Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

The fascinating physical properties that arise in materials limited to dimensions of 1-100 nm have gained noteworthy interest from the scientific community. Accordingly, there has been a lot of attention paid to the synthesis of discrete nanoparticles (NPs) and they are being investigated for a range of advanced technologies. Nonetheless, efficient use of nanomaterials in device applications require them to be assembled into solid state macro-structures while retaining their unique, nanoparticulate properties. To date, most commonly investigated assembling techniques include: covalent coupling of NPs surface groups, control evaporation of the solvent to produce ordered supercrystals or non-ordered glassy films, and polymer or bimolecular mediated self-assembly. However, in each of these cases, the interactions among discrete NPs are mediated by intervening ligands, the presence of which are detrimental for efficient electronic transport and interparticle coupling that limit performance in optoelectronic,electro-catalytic, and chemical sensor studies. Thus, novel and efficient strategies that can be predictably manipulated for direct, self-supported assembly of NPs are of critical need. A method that has proved useful to construct direct interfacial linkages of colloidal NPs is the sol-gel technique.Oxidative removal of surfactant ligands has been shown to produce self-supported NP monoliths that in most cases retain the physical properties of primary NPs.The ability to create direct interfacial bonds contributes to enhanced electrical and thermal transport as well as tunable interparticle interactions, expanding the potential range of NP technologies. During oxidation, low coordinated active sites are produced on the NP surface that interacts with a nearby NP to reduce the surface energy. The formed active sites are highly reactive allowing the NPs to establish direct interfacial linkages, polymerize into low dimensional clusters, and consequently highly porous superstructures that augment the unique, nanoparticulate properties. An added advantage of this chemistry is the ability to couple chemically similar or dissimilar systems with the potential to achieve novel/tunable physical properties. In this dissertation, application of sol-gel chemistry in efficient integration of similar and dissimilar nanoscale materials will be discussed with an aim of achieving improved optoelectronic and electro-catalytic properties. Hybrid nanomaterials composed of metal-semiconductor components exhibit unique properties in comparison to their individual counterparts, making them of great interest for optoelectronic technologies. The direct cross-linking of NPs via sol-gel chemistry provides a versatile route to tune interfacial interactions in a manner that has not been thoroughly investigated. Thus, the first part of the dissertation will illustrate the synthesis of CdSe/Ag hetero-nanostructures (aerogels) via oxidation induced self-assembly of thiol-coated NPs and investigate the evolution of optical properties as a function of Ag composition. Two hybrid systems were investigated, where the first and second excitonic energies of CdSe were matched with plasmonic energy of Au and Ag NPs. The optical properties of the CdSe/Ag hybrids were systematically examined through UV-visible, photoluminescence, and time resolved photoluminescence spectroscopy. A new emission (640 nm) from CdSe/Ag aerogels was emerged at Ag loading as low as 0.27 % whereas absorption band tailing and PL quenching effects were observed at higher Ag and Au loading, respectively. The TRPL decay time of the new emission (~600 ns) is markedly different from those of the band-edge (1.83 ± 0.03 ns) and trap state (1190 ± 120 ns) emission maxima of phase pure CdSe, supporting the existence of alternate radiative relaxation pathways in sol-gel derived CdSe/Ag hybrids. An added benefit of newly developed sol-gel chemistry is the potential to produce porous, conducting nanoarchitectures that provide a facile pathway for efficient transfer of charge carriers and small molecules. Thus, aerogels composed entirely of noble metal NPs are expected to exhibit high electrical conductivity making them promising for electrocatalysis. Thus, the second part of the dissertation will describe the extension of NP condensation strategy for the fabrication of ternary noble metal (Au/Ag/Pd, Au/Ag/Pt) aerogels for electro-oxidation of alcohols. The precursor alloy NPs were produced via stepwise galvanic replacement of thiol-coated Ag NPs. The resultant alloy NPs were self-assembled into large, free-standing aerogels that exhibit direct interparticle connectivity, high surface area (282 – 98 m2/g) and mesoporosity (2 – 50 nm) via controlled oxidation of the surfactant ligands. The gelation kinetics has been controlled by varying the oxidant/surfactant molar ratio that governs the dealloying of Ag from ternary superstructures with in-situ generated HNO3. The monolithic Au/Ag/Pd alloy aerogels exhibit higher catalytic activity and durability compared to the discrete alloy NPs (~ 20-30 times) and commercial Pd/C catalyst (2-3 times). On the other hand, Au/Ag/Pt alloy aerogels showed excellent stability at higher concentration of methanol (12 M) during electro-oxidation studies, suggesting its superior electro-catalytic activity. The synergistic effect of tri-metallic alloy mitigates the catalyst poisoning and increases the stability and durability whereas the self-supported superstructure with direct interparticle connectivity, high surface area and porosity offers a facile conduit for molecular and electronic transport, enabling the ternary aerogels an efficient electro-catalyst.

The antigens of Trichomonas vaginal is grown jn Diamond 1 s medium modified by Klass were analyzed by gel diffusion methods. Three methods were employed in the extraction of the antigens. They were Genetron extract, Borate Buffer Saline extract, and alcohol extract. The alcohol extract was made up of four fractions (TF1 , TF2, TF3, TF4). The antisera used as analytic agents were made in two rabbits obtained from the Center for Disease Control Breeding Colony. All the antigens were compared to show bands of identity, non-identity, and partial identity, and to determine the number of bands produced by each extract. Genetron extract antigen and Borate Buffer Saline extract antigen reacted strongly with the homologous antiserum made in rabbit 3 (R3), producing 4 bands each, while alcohol extract reacted minimally. Fractions TF1 and TF4 produced 3 bands each and fraction TFz and TF3 produced 2 bands each Two bands of precipitate were found to be common to all the antigens, suggesting the similarity of the antigens. In rabbit 4 (R4), 3 bands were produced by each antigen and they were all identical, confirming the similarity of the antigens. Rabbit 3 antiserum reacted more strongly than rabbit 4, even though all the rabbits were inoculated on the same dates with the same number of live Trichomonas vaginalis antigens under the same conditions.

Photodynamic therapy (PDT) is a cancer treatment method in which a photosensitizer, light of a particular wavelength, and also oxygen are used to destroy cancerous cells. Cancer cells absorb the photosensitizing agent which is injected into the body, and it is triggered to cause cell destruction upon absorption of light. This occurs because of the excitation of the photosensitizer produces reactive oxygen species that induce a cascade of cellular and molecular events in the body. Photosensitizing agents that can photo-cleave DNA at long wavelengths are highly demanded in PDT, because the long wavelengths of light can penetrate through tissue deeply compared to visible light. While most of the photosensitizers are activated at wavelengths less than 690 nm, penetration of light continues to increase at increasing wavelengths. In this thesis, photosensitizers that can be activated to oxidize DNA with long wavelengths of light will be discussed. Using quinoline cyanine dyes, here we report the first example of DNA photocleavage at a wavelength of light above 800 nm.

Thirty-two silicone breast implant patients scored in the mild to moderate range of impairment on the Halstead-Reitan Neuropsychological Battery. An unusual number of patients had positive tests for antinuclear antibody on immunological testing and a high incidence of EEG abnormalities were found. Personality testing revealed an MMPI profile which is typical for neuropsychologically impaired subjects but components were consistent with extreme emotional distress. None of the subjects were near the cutoff score for malingering or faking bad on the F-K index of the MMPI. There was no apparent relationship between length of exposure and the severity of neurological impairment. Also, explanted subjects performance was not improved when compared to subjects whose implants were still in place.

This work utilized the sol-gel process in two ways. First, macroporous silica thin films were developed using a combination of casting techniques and templating. Macroporsity was introduced to the silica thin films by either doping the silica sol before casting or by ordering the template on a substrate and then casting a sol over it. These techniques were first used to create silica thin films with long microchannel pores (200 nm x 60 µm) from a doped sol with the bacteria, B. Megaterium, as the template for nanomaterial formation. To enable the formation long microchannels, the flexible bacteria chains were aligned by using light scratches on the substrate surface as anchors for the bacteria’s adhesive cell capsule. Polystyrene (PS) sphere templates were then used in several studies to obtain silica thin films with well-ordered “nanowells,” single-layer hemispherical pores that allowed direct access to the substrate beneath the film. Copper and gold nanoparticles were integrated into moderately packed films by electrodepostion and monolayer self-assembly, respectfully. The size of the nanoparticles was controlled by the time of the electrodeposition or the time of exposure to an electroless growth solution. The final study with polystyrene latex sphere templates produced high quality, well-packed films containing well-defined nanowells over almost the entire conductive substrate. This was accomplished by separating the ordering of the templates on the substrate from film formation. Electroless growth was used to control the size and shape of the gold nanoparticles and the electrochemical properties of the resultant films were studied, showing an enhanced response to negatively charged redox probes. Sol-gel techniques were then used to create high aspect ratio silica nanotubes and pillars. The electroassisted deposition of silica was carried out in the pores of track-etched membranes, allowing supported nanotubes with dimensions of 100 – 400 nm x 10 µm to be obtained. The mechanism of silica formation in the tubular template was studied and it was found that growth occurred first by nanotube formation, followed by further growth through tube from the electrode to the other side of the pore. This allowed for partially filled tubes and solid pillars to be obtained. The method was found to be flexible and characteristics such as tube length, chemical functionality and porosity to be controlled.

Gegenstand der vorliegenden Arbeit ist die Synthese, Charakterisierung und Optimierung von Kohlenstoff-Aerogelen (C-Aerogele) für den Einsatz als Hochtemperaturwärmedämmung (> 1000°C). C-Aerogele sind offenporöse monolithische Festkörper, die durch Pyrolyse von organischen Aerogelen entstehen. Die Synthese dieser organischen Vorstufen erfolgt über das Sol-Gel-Verfahren. Zur Charakterisierung der Morphologie wurde die innere Struktur der Aerogele mittels Raster- und Transmissionselektronenmikroskopie, Röntgendiffraktometrie (XRD), Raman-Spektroskopie, Stickstoffsorption und Röntgenkleinwinkelstreuung (SAXS) untersucht. Die thermischen Eigenschaften der Aerogele wurden mit Hilfe von Laser-Flash Messungen, dynamischer Differenzkalorimetrie (DSC), thermographischen und infrarot-optischen (IR) Messungen quantifiziert. Die innere Struktur von Aerogelen besteht aus einem dreidimensionalen Gerüst von Primärpartikeln, die während der Sol-Gel Synthese ohne jede Ordnung aneinander wachsen. Die zwischen den Partikeln befindlichen Hohlräume bilden die Poren. Die mittlere Partikel- und Porengröße eines Aerogels kann durch die Konzentration der Ausgangslösung und der Katalysatorkonzentration einerseits und durch die Synthesetemperatur und –dauer andererseits eingestellt werden. Der Bereich der mittleren Partikel- und Porengröße, der in dieser Arbeit synthetisierten Aerogele, erstreckt sich von einigen 10 Nanometern bis zu einigen Mikrometern. Die Dichten der Proben wurden im Bereich von 225 kg/m3 bis 635 kg/m3 variiert. Die Auswirkungen der Pyrolysetemperatur auf die Struktur und die thermischen Eigenschaften der C-Aerogele wurden anhand einer Probenserie erstmalig systematisch untersucht. Die Proben wurden dazu bei Temperaturen von 800°C bis 2500°C pyrolysiert bzw. temperaturbehandelt (geglüht). Um die einzelnen Beiträge zur Wärmeleitfähigkeit trennen und minimieren zu können, wurden die synthetisierten Aerogele thermisch mit mehreren Meßmethoden unter unterschiedlichen Bedingungen charakterisiert. Temperaturabhängige Messungen der spezifischen Wärmekapazität cp im Bereich von 32°C bis 1500°C ergaben für C-Aerogele verglichen mit den Literaturdaten von Graphit einen ähnlichen Verlauf. Allerdings steigt cp etwas schneller mit der Temperatur an, was auf eine „weichere“ Struktur hindeutet. Die maximale Abweichung beträgt etwa 11%. Messungen an einer Serie morphologisch identischer Aerogelproben, die im Temperaturbereich zwischen 800°C und 2500°C pyrolysiert bzw. geglüht wurden, ergeben eine Zunahme der Festkörperwärmeleitfähigkeit mit der Behandlungstemperatur um etwa einen Faktor 8. Stickstoffsorptions-, XRD-, Raman- und SAXS-Messungen an diesen Proben zeigen, dass dieser Effekt wesentlich durch das Wachstum der graphitischen Bereiche (Mikrokristallite) innerhalb der Primärpartikel des Aerogels bestimmt wird. Berechnungen auf Basis von Messungen der Temperaturleitfähigkeit weisen außerdem auch auf Veränderungen der Mikrokristallite hin. Gasdruckabhängige Messungen der Wärmeleitfähigkeit und der Vergleich zwischen Messungen unter Vakuum und unter Normaldruck an verschiedenen Aerogelmorphologien liefern Aussagen über den Gasanteil der Wärmeleitfähigkeit. Dabei zeigt sich, dass sich der Gasanteil der Wärmeleitfähigkeit in den Poren des Aerogels verglichen mit dem freien Gas durch die geeignete mittlere Porengröße erwartungsgemäß erheblich verringern lässt. Diese Ergebnisse stimmen in Rahmen der Messunsicherheit mit der Theorie überein. Durch infrarot-optische Messungen an C-Aerogelen konnte der Extinktionskoeffizient bestimmt und daraus der entsprechende Beitrag der Wärmestrahlung zur Wärmeleitfähigkeit berechnet werden. Temperaturabhängige Messungen der thermischen Diffusivität erlaubten mit der zur Verfügung stehenden Laser-Flash Apparatur die Bestimmung der Wärmeleitfähigkeit bis zu Temperaturen von 1500°C. Die Temperaturabhängigkeit der Wärmeleitfähigkeit der C-Aerogele zeigt eine Charakteristik, die mit den separat gemessenen bzw. berechneten Beiträgen zur Wärmeleitfähigkeit und der Theorie im Rahmen der Messunsicherheit gut übereinstimmen. Auf der Basis der gewonnenen Messdaten ist es möglich, die Wärmeleitfähigkeit von Aerogelen für Anwendungen über die maximale Messtemperatur von 1500°C durch Extrapolation vorherzusagen. Die niedrigste Wärmeleitfähigkeit der im Rahmen dieser Arbeit synthetisierten C-Aerogele beträgt danach etwa 0,17 W/(m•K) bei 2500°C unter Argonatmosphäre. Kommerziell erhältliche Hochtemperatur-Wärmedämmstoffe, wie z. B. Kohlefaserfilze oder Kohlenstoffschäume weisen Wärmeleitfähigkeiten im Bereich von etwa 0,7 bis 0,9 W/(m•K) bei einer Temperatur von 2000°C auf. Die Messungen zeigen, dass die vergleichsweise niedrigen Wärmeleitfähigkeiten von C-Aerogelen bei hohen Temperaturen durch die Unterdrückung des Gas- und Strahlungsbeitrags der Wärmeleitfähigkeit bedingt sind. / The scope of the present work is the synthesis, the characterisation and the optimisation of carbon (c-) aerogels as high temperature insulation (> 1000°C). Carbon aerogels are open porous monolithic solids which are produced by pyrolysis of organic aerogels. These organic precursors are synthesized via the sol-gel route. For the structural characterisation of the aerogels the samples were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction (XRD), Raman spectroscopy, nitrogen sorption measurements and small angle X-ray scattering (SAXS). The thermal properties of the aerogels were quantified by laser flash measurements, differential scanning calorimetry (DSC), thermographic and infrared optical measurements. The inner structure of the aerogels consists of a three dimensional skeleton of primary particles which grow during the sol-gel synthesis and are connected to each other without any orientation. The voids between the particles are the pores. The mean particle and pore size of the aerogel can be tailored specifically via the concentration of the catalyst and the degree of dilution of the educt solution on the one hand and the synthesis time and -temperature on the other hand. The range of the mean particle and pore sizes of the aerogels synthesized within this work extends from some tens of nanometers to some microns. The density of the samples was varied in the range from 225 kg/m3 to 635 kg/m3. The impact of pyrolysis and annealing temperature on the morphology and the thermal properties of carbon aerogels was investigated for the first time systematically on one series of samples. For that purpose the samples were pyrolysed and annealed in the range of 800 to 2500°C. To separate and minimize the individual contributions, the thermal conductivity of the synthesized c-aerogels were thermally characterized by different measuring methods under various conditions. The measurements of the specific heat in the range of 32 to 1500°C yield values similar to the literature data of graphite; however slightly systematic higher values of up to 11% were observed as expected for “softer” solids with high interfacial surface areas. Measurements of a series of carbon aerogels with identical morphology, however different annealing temperatures, show an increase of the solid thermal conductivity with increasing annealing temperature of up to a factor of about 8 for temperatures between 800°C and 2500°C. Nitrogen sorption-, XRD-, Raman-, and SAXS-measurements reveal that this effect is dominated by the growth of graphitic domains (microcrystallites) within the primary particles of the aerogel. In addition calculations based on measurements of the thermal diffusivity indicate changes of the microcrystallites. Measurements of the thermal conductivity of aerogels with different morphologies as a function of gas pressure and the comparison of the data taken under vacuum and normal pressure yield informations about the gaseous contribution to the thermal conductivity. As expected, the gaseous thermal conductivity within the pores of the aerogel can be reduced compared to the free gas when the pore size is in the range of the mean free path of the gas molecules or smaller. The results agree with the theory within the measuremental uncertainties. Infrared optical measurements provide the extinction coefficient of carbon aerogels, from which the radiative contribution to the thermal conductivity could be determined. The laser flash equipment available at the ZAE Bayern allows measurements of the thermal diffusivity up to 1500°C from which the thermal conductivity can be determined. The thermal conductivity of carbon aerogels as a function of temperature is well described by a superposition of the single contributions determined separately and the theoretical predictions within the uncertainties. Based on the experimental data it is possible to extrapolate the thermal conductivity of carbon aerogels for applications beyond the maximum temperature investigated (1500°C). Thus the lowest thermal conductivity of the carbon aerogels synthesized in the scope of this work is about 0,17 W/(m•K) at 2500°C in argon atmosphere. This value is about a factor 4 lower than for the best commercially available insulation material.

Entwicklung eines dreidimensionalen Fibringelmodells zur In-Vitro-Analyse von Fibrose und Angiogenese Alginat-mikroverkapselter Langerhans-Inseln / Immunoprotection of the pancreatic islets by encapsulation with alginate can potentially provide their transplantation without immunosuppression. The fundamental obstacle to large-scale clinical transplantation of encapsulated islets is limited graft survival. Critical for adequate long-term function of the graft is the absence of fibrotic overgrowth and sufficient supplementation with oxygen and nutrients. The aim of this study was to develop a model to investigate molecular and cellular mechanisms of fibrosis and vascularization of alginate-encapsulated islets. A 3D fibrin-gel model was developed to assess the mitogenic and angiogenic activity of encapsulated islet cells and encapsulation material per se. The 3D fibrin-gel matrix, containing filled or empty capsules, was seeded with fibroblasts and endothelial cells. Their migration and prolifiration were evaluated by phase-contrast microscopy and histology. Viability (FDA/PI) and function (insulin-ELISA) of encapsulated islets were assessed at different time-points. Inflammatory and angiogenic cytokines were tested with ELISA. Embedded into the 3D fibrin-gel, encapsulated islet cells preserved their viability and function to day +14 in culture. Encapsulated islet cells influenced migration, proliferation and cytokine production of fibroblasts when these were seeded into the 3D fibrin gel: fibroblasts migrated directly to encapsulated islets and grew firmly around the capsules, migration to empty capsules was much slower and overgrowth less prominent. TNFa production increased significantly after 10 days incubation of encapsulated islets with fibroblasts, but not with empty fibroblasts. Co-culture of encapsulated islets with endothelial cells induced the formation of vascular-like tubular structures around the capsules . This model was useful to test the mitogenic and angiogenic properties of the encapsulation material (purified versus non-purified alginates). Adhesion of endothelial cells to collagen-layered capsules was much more prominent than to non-layered capsules; endothelial cells strongly proliferated, forming a monolayer on the capsule surface. Moreover, they migrated into the fibrin-gel-matrix, forming new tube-like structures. These processes were accelerated by VEGF. The 3D fibrin-gel model is very useful for studying the mechanisms of fibrosis and vascularization of encapsulated islets in vitro. In vivo conditions can be imitated, and factors involved in these processes can be analyzed separately.

The aim of this work was to test and tailor new sol gel derived hybrid polymer coatings for the incorporation of photochromic spirooxazines and chromenes. The development and optimisation of work was performed via two different routes (dye and matrix ones), that led to photochromic multi-layer coating systems with coloration depth and photostabilities comparable to commercially available products. Hybrid sol-gel derived polymers were found to be suitable host materials for photochromic dyes. Matrix properties and the type of entrapment heavily influence the photochromic activity, as well as the degradation rate and the kinetics of incorporated dyes. Dyes incorporated within more polar and rigid matrices were found to show slower kinetics and higher coloration but associated with faster photodegradation. On the other hand, hosts with less polar sites, low residual water concentration and low rigidity are preferable in terms of photostability. Significant differences were found for physically incorporated and covalently grafted chromophores. Using silylated dyes that can participate in the sol-gel process, the photodegradation rate of the whole system can be decreased as compared to the physically entrapped systems. The higher photostability and slower kinetics for covalently bonded photochromes is probably due to sterical hindrance. Addition of proper stabilisers increases the photostability: The employment of UV light stabilisers, excited state quenchers and HALS was found to be beneficial but not sufficient. Besides the presence of stabilisers, also the reduction of oxygen migration into the coating (by a hard top coat and an inorganic anti reflective coating) strongly increases stability of photochromes. Finally, it was found that the separation of photochromes within two (or more) different layers leads to a further improvement of the coloration and fatigue behaviour of the whole coating stack, presumably by preventing the contact of dye molecules with excited states of other molecules or their degradation products. These latter findings are considered to pave the way for stable photochromic coatings based on hybrid polymers. Future development should be directed towards more photostable yellow and red switching dyes. The results of the present investigations should help to choose the most suitable molecular environments for the tested photochromes in terms of photostability, kinetics and activity, which is considered relevant with respect to potential applications, in particular in the ophthalmic sector. Furthermore, the interesting combination of properties of this type of materials offers a large potential with regard to many applications, such as coatings for sunglasses, radiation protectors, filters, sunroofs, reversible markings, printing applications and smart textiles. / Das Ziel dieser Arbeit war es, neue, über das Sol Gel Verfahren hergestellte Beschichtungsmaterialien zu entwickeln, die als Matrices für photochrome Spirooxazine und Chromene geeignet sind. Die Entwicklungs- und Optimierungsarbeit erfolgte über zwei Routen (Farbstoff- und Matrix-Rout) und führte zu komplexen photochromen Mehrschichtaufbauten, deren Einfärbungs und Photostabilitätseigenschaften mit kommerziell erhältlichen Produkten vergleichbar sind. Über das Sol-Gel Verfahren hergestellte hybride Polymere stellen geeignete Wirtsmaterialien für photochrome Farbstoffen dar. Die Eigenschaften der Matrix und die Einbauweise beeinflussen sowohl die photochrome Aktivität, als auch die Degradationsgeschwindigkeit und Kinetik der eingebauten Farbstoffe. Farbstoffe integriert in rigide Matrices höherer Polarität zeigen geringere Schaltgeschwindigkeit und stärkere Einfärbung, jedoch verknüpft mit höherer Degradationsgeschwindigkeit. Andererseits Matrixmaterialien mit eher unpolarem Charakter, niedriger Konzentration an Restwasser, und niedriger Rigidität sind zu bevorzugen, wenn gute Photostabilität erreicht werden soll. Wesentliche Unterschiede bestehen zwischen chemisch angebundenen und physikalisch eingebauten Farbstoffen. Durch den Einsatz von silylierten Farbstoffen, die am Sol Gel-Prozess partizipieren können, kann eine Verringerung der Photodegradationsgeschwindigkeit im Vergleich zu physikalisch eingebauten Farbstoffen erreicht werden. Höhere Photostabilität und langsamere Schaltkinetikt sind vermutlich auf sterische Hinderung zurückzuführen. Der Zusatz geeigneter Stabilisatoren erhöht die Photostabilität: Der Einsatz von UV Stabilisatoren, Excited State Quenchern und HALS ist vorteilhaft aber nicht ausreichend. Neben der Präsenz von Stabilisatoren, führt auch die Verringerung der Sauerstoffpermeation (durch eine harte Deckschicht und eine reflexionsmindernde PVD Beschichtung) zu einer Stabilitätserhöhung. Schließlich wurde gefunden, dass die räumliche Trennung der Farbstoffe in zwei (oder mehr) unabhängigen Schichten ebenfalls die Färbetiefe und Photoresistenz der Beschichtungen erhöhte, vermutlich dadurch, dass der Kontakt von Farbstoffmolekülen mit angeregten Zuständen anderer Moleküle oder ihren Degradationsprodukten verhindert oder zumindest eingeschränkt wird. Diese Befunde können den Weg für stabile photochrome Beschichtungen auf de Basis von Hybridpolymeren ebnen. Weiterer Optimierungsbedarf wird in den bisher erzielbaren Farbtönen gesehen. Zukünftige Entwicklungen sollten sich auf photostabilere gelb und rot schaltende Farbstoffe konzentrieren. Die Ergebnisse der vorgelegten Untersuchungen können bei der Auswahl der am besten geeigneten, molekularen Umgebung für erprobte Photochrome in Bezug auf Photostabilität, Kinetik und Aktivität helfen. Dies ist von großer Bedeutung im Hinblick auf mögliche Anwendung vor allem im ophthalmischen Bereich. Darüber hinaus bergen die interessante Eigenschaftskombinationen dieser Art von Materialien großes Potential für ein weites Feld möglicher Anwendungen (Sonnenbrillen, Strahlungsschutz, Filter, Sonnendächer, schaltbare Markierungen, Druck, Textilien).

Faculty of Science School of Chemistry 9911467t EMMA.MOKOENA@sasol.com / The objective of the study was to prepare novel silica materials and then use them as supports/binders for the Fisher-Tropsch (F-T) reaction. Hence the thesis is divided into two parts - (i) the synthesis of silica materials (ii) use of silica materials as supports. PART I The studies that were carried out in this thesis evaluated the effect of templates and synthesis conditions on the nano- and microstructure and properties of silica materials that are obtained by the sol-gel method. The studies with DL-tartaric acid and citric acid as templates revealed that synthesis conditions (temperature, NH4OH concentration, water/ethanol concentration, time before NH4OH addition, static versus stirred conditions, stirring rate and solvent) all have an effect on the microstructure of the silica and influence the formation of particular silica morphologies. DL-tartaric acid produced longer and more uniform tubes when compared to citric acid. Tubes that are formed by DL-tartaric acid are hollow and open ended; however the ones formed in citric acid are a mixture of filled and hollow but closed tubes. Hollow spheres are exclusively formed when citric acid is used under certain conditions while only filled spheres are formed when DL-tartaric iii acid is used. The surface areas of the silicas formed from DL-tartaric acid are lower that the surface areas obtained for materials produced by citric acid. The nitrogen adsorption-desorption isotherms of silica materials obtained from both templates showed that the materials were mesoporous with some microporosity present in them. Studies with mucic and tartronic acids as templates also showed that the template as well as the synthesis conditions (such as solvent, temperature and stirring) affect the resulting silica morphology. Mucic acid produced silica materials with high surface areas, mesopores and a morphology that reveals fragmented tubes. Tartronic acid produced hollow tube materials with low surface areas and a combination of micro- and mesopores. The yield of the tubes was higher at lower temperatures for both templates. When sugars (e.g. glucose) were used only spherical particles were obtained and some sugars gave particle sizes that are smaller than the ones that are normally obtained by the sol-gel method. PART II Catalysts (Fe/Cu/K) supported on a range of silica materials with different morphologies (hollow nanotubes, hollow spheres, Stöber/closed spheres) were evaluated in the Fischer-Tropsch reaction (8 bar, 250 °C, 400 h-1 GHSV). The supported iron catalysts modified the physico-chemical properties and activity of iv the catalysts but not the catalyst selectivity. A Ruhrchemie catalyst (known F-T catalyst standard) was also evaluated under the same reaction conditions as the new catalysts for comparison purposes. The Ruhrchemie catalyst was found to be the most active catalyst followed by the catalyst supported on nanotubes, Stöber spheres and hollow spheres respectively. Catalysts containing 18% silica showed the best activity compared to the 9% and 27% silica catalysts. The product distribution and WGS activity were largely influenced by the potassium that is present in the samples and not the support type. Mössbauer spectroscopy showed that some active catalysts contained χ' – Fe2.5C and some superparamagnetic iron oxides or carbides while other catalysts also contained α – Fe and Fe3O4 in addition to χ' – Fe2.5C and some superparamagnetic iron oxides or carbides species. This finding supports the hypothesis that carbide formation is a requirement for active F-T catalysts. It also suggests that metallic iron is necessary for carbiding to occur, hence the need for a reduction pre-treatment.