Thesis (Doctoral)--Bayerischen Ludwig-Maximilians-Universität zu München, 1934.

Dissertation (Ph.D.)--University of Toledo, 2010. / "Submitted to the Graduate Faculty In partial fulfillment of the requirements for the Doctor of Philosophy Degree in Biomedical Science." Title from title page of PDF document. "A Dissertation entitled"--at head of title. Non-Latin script record Bibliography: p. 68-101.

Thèse. Doct. ing.--Bordeaux I, 1973. N°: 194. / Bibliogr. p. 87-89.

Recently a large amount of interest has developed around separating out impurities of small size; pertinent examples are found within fuel and solvent processing. For such applications a leading candidate process is nanofiltration. This thesis focuses on SRNF (solvent resistant nanofiltration) composite membranes consisting of a dense polymer active layer bonded to a stronger, but ultimately more porous, support layer. The composite membranes that have been produced during the course of this work consist of a PDMS (polymdimethylsiloxane) active layer bonded to a commercially available support layer of PAN (polyacrylonitrile). To create the membrane a monomer was spread over the support layer and then polymerised to form the matrix which was responsible for separation. Commercially, either heat or radiation is often applied to cause polymerisation, however the membranes in the current work have been formed by the used of a homogeneous catalyst. This thesis investigates the transport and separation dynamics of the produced membranes for a series of fuel simulants composed of organometallics and poly-nuclear aromatic solutes dissolved in aromatic and alkane solvents. Membrane composition and the extent of polymer swelling were found to be the two key factors which had the greatest influence on solvent flux and solute rejection. By increasing catalyst concentration it was found that the dual effects of increased rejection and reduced flux occurred, with the converse also being true. The effective pore size of the membrane could also be controlled by varying the catalyst amount during manufacture as this directly affected the limit of crosslinking which formed. Polymer swelling was the most pronounced using solvents with a solubility parameter close to that of the polymer. The membrane transport mechanism was most accurately forecast by the solution diffusion model for flux predictions and the convection diffusion model for rejection predictions, however all the models tried were in close agreement. This was postulated to be due to the swelled polymer matrix which allows for both convective and diffusive transport to occur.

Submitted in fulfilment of the academic requirements for the Degree of Masters in Technology: Chemical Engineering, M.L. Sultan Technikon, 2002. / Crossflow microfiltration (CFMF) using a fabric support has been successfully used to treat a range of problematic waters. Experimental evidence indicates that the formation of a dynamic membrane or precoat on a woven-fibre microfilter can significantly increase the performance of the filter, that is, the production rate and rejection. The use of precoats in filtration applications is based on the precoat's unique microstructure that is able to trap sub-micron particles while maintaining a permeable filter cake. However, to date the precoating step has been more of an art than a science. Very little knowledge exists on the best type of precoat to use, or the the optimal velocity, pressure and concentration to form a stable precoat. Further, although various models have been proposed for CFMF, their still exists a lack of knowledge of the mechanisms by which precoats improve performance. / M

Abstract Anion exchanger 2 (AE2) is a member of the anion exchanger gene family, which includes three additional members, AE1, AE3, and AE4. They are also known as Na+-independent Cl-/HCO3- exchangers, and their major function is to regulate intracellular pH and chloride concentration. All four isoforms have several N-terminally truncated variants that are often expressed cell type specifically. Red blood cells express the full-length AE1 isoform that interacts with ankyrin, an adapter protein linking plasma membrane to the spectrin-based membrane skeleton. This membrane skeleton association is essential for maintaining the membrane integrity of red blood cells. AE3 variants are mainly found in the brain and heart, whereas AE4 is localized in the kidney. Anion exchanger 2 is expressed in every cell line and tissue studied thus far, and it has been mainly localized to the plasma membrane. However, we found two types of localization/targeting of the AE2 protein in several of the cell lines studied. The protein was localized to either the plasma membrane or the Golgi complex, depending on the cell type. The AE2 variant expressed in these cells was identified as the full-length AE2 protein. The determinants of differential intracellular targeting were assessed. We hypothesized that Golgi-AE2 is anchored to the Golgi membranes via its association with the Golgi membrane skeleton. We were able to show that the Golgi localization of AE2 correlated with the cell type specific expression of Ank195, a Golgi membrane skeletal protein. In cells where AE2 was targeted to the plasma membrane, Ank195 was not expressed. In addition, the detergent insolubility and co-redistribution properties of AE2 and Ank195 strongly suggested that these proteins interact with each other. The Golgi membrane skeleton has been shown to be necessary for maintaining the Golgi structure. Our studies were consistent with these findings, showing that in cells in which AE2 expression was reduced by using AE2-specific antisense oligonucleotides, the Golgi complex was dispersed. The spectrin-based membrane skeleton was probably partially detached from the Golgi membranes leading to breakdown of the Golgi structure and disorganization of the microtubules associated with it. The present findings suggest that the targeting of AE2 is cell type specific, and that Golgi-localized AE2 serves as a membrane association site for the spectrin-based Golgi membrane skeleton, thereby participating in the maintenance of the Golgi structure.

The membrane-spanning phospholipids of the domain Archaea are postulated to provide membrane stability; this thesis reports the design and synthesis of a synthetic membrane-spanning macrocyclic lipid to test this hypothesis. Protected glutaric anhydride reacted with 10-undecyn-1-ol to produce a glutarate monoester. Copper-mediated azide-alkyne coupling (CuAAC) using 1,5-diazido-3-oxapentane(bis-azide) afforded a dicarboxylicacid with a hydrophobic chain of sufficient length to span a 35 Å bilayer membrane. The carboxylic acids were each esterified with an equivalent of 10-undecyn-1-ol. After optimization an 87% yield was obtained in the closure of the 72-membered macrocycle with the bis-azide using CuAAC. Deprotection and coupling with p-nitrophenyl phosphorodichloridate completed the synthesis. Two other phospholipids, a linear bolaamphiphile derived from the precursor to the second click reaction, and a linear amphiphile created from a glutarate bis-dodecyl ester, were also synthesized to provide controls for probing the orientation of the macrocyclic phospholipid in the bilayer membrane of vesicles. The amphiphile, linear bolaamphiphile, and macrocyclic bolaamphiphile were synthesized in 4, 5, and 6 steps with yields of 19, 4, and 5% respectively. The hydrophilic head group of the macrocyclic phospholipid was designed to release p-nitrophenolate in basic conditions from the p-nitrophenylphosphate head group to produce an absorbance at 400 nm. This assay was expected to elucidate the membrane-spanning orientation of the phospholipid in the bilayer membrane of vesicles. The final target compound failed to release p-nitrophenolate under basic conditions and underwent phosphate elimination to produce an α, β-unsaturated ester instead. Although the macrocyclic lipid produced associates with membranes and may be membrane-spanning, this lipid design was unable to reveal its membrane orientation. / Graduate

Le but de ces travaux était de développer des membranes non oxydes a-SiCxNy:H par PECVD, permsélectives à H2 et avec une bonne stabilité hydrothermale jusqu’à 400° C, afin d’envisager la mise au point d’un module membranaire s’intégrant dans une chaîne de purification de l’hydrogène. Des dépôts ont été réalisés dans deux types de réacteurs PECVD basse-fréquence (BF) et micro-ondes (MO), en utilisant les précurseurs HMDSN et NH3, et l’argon en tant que gaz vecteur. Dans un premier temps, différentes conditions de synthèse ont été étudiées afin d’obtenir une riche variété de matériaux déposés en couche mince soit sur silicium monocristallin (pour caractérisations physico-chimiques), soit sur supports mésoporeux plans (pour caractérisation du transport de gaz). Dans le réacteur BF, les paramètres tels que la température (25 - 300° C) et la pression en NH3 (0 - 0,4 mbar) lors de la synthèse ont été étudiés. En réacteur MO, ces études ont été complétées par la variation de la puissance (100 – 200W). L’influence de ces paramètres sur structure microporeuse des matériaux a été prouvée, et des corrélations avec les performances des membranes pour la séparation d’hydrogène ont été établies. Pour les deux types de réacteurs, un comportement de tamis moléculaire avec un bon compromis entre perméance et sélectivité pour He a été démontré. Dans un second temps, les travaux se sont tournés vers un transfert de la technologie vers l’industrie a été considéré en deux étapes. La première étape du transfert a été de remplacer les gaz purs (He, N2, CO2) par un mélange gazeux (H2/CO/CO2/CH4) sec ou sous atmosphère humide, en conservant la géométrie plane pour les supports. Les résultats prouvent que, malgré une légère diminution de la perméance pour les gaz de petites tailles inhérent au remplacement de He par H2, les membranes restent efficaces pour la séparation de H2. De plus, la présence d’humidité à 150° C semble augmenter les performances et prouve la stabilité hydrothermale des membranes à cette température. La seconde étape du transfert concerne le passage d’une géométrie de substrat plane à tubulaire avec dépôt des membranes PECVD sur la surface externe des supports tubulaires. Les résultats montrent que la qualité de surface de ces substrats est principalement responsable de la diminution des performances des membranes, même si la stabilité hydrothermale semble être conservée. / The aim of this work was to develop innovative a-SiCxNy:H membranes prepared by PECVD, with good selectivity for gas with small kinetic diameters (H2/He) and with good hydrothermal stability. For this purpose, membrane depositions were carried out in two types of reactors (low frequency LF and microwave MW) using both HMDSN and NH3 as precursors and argon as a carrier gas. First, different synthesis conditions were investigated in order to obtain a large range of materials deposited as thin layers on monocrystalline silicon (for physicochemical characterizations) and mesoporous planar substrates (for membrane characterization). In the LF reactor, parameters such as deposition temperature and NH3 pressure during the synthesis were studied. In MW reactor, these studies were supplemented by the change of electric power applied to the plasma. The influence of these parameters on the microporous structure of the materials has been proven, and correlations with the membranes ability to selectively permeate hydrogen have been established. For both types of reactors, a molecular sieving behavior was obtained with the following performance: single gas He permeance > 10-7 mol.m-2.s-1.Pa-1 and He/CO2 ideal selectivity = 50 at 400°C. Secondly, the first steps for a transfer of this lab scale technology towards industry are investigated. At first, single gas (He, N2 and CO2) were replaced by a gas mixture containing H2, CO, CO2 and CH4 for studying separation factors both in dry and wet conditions, while keeping a planar mesoporous substrate. The results showed that, despite a slight decrease in H2 permselectivity, the membrane was still a good candidate for this purpose. In addition, the presence of moisture at 150°C seemed to slightly increase performance and proved the hydrothermal stability of the membrane at this temperature. The second step corresponds to the transfer from planar to tubular geometry, with the PECVD membranes deposited on the outer surface of the tubes. The results showed that the geometric stresses and the possible mesoscopic defects of these substrates greatly reduced the H2 selectivity of the deposited a-SiCxNy:H membrane materials, although their molecular sieving behavior and thermal stability at 400°C were kept.

Magister Scientiae - MSc / Over the past 40 years, research pertaining to membrane technology has lead to the development of a wide range of applications including beverage production, water purification and the separation of dairy products. For the separation of gases, membrane technology is not as widely applied since the production of suitable gas separation membranes is far more challenging than the production of membranes for eg. water purification. Hydrogen is currently produced by recovery technologies incorporated in various chemical processes. Hydrogen is mainly sourced from fossil fuels via steam reformation and coal gasification. Special attention will be given to Underground Coal Gasification since it may be of great importance for the future of South Africa. The main aim of this study was to develop low temperature CsHSO4/SiO2 composite membranes that show significant Idea selectivity towards H2:CO2 and H2:CH4. / South Africa

Hybrid membranes represent a promising alternative to the limitations of organic and inorganic materials for high productivity and selectivity gas separation membranes. In this study, the previously developed concept of emulsion-polymerized mixed matrix (EPMM) membranes was further advanced by investigating the effects of surfactant and compatibilizer on inorganic loading in poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)-based EPMM membranes, in which inorganic part of the membranes originated from tetraethylorthosilicate (TEOS). The polymerization of TEOS, which consists of hydrolysis of TEOS and condensation of the hydrolyzed TEOS, was carried out as (i) one- and (ii) two-step processes. In the one-step process, the hydrolysis and condensation take place in the same environment of a weak acid provided by the aqueous solution of aluminum hydroxonitrate and sodium carbonate. In the two-step process, the hydrolysis takes place in the environment of a strong acid (solution of hydrochloric acid), whereas the condensation takes place in weak base environment obtained by adding excess of the ammonium hydroxide solution to the acidic solution of the hydrolyzed TEOS. For both one- and two-step processes, the emulsion polymerization of TEOS was carried out in two types of emulsions made of (i) pure trichloroethylene (TCE) solvent, and (ii) 10 w/v% solution of PPO in TCE, using different combinations of the compatibilizer (ethanol) and the surfactant (n-octanol). The experiments with pure TCE, which are referred to as a gravimetric powder method (GPM) allowed assessing the effect of different experimental parameters on the conversion of TEOS. The GPM tests also provided a guide for the synthesis of casting emulsions containing PPO, from which the EPMM membranes were prepared using a spin coating technique. The synthesized EPMM membranes were characterized using 29Si nuclear magnetic resonance (29Si NMR), differential scanning calorimetry (DSC), inductively coupled plasma mass spectrometry (ICP-MS), and gas permeation measurements carried out in a constant pressure (CP) system. The 29Si NMR analysis verified polymerization of TEOS in the emulsions made of pure TCE, and the PPO solution in TCE. The conversions of TEOS in the two-step process in the two types of emulsions were very close to each other. In the case of the one-step process, the conversions in the TCE emulsion were significantly greater than those in the emulsion of the PPO solution in TCE. Consequently, the conversions of TEOS in the EPMM membranes made in the two-step process were greater than those in the EPMM membranes made in the one-step process. The latter ranged between 10 - 20%, while the highest conversion in the two-step process was 74% in the presence of pure compatibilizer with no surfactant. Despite greater conversions and hence the greater inorganic loadings, the EPMM membranes prepared in the two-step process had glass transition temperatures (Tg) only slightly greater than the reference PPO membranes. In contrast, despite relatively low inorganic loadings, the EPMM membranes prepared in the one-step process had Tgs markedly greater than PPO, and showed the expected trend of an increase in Tg with the inorganic loading. These results indicate that in the case of the one-step process the polymerized TEOS was well integrated with the PPO chains and the interactions between the two phases lead to high Tgs. On the other hand, this was not the case for the EPMM membranes prepared in the two-step process, suggesting possible phase separation between the polymerized TEOS and the organic phase. The latter was confirmed by detecting no selectivity in the EPMM membranes prepared by the two-step process. In contrast, the EPMM membranes prepared in the one-step process in the presence of the compatibilizer and no surfactant showed 50% greater O2 permeability coefficient and a slightly greater O2/N2 permeability ratio compared to the reference PPO membranes.