da viscosidade do meio. Os dados foram tratados com base nos modelos colisional e friccional, obtendo indicação clara da operação de um efeito de gaiola do solvente no processo de quimi-excitação da reação neste sistema de alta eficiência. A influência da polaridade do meio sobre os parâmetros de quimi-excitação da reação peroxi-oxalato foi analisada, de maneira análoga, em misturas entre tolueno e acetato de etila e entre acetato etila e acetona. Os rendimentos quânticos singlete aumentam inicialmente em função da polaridade do meio até um valor máximo, a partir do qual eles sofrem diminuição com o aumento da polaridade. Este comportamento indica a melhor solvatação dos pares de íons radicais pelo aumento da polaridade de solvente levando ao aumento dos rendimentos, entretanto, polaridades maiores do meio podem levar à formação de pares de íons separados por solvente e íons separados, desta maneira diminuindo a eficiência da quimi-excitação. Os parâmetros de quimiluminescência da reação peroxi-oxalato foram ainda estudados em uma série de solventes puros com diferentes valores de polaridade e viscosidade. Os rendimentos quânticos obtidos foram correlacionados com os parâmetros de viscosidade, polaridade e polarizabilidade, utilizando-se uma regressão linear múltipla. Deste ajuste se pode confirmar que a viscosidade exerce a maior influência sobre os rendimentos quânticos e o aumento da polaridade contribui também para maiores rendimentos, entretanto, os parâmetros de ajuste contêm erros muito grandes devido à dispersão dos valores. Contrariamente, o aumento da polarizabilidade do meio parece diminuir a eficiência de quimi-excitação. / In order to contribute to the elucidation of the chemiexcitation mechanism of peroxyoxalate reaction, the most efficient chemiluminescence reaction known that involves the intermolecular \"Chemically Initiated Electron Exchange Luminescence\" - CIEEL mechanism, kinetically studies were performed and chemiexcitation quantum yields determined in different solvents and solvent mixtures. The reaction kinetics of bis(2,4,6-trichlorophenyl) oxalate with hydrogen peroxide catalyzed by imidazole in the presence of 9,10-diphenylanthracene as an activator (ACT) was studied in different solvents. The behavior of the observed rate constants in function of solvents polarity and viscosity indicates that the initials reaction steps leading to high energy intermediate formation (HEI) do not change drastically in function of the solvent properties, allowing to choose suitable solvents and solvent mixtures for a study of its the chemiexcitation mechanism. The viscosity influence on the singlet quantum yields (Φs) and singlet quantum yields at infinite ACT concentration (Φs∞ - obtained from double reciprocal plots between Φs and [ACT]) was studied in mixtures of ethyl acetate and dimethyl phthalate (which have different viscosities and similar polarity parameters), indicating a considerable increasing in singlet quantum yields with the increasing of medium viscosity. Data were analyzed by the collisional and the free volume model, which clearly indicates the occurrence of a solvent cage effect in the chemiexcitation process of this high efficient system. The influence of medium polarity on the chemiexcitation parameters of the peroxyoxalate reaction were studied, in a similar way, in mixtures of toluene and ethyl acetate and in mixtures of ethyl acetate and acetone. Singlet quantum yields increase in function of medium polarity for low polar solvents, reaching a maximum value, where a further polarity increase leads to a decrease in quantum yields. This behavior indicates better solvation of radical íon pairs by solvent polarity increase, leading to increased quantum yields, however, higher solvent polarities can lead to the formation of solvent separated ion pairs and individually solvate ions, thereby decreasing chemi-excitation efficiency. Chemiluminescence parameters of the peroxyoxalate reaction were also studied in pure solvents with different viscosities and polarities. The obtained singlet quantum yields were correlated with viscosity, polarity and polarizability parameters by multiple linear regression analysis. The correlations obtained show that viscosity exerts the most significant influence on the quantum yields and an increase in solvent polarity also contributes to higher quantum yields; however, these fitting parameters possess high standard deviations due to the considerable dispersion of quantum yield values. Contrary, an increase in medium polarizability appears to decrease the chemi-excitation efficiency.