Perlcellulose stellt ein interessantes Material für den Einsatz in der wässrigen Größenausschlusschromatgraphie (SEC) dar. Sie ist aufgrund ihrer guten Modifizierbarkeit zudem ein perfektes Ausgangsmaterial für Protein-Aggregationsuntersuchungen. Ein Protein von besonderem praktischem Interesse ist Insulin. Dessen Fehlfaltung und Aggregation verursacht eine Reihe von schwerwiegenden Problemen (z.B. in Drug-Delivery-Systemen). Hierbei erfolgt eine Umwandlung von alpha-Helix- in beta-Faltblatt-Strukturen wobei sich unlösliche Fibrillen bilden. Deren Rückfaltung mit Hilfe fluorierter Alkohole sowie mit fluorierten Nanopartikeln wurde in der Literatur beschrieben. Der Ansatzpunkt dieser Arbeit war es zu untersuchen, ob Fluor auf Oberflächen mit hohem Anteil von Hydroxygruppen eine Rückfaltung von Proteinen wie Insulin bewirken kann. Das Ziel war es, schaltbare stationäre Phasen zu erhalten, mit denen sowohl eine Rückfaltung als auch die Trennung von Proteinen durchgeführt werden können. Zunächst erfolgte die Charakterisierung geeigneter Perlcellulosen, wobei erstmals eine Kombination der „klassischen“ Porosimetrie (Hg-Intrusion, N2-Sorption) mit SAXS und Inverser SEC zur Untersuchung der Porenstruktur von Cellulose angewandt wurde. Es konnte die reversible Schrumpfung der Poren während der Trockungsprozesse beschrieben werden. Die Immobilisierung von Fluor auf der Oberfläche von Cellulosepartikeln erfolgte u.a. durch Pfropfung von fluorierten Acrylaten mittels Cer(IV)-Redoxinitiierung. Es gelang eine homopolymerfreie Pfropfung, wobei es zu keiner Veränderung der Porenstruktur kam. Die Kontrolle der Proteinadsorption auf der modifizierten Oberfläche mittels chemischer Stimuli konnte beschrieben werden. Aggregationsuntersuchungen mittels SEC, DLS und SAXS ergaben, dass fluormodifizierte Perlcellulose keine Verzögerung der Insulinaggregation bewirkt. Jedoch zeigte sich, dass unmodifizierte Perlcellulose eine signifikante Verzögerung der Aggregation bewirken kann. / Porous bead cellulose is an interesting material for the application in aqueous size exclusion chromatography (SEC). Its good modifiability makes it furthermore to a perfect starting material for protein aggregation studies. A protein with huge practical importance is insulin. Misfolding and aggregation of insulin creates serious problems e.g. in drug delivery systems. Thereby it undergoes a change from alpha-helix to beta-sheet structure and forms insoluble fibrils. A back-folding with (toxic) fluorinated alcohols and fluorinated nanoparticles was already shown in literature. The approach for this work was that fluorine (CF3-) on a surface with high hydroxyl-content can induce the back folding of proteins like insulin. The purpose was to get stationary phases that can induce back folding and separation of proteins on a single column. At first a characterization of suitable cellulose beads with focus on different porosimetry methods was done. For the first time a combination of “classical” porosimetry methods (Hg-Intrusion; N2-Sorption) with SAXS and inverse SEC was applied for porous cellulose particles. A reversible shrinking of pores during drying process was shown. Immobilization of fluorine on the surface of cellulose beads was done by grafting of fluorinated acrylates via cer(IV)-redox-initiation and by polymer analogous reaction with fluorinated iodo alkanes. Homopolymer free graft-copolymerization was achieved, whereas no effect on pore structure was observed. The control of protein adsorption on surface by chemical stimuli was shown. Aggregation studies using SEC, DLS and SAXS showed that fluoro-modified cellulose beads do not delay insulin-aggregation due to strong adsorption effects. Though a significant aggregation delay for insulin with unmodified cellulose beads was discovered.

This thesis aims to find out the effective diffusivity (Deff) of a porous material – γ-alumina, using an unsteady state method with two inert gases at ambient condition with no reactions. For porous materials, Deff is important because it determines the amount of reactants that transfers to the surface of pores. When Deff is known, the apparent tortuosity factor of γ-alumina is calculated using the parallel pore model. The apparent tortuosity factor is important because: (a) it can be used to back-calculate Deff at reacting conditions; (b) once Deff with reactions is known, the Thiele modulus can be calculated and hence the global reaction rate can be found; (c) apparent tortuosity factor is also important for modelling purposes (e.g. modelling a packed-bed column or a catalytic combustion reactor packed with porous γ-alumina in various shapes and monoliths). Experimental measurements were performed to determine the effective diffusivity of a binary pair of non-reacting gases (He in N2, and N2 in He) in spherical γ-alumina pellets (1 mm diameter), and in γ-alumina washcoated monoliths (washcoat thickness 20 to 60 µm, on 400 cpsi (cells per square inch) cordierite support). The method used is based on the chromatographic technique, where a gas flows through a tube, which is packed with the sample to be tested. A pulse of tracer gas is injected (e.g. using sample loops: 0.1, 0.2, 0.5 ml) and by using an on-line mass spectrometer the response in the outlet of the packed bed is monitored over time. For the spherical pellets, the tube i.d. = 13.8 mm and the packed bed depths were 200 and 400 mm. For monoliths the tube i.d. = 7 mm and the packed lengths were 500 and 1000 mm. When the chromatographic technique was applied to the monoliths, it was observed that experimental errors can be significant, and it is very difficult to interpret the data. However, the technique worked well with the spherical pellets, and the effective diffusivity of He in N2 was 0.75 – 1.38 × 10-7 m2 s-1, and for N2 in He was 1.81 – 3.10 × 10-7 m2 s-1. Using the parallel pore model to back-calculate the apparent tortuosity factor, then a value between 5 to 9.5 was found for the pellets.

Cette thèse concerne la caractérisation expérimentale d’un sable limoneux provenant du barrage de Livet – Gavet (38) dans le cadre du projet ANR TerreDurable avec plusieurs objectifs : 1- Caractériser au travers d’essais de laboratoire le comportement hydromécanique d’un sable fin limoneux (sol A1 dans la classification GTR) en fonction de son état de saturation. Lors de cette étude, un accent particulier est porté sur la caractérisation de ce comportement dans le domaine proche de la saturation. 2- Interpréter le comportement hydrique du matériau sur chemin de drainage – imbibition en relation avec l’analyse de sa microstructure. 3- Fournir d’un point de vue général une base de données et d’analyses exhaustive permettant le développement et la calibration de modèles de comportement des sols fins proches de la saturation, en particulier en considérant des chemins de chargement hydromécanique complexes. Pour l’ensemble de cette étude, le matériau est considéré sous deux états : soit à l’état de pâte (matériau normalement consolidé) préparée à une teneur en eau proche de la limite de liquidité, soit sous forme compactée (matériau sur-consolidé) à différentes énergies de compactage et différentes teneurs en eau initiales. / This thesis concerns the experimental characterization of a silty sand from the Livet - Gavet dam (38) as part of the ANR TerreDurable project, for following objectives: 1- Through laboratory tests, characterize the hydro-mechanical behaviour of a fine silty sand (Type A1 in the GTR classification) according to its saturation state. In this study, particular emphasis is placed on the characterization of this behaviour in the near-saturated domain. 2- Interpret the water behaviour of material on the drainage - imbibition cycles, in relation to the analysis of its microstructure. 3- From a general point of view, provide a comprehensive database and analysis allowing the development and calibration of models of near-saturated fine soil's behaviour, in particular, by considering complex hydro-mechanical loading paths. For all tests in this study, the material is considered in two states: either in the state of paste (normally consolidated material) prepared at water content close to the limit of liquidity, or in compacted state (over consolidated material) at different compaction energies and different initial water contents.

The master´s thesis focuses on high-alumina refractory materials used mainly in aluminia metallurgy. Teoretical part of this thesis is aimed at distribution of refractory materials, possibilities of its production and raw material basis. Characteristic properties are described as well as application possibilities in aluminium technology. In final part of this thesis experimental data are evaluated to obtain physical, mechanical, chemical properties of high-alumina refractory materials. Those are used for economical optimalization of raw materials.

The diploma thesis deals with the observation and diagnostics of transformations that take place in stone slabs of different mineralogical composition during heating to high temperatures. The theoretical part of the thesis deals with a summary of available information about selected types of rocks. Furthermore, it presents findings from the experimental thermal loading of a granite sample. The principles and instruments of laboratory experimental methods that are used to judge the resistance of rocks are described in detail. In the experimental part, the testing methodology is proposed, the procedure of production of rock test specimens is described and the way in which the thermal loading of stone slabs took place is explained. The results of the experiments are shown in the tables and graphs. A comparison of individual tests and properties of selected samples and evaluation of the obtained results is performed.

Monolithische Phasen werden seit ca. 20 Jahren entwickelt und sind in den letzten Jahren eine attraktive Alternative zu etablierten mit Partikeln gefüllten Säulen geworden. Sie werden in anorganische Phasen und organische Polymermonolithe unterteilt. Monolithe bestehen aus einem einzigen, durchgehenden Stück. Charakteristisch ist das sie durchziehende Porennetzwerk, durch das der Eluent mit geringerem hydraulischen Widerstand fließen kann und das somit schnellere Flussraten ermöglicht. Polymermonolithe werden vorwiegend für die Separation großer Biomoleküle aufgrund eines durch Konvektion beschleunigten Massentransfers eingesetzt. Zudem sind sie über einen breiten pH-Wert-Bereich stabil und können direkt (in situ) im gewünschten Format polymerisiert werden. In der vorliegenden Arbeit gelang die Herstellung neuartiger epoxidbasierter Phasen nach einem von Weller et al. entwickelten Konzept, die im Affinitätsexperiment angewendet wurden. Die Herstellung erfolgte durch Autopolymerisation polyfunktioneller Glycidylether. Für die Funktionalisierung wurden nicht polymerisierte Epoxide genutzt. Als Monomere dienten TEPIC, GE 100 sowie GE 500. Die Arbeiten konzentrierten sich vor allem auf die bei Raumtemperatur durchführbaren Synthesen mit dem höher funktionellen GE 500. Die Polymerisationsbedingungen wurden hinsichtlich Porogenmischung und -anteil optimiert. Eine mit 75 Vol.-% Porogen (Dioxan/ MTBE (2:3)) hergestellte und mit rProtein A funktionalisierte Kapillarsäule (66 %, 12 µm, 7m2/g) ergab im Affinitätsexperiment eine Kapazität von 0,44 mg/mL aus Kaninchenserum isolierbarem IgG. Durch Beimischung von 60 % BDE konnte der Epoxidgehalt vervierfacht und die Porengröße auf 400 nm bei 59 % Porosität reduziert werden. Die spezifische Oberfläche wurde verdreifacht und die Kapazität präparierter Disks auf 0,90 mg/mL etwa verdoppelt. Die in dieser Arbeit entwickelten Disks können zur Isolierung von IgG aus einer komplexen Probe, wie beispielsweise Blutserum, eingesetzt werden. / Monolithic supports have been developed since 20 years and have become an attractive alternative to well-established columns packed with particles over the past years. They are classified into inorganic media and organic polymer monoliths. Monoliths consist of a single, continuous piece with an integrated characteristic porous network through which the eluent can flow with lower hydraulic resistance and which consequently offers higher flow rates. Due to an accelerated mass transfer caused by convection polymer monoliths are mainly used for separation of large biomolecules. In addition, they are stable over a wide pH range and can be polymerized directly (in situ) in the desired format. In the present work the successful preparation of new epoxide-based supports according to a concept introduced by Weller et al. as well as their application in affinity chromatography are reported. Their preparation was carried out by self-polymerization of polyfunctional glycidyl ethers and for functionalization non-polymerized epoxide groups were used. As monomers TEPIC, GE 100 and GE 500 were utilized. The work has focused especially on the polymerization of the higher functional GE 500, which can be perfomed at room temperature and was optimized in terms of both composition and amount of porogen. The extraction of IgG from rabbit serum with a capillary column (66 %, 12 µm, 7m2/g) prepared by 75 vol.-% porogen (dioxane/ MTBE (2:3)) and functionalized with rprotein A resulted in a capacity of 0,44 mg/mL. By addition of 60 % BDE the epoxide content was quadrupled and the pore size reduced to 400 nm while maintaining consistently high porosity of 59 %. The specific surface area was tripled and the capacity of prepared disks approximately doubled to 0,90 mg/mL. The disks developed in this work can be applied for the isolation of IgG from complex samples such as serum.