Proteins that recognise the sugar surface structures on cells have an enormous potential to be used as tools in the characterisation of these structures. A group of proteins, called lectins, have been identified that can bind to carbohydrate complexes on the receptors of cells. The crude extract from Grevillea robusta seeds was found to contain lectin-like proteins that were different from most other lectins, as they would specifically target the receptors of white blood cells and not those found on red blood cells. Therefore, the lectin isolated from G.robusta could be used as a tool to identify the specific surface structures on white blood cells. The lectin was isolated using affinity chromatography where a complex (oligosaccharide) matrix was used. Agglutination, binding and sugar inhibition assays confirmed the isolated protein was a lectin. The lectin was found in low amounts (up to 5% of the total protein content) within the seeds of G.robusta. As a result of this low yield, the identification of the lectin by PAGE was difficult because the levels of protein were beyond the detection limit of the commercial staining reagents. The lectin was called the GR2 protein and was characterised as a monocot mannose binding lectin based on its sugar specificity for only mannose. A serine protease inhibitor was isolated from the seeds of G.robusta using two different chromatography methods, reverse phase HPLC (GR1.HPLC) and gel filtration chromatography (GR1.GF). Ion exchange chromatography was used to initially separate the proteins in the crude extract and the fraction containing the GR1 protein was further purified using reverse phase HPLC (GR1.HPLC). N-terminal sequencing results of the GR1.HPLC protein, showed evidence of proteolytic cleavage during the extraction process, which lead to the second purification method being established. Protease inhibitors were added to the buffers prior to being purified by gel filtration chromatography, which resulted in the GR1 protein being isolated from the crude extract without the presence of the contaminating protein. Mass spectroscopy identified the molecular weight of the GR1 protein to be 6669Da and the full amino acid sequence was derived by cDNA techniques. Sequence alignment studies of the GR1 protein showed significant similarities with the Bowman-Birk inhibitor. The positioning of the cysteine residues were conserved throughout the Bowman-Birk superfamily, however these residues were not conserved within the GR1 protein. Competitive inhibition assays on the GR1 protein revealed the protein could inhibit both trypsin and chymotrypsin at similar levels to that seen for the Bowman-Birk inhibitor. Therefore, the GR1 protein was characterised as a member of the Bowman-Birk superfamily of serine protease inhibitors. The three-dimensional structure of the GR1 protein was determined using two-dimensional NMR spectroscopy. Computer programs such as XEASY, DYANA and SYBYL® were used to tabulate the information taken from the 2D experiments, generate structures and minimise these structures respectively. The solution structure of the GR1 protein was found to contain a region of antiparallel β-sheet structure that corresponded to the trypsin binding site and the remainder of the protein consisted of loops and turns that were held together by disulfide bridges (the chymotrypsin-binding region). Structural similarities between the GR1 protein and the Bowman-Birk inhibitor existed only in the trypsin-binding site of the Bowman-Birk inhibitor. The GR1 protein is the first member of the Proteaceae family to be characterised as a Bowman-Birk inhibitor. This thesis outlines the isolation and biochemical characterisation of the two proteins found within Grevillea robusta and also describes the steps involved and results obtained in determining the three-dimensional structure of the GR1 protein.

<p>To improve the adsorption capacity of polyacrylonitrile (PAN) fibres, hydrophilic amidoxime fibres were prepared by subsequent conversion of the cyano groups to an amidoxime group by reacting with hydroxylamine at 80&deg / C at an optimum amidoximation time of 2 hrs. The amidoxime fibre was hydrolyzed/alkali treated in a solution of sodium hydroxide to enhance or improve the adsorption properties. This was followed by characterization of the amidoxime and hydrolyzed fibres using Scanning electron microscopy (SEM) / Fourier transform Infrared Spectroscopy (FTIR) and exchange capacity (cationic and anionic). SEM showed that the hydrolysis process made the surface of Amidoxime fibre rougher than that of Polyacrylonitrile fibre. FTIR revealed that the hydrolyzed Amidoxime fibres contained conjugated imine (-C=N-) sequences. Functionalization enhanced the sorption of amidoxime fibres by an increase of 20 % in the cationic exchange capacity. This was achieved by the part conversion of the cyano groups into the carboxylic acid groups. The fibres showed faster kinetics largely due the available exchange sites on the surface of the fibres hence the equilibration was achieved much quicker.</p>

Open-framework inorganic materials constitute an important area of study in materials chemistry, because of their potential applications in areas such as sorption and catalysis. After the discovery of nanoporous aluminium phosphates (AlPOs) by Flanigen et al in 1982, there has been a tremendous growth in the area of porous solids that are based on phosphates. Apart from phosphates, phosphites, arsenates, sulfates, sulfites, selenates, selenites etc. have also been investigated. In addition to the different anions, the framework compounds now encompass almost all the elements of the periodic table. The compounds exhibit wide variety and structural diversity. New building units, such as thiosulfate and borate have also been explored as a network builder in the formation of framework structures. In this thesis, the results of the investigations on open-framework metal thiosulfates, metal borates and metal sulfates are presented. The studies are aimed not only at the synthesis of the new compounds based on the new anions, but also their possible applications. In Chapter 1 of the thesis an overview of inorganic open-framework materials with different anions is presented. In Chapter 2 (Part A), the synthesis, structure and transformation of inorganic-organic hybrid open-framework cadmium thiosulfate are presented. The lack of stability of the thiosulfate ion in solution prompted the exploration of new approaches such as low temperature solvothermal methods, use of rigid linkers etc. The transformations of lower to higher dimensional structures have been accomplished. The possible mechanisms for such transformations were investigated. In Part B, the physical and chemical properties of the hybrid cadmium thiosulfate frameworks are presented. The studies indicate that the anionic dyes selectively adsorb on the compounds in the water medium and also desorb reasonably in alcoholic medium. The cadmium thiosulfate compounds appear to be reasonable photocalysts for the photodecomposition of the cationic dyes under UV irradiation as well as under sunlight with good recyclability. The compounds also exhibit heterogeneous catalytic behavior (Lewis acidity) for the cyanosilylation of the imines. In Chapter 3, a new family of organically templated open-framework borate materials is presented. The zinc and aluminoborate structures, prepared in the present study, are rationalized using the HSAB theory. The [B4O9H2] units polymerize differently to form different zinc borate structures. The amine molecules act as a ligand by binding with the metal. The nature of the amine appears to control the dimensionality of the final zinc borate structures. The zinc borate compounds exhibit absorption of UV-light (λ = 365 nm) suggesting that the zinc borate compounds could be exploited for UV-blocking applications. Organically templated aluminoborates have connectivities between the Al3+ ions and the [B5O10] cyclic pentaborate units. The aluminoborate structures exhibit graphite layer and three-dimensional diamond structure. Detailed studies and comparison of the various amine templated open-framework aluminoborate structures reveals subtle relationships between the organic amines (shape and length of the amines) and the final framework structures. In Chapter 3, the synthesis, structure and catalytic studies of a variety of cadmium sulfate phases have been carried out. Polyazaheterocyclic ligands were employed to study their possible role in the formation of such structures. All the compounds have structures built up by the connectivity involving the cadmium octahedra and the sulfate tetrahedra in which the heterocyclic organic molecules act as the ligand. The connectivity between the Cd2+ and (SO4)2− ions form one-, two-and three-dimensionally extended cadmium sulfate phases, though the starting source is cadmium sulfate (CdSO4.8/3H2O) in all the cases. The connectivity between Cd2+ ion and the heterocyclic ligand also gives rise to one-and two-dimensional structures. The interconnectivity between the two units gives rise to the final observed structure. As part of the study, a variety of properties i.e. adsorption-desorption, photocatalytic degradation and cyanosilylation reaction, exhibited by the cadmium sulfate compounds have been investigated and the properties are comparable to the cadmium thiosulfate phases. AlPOs are well known for their many important properties. The wide varieties in their structures and heterogeneous catalytic properties have been extensively investigated. The photocatalytic behaviors, on the contrary, have not been investigated in detail. The photocatalytic properties of the metal-doped AlPOs, for the photodegrdation of organic dyes have been investigated in the Chapter 5. The metal ions (Mg2+, Zn2+ and Co2+) have been substituted in place of Al3+ and Ti4+ in place of both the Al3+ and P5+ in a variety in AlPO structures and the synthesized phases are characterized by a variety of techniques. Photodecomposition studies of organic dye molecules under UV-light were carried out in aqueous medium. The studies suggest that the photocatalytic activity is reasonable and appears to depend on the dopant concentration. Ti-substituted phase exhibits the maximum catalytic activity.

Electrodialysis performance strongly depends on the boundary layer near ion exchange membranes. The thickness of the boundary layer has not been clearly evaluated due to its substantial fluctuation around the spacer geometry. In this study, the boundary layer thickness was defined with three statistical parameters: the mean, standard deviation, and correlation coefficient between the two boundary layers facing across the spacer. The relationship between the current and potential under conditions of the competitive transport between mono- and di-valent cations was used to estimate the statistical parameters. An uncertainty model was developed for the steady-state ionic transport in a two-dimensional cell pair. Faster ionic separations were achieved with smaller means, greater standard deviations, and more positive correlation coefficients. With the increasing flow velocity from 1.06 to 4.24 cm/s in the bench-scale electrodialyzer, the best fit values for the mean thickness reduced from 40 to less than 10 μm, and the standard deviation was in the same order of magnitude as the mean. For the partitioning of mono- and di-valent cations, a CMV membrane was examined in various KCl and CaCl₂ mixtures. The equivalent fraction correlation and separation factor responded sensitively to the composition of the mixture; however, the selectivity coefficient was consistent over the range of aqueous-phase ionic contents between 5 and 100 mN and the range of equivalent fractions of each cation between 0.2 and 0.8. It was shown that small analytic errors in measuring the concentration of the mono-valent cation are amplified when estimating the selectivity coefficient. To minimize the effects of such error propagation, a novel method employing the least square fitting was proposed to determine the selectivity coefficient. Each of thermodynamic factors, such as the aqueous- and membrane-phase activity coefficients, water activity, and standard state, was found to affect the magnitude of the selectivity coefficient. The overlimiting current, occurring beyond the electroneutral limit, has not been clearly explained because of the difficulty in solving the singularly perturbed Nernst-Planck-Poisson equations. The steady-state Nernst-Planck-Poisson equations were converted into the Painlevé equation of the second kind (P[subscript II] equation). The converted model domain is explicitly divided into the space charge and electroneutral regions. Given this property, two mathematical formulae were proposed for the limiting current and the width of the space charge region. The Airy solution of the P[subscript II] equation described the ionic transport in the space charge region. By using a hybrid numerical scheme including the fixed point iteration and Newton Raphson methods, the P[subscript II] equation was successfully solved for the ionic transport in the space charge and electroneutral regions as well as their transition zone. Above the limiting current, the sum of the ionic charge in the aqueous-phase electric double layer and in the space charge region remains stationary. Thus, growth of the space charge region involves shrinkage of the aqueous-phase electric double layer. Based on this observation, a repetitive mechanism of expansion and shrinkage of the aqueous-phase electric double layer was suggested to explain additional current above the limiting current. / text

<p>To improve the adsorption capacity of polyacrylonitrile (PAN) fibres, hydrophilic amidoxime fibres were prepared by subsequent conversion of the cyano groups to an amidoxime group by reacting with hydroxylamine at 80&deg / C at an optimum amidoximation time of 2 hrs. The amidoxime fibre was hydrolyzed/alkali treated in a solution of sodium hydroxide to enhance or improve the adsorption properties. This was followed by characterization of the amidoxime and hydrolyzed fibres using Scanning electron microscopy (SEM) / Fourier transform Infrared Spectroscopy (FTIR) and exchange capacity (cationic and anionic). SEM showed that the hydrolysis process made the surface of Amidoxime fibre rougher than that of Polyacrylonitrile fibre. FTIR revealed that the hydrolyzed Amidoxime fibres contained conjugated imine (-C=N-) sequences. Functionalization enhanced the sorption of amidoxime fibres by an increase of 20 % in the cationic exchange capacity. This was achieved by the part conversion of the cyano groups into the carboxylic acid groups. The fibres showed faster kinetics largely due the available exchange sites on the surface of the fibres hence the equilibration was achieved much quicker.</p>

Coal Seam Gas (CSG) is a form of natural gas (mainly methane) sorbed in underground coal deposits. Mining this gas involves drilling a well directly into an underground coal seam, and pumping out the water (CSG water) flowing through it. Presently, CSG is under exploration in New Zealand (NZ); however, there is concern about CSG water disposal in NZ mainly because of the controversy that this activity has generated in some basins in the United States (US). The first part of this thesis studies CSG water from a well in Maramarua (NZ) and compares it to water from US basins. The NZ CSG water from this well had high pH (7.8), alkalinity in the order of 360 mg/l as CaCO₃, high sodium (334 mg/l), bicarbonate (435 mg/l), and chloride (146 mg/l). These ions also occur in US CSG waters, and their concentrations follow the same trend - high sodium, bicarbonate, and chloride with low calcium, magnesium, and sulphate concentrations. Prior to this work, little detailed analyses of CSG water quality variability from a well had been carried out. A Factor Analysis of 33 Maramarua samples was conducted and revealed that about one third of the variations were due to sample degassing, which induced calcium carbonate precipitation - this was supported by experimental work (sample sparging) and geochemical modelling (MINTEQA2). This finding is important for CSG water management because, as calcium concentrations decrease, higher SAR values are generated, and this can cause problems if CSG waters are disposed on land. In the second part, this thesis assesses the potential environmental effects of disposing CSG waters in NZ by formulating management options and a simple wastewater treatment system. This was carried out by studying the ecological response (soils, plant, and aquatic life) resulting from CSG water disposal operations in the US, and by applying relevant salinity and sodicity guidelines to the interaction between soils and CSG waters from Maramarua. This work showed that similar problems are likely to occur in NZ if CSG water disposal takes place without proper controls. Such a study has never been carried out in a region before actual CSG development has taken place, so this work shows how to quantify the effects arising from CSG water disposal prior to full scale production. This can be particularly useful for CSG stakeholders wanting to develop this resource in other regions around the world. A simple treatment system using Ngakuru zeolites has proven effective in reducing the SAR of Maramarua CSG water. Laboratory results indicate that these zeolites work by exchanging sodium cations in the water by other cations contained within the zeolite structure but with slow ion exchange kinetics. The calculated sodium absorption capacity for these natural zeolites ranged from 11.3 meq/100g to 16.7 meq/100g (flow-through conditions without previous regeneration). In addition, these experiments showed that the ion exchange process is accompanied by some dissolution (sulphate, boron, TOC, sodium, calcium, magnesium, potassium and reactive silica), but mainly at the beginning of the treatment process. Nevertheless, using this system, 180 grams of zeolite material were used to treat an initial 1.83 litres of Maramarua CSG water thus reducing potential soil infiltration problems to nil. As more CSG water was treated, the zeolites kept reducing SAR values but at a lesser rate until 4.53 litres of CSG water had been treated. A step-by-step methodology to assess treatment design options for these materials has been developed and will aid future researchers and engineers. This thesis presents the first comprehensive study of CSG water management in NZ. It also presents an ion exchange treatment system using natural zeolites already available in NZ. In conclusion, the research finds that, whether through adequate management or active treatment, CSG waters can be safely disposed without creating major environmental problems, and can even be used in beneficial applications.

In South Africa, being the second largest global coal exporter, coal mining plays a pivotal role in the growth of our economy, as well as supplying our nation’s ever increasing electricity needs; while also accounting for more than 10% of the 20 x 109 m3 water used annually in the country. Coal mining may thus be classified as a large-scale water user; known to inevitably generate wastewater [acid mine drainage (AMD)] and other waste material, including fly ash (FA). Current and conventional AMD treatment technologies include precipitation–aggregation (coagulation/flocculation) – settling as hydroxides or insoluble salts. The process stream resulting from these precipitation processes is still highly saline, therefore has to undergo secondary treatment. The best available desalination techniques include reverse osmosis (RO), electro dialysis (ED), ion exchange and evaporation. All available treatment methods associated with raw AMD and its derived process stream fall prey to numerous drawbacks. The result is that treatment is just as costly as the actual coal extraction. In addition, remediation only slows the problem down, while also having a short lifespan. Research conducted into converting fly ash, an otherwise waste material, into a marketable commodity has shown that direct mixing of known ratios of FA with AMD to a pre-determined pH, erves a dual purpose: the two wastes (AMD and FA) could be neutralized and produced a much cleaner water (secondary co-disposal [FA/AMD]-process water), broadly comparable to the process water derived from precipitation-aggregation treated AMD. The collected post process solid residues on the other hand, could be used for production of high capacity ion exchange material (e.g. zeolite A, faujasite, zeolite P, etc.). The produced ion exchange material can subsequently be utilized for the attenuation of metal species in neutralized FA/AMDprocess waters. / Magister Scientiae - MSc

The objective of this study was to investigate the feasibility of the application of low cost high capacity inorganic ion exchange material, synthesized form collected fly ash and acid mine drainage solid residues, for the decontamination of secondary co-disposal process waters, with emphasis on investigating the processes governing the solid/solution interface.

La création du premier laser en 1960 puis l’envol des télécommunications par fibres optique a généré le développement des circuits optiques intégrés. Ces derniers sont des solutions efficaces aux problèmes d’encombrement et d’instabilité. Un contrôle accru des signaux passe cependant par l’exploitation de la polarisation qui permet notamment d’augmenter les débits, de fiabiliser les signaux et de protéger les sources par une isolation optique. Cette dernière application fait partie d’un vaste projet mené par l’IMEP-LAHC en collaboration avec le laboratoire Hubert Curien de Saint-Etienne. L’isolateur sur verre comprend l’intégration d’un séparateur de polarisation, d’un rotateur Faraday et d’un rotateur réciproque de polarisation à 45°. L’objectif de ces travaux «était de démontrer la faisabilité de la dernière fonction. La réalisation s’est basée sur l’exploitation d’échanges d’ions assistés par un champ électrique (EAC). Une première étape a consisté à maîtriser les effets de bords inhérents aux EAC, afin de modeler le cœur d’un guide d’onde et incliner les axes neutres de polarisation. Ceci a été obtenu en cascadant deux EAC, le premier créant un guide d’indice de réfraction uniforme, le deuxième modelant son cœur. Le contrôle de la position des axes neutres a ainsi été démontrée pour la première fois dans cette technologie puisqu’une inclinaison à (46,6 ± 0,1)° en entrée et (42,3 ± 0,1)° en sortie a été mesurée. L’étude numérique du procédé de fabrication du rotateur réciproque a également été effectuée et l’adiabaticité du composant a été validé analytiquement. Une première réalisation a mis en évidence un problème de pertes élevées liées au dégazage des sels d’échange. Des pistes d’optimisation sont donc avancées. Une suggestion d’amélioration du rotateur Faraday est également présentée. Elle exploite les progrès obtenus sur les EAC et démontre la faisabilité de guides d’ondes à biréfringence négative. Finalement un procédé de fabrication de l’isolateur complet, compatible avec le budget thermique, est proposé. / The fabrication of the first laser in 1960 and the growth of fiber optics telecommunications have led to the development of integrated optics circuits. Theses lasts are efficient solutions to compacity and misalignment problems. Moreover, polarization management in integrated circuits enables to increase the data rate, to guaranty the signals reliability or to protect optical sources. The work presented here is dedicated to this last application, which is the motive of a long-term collaboration between IMEP-LAHC and the Hubert Curien institute in Saint-Etienne. Indeed, we proposed to fabricate a 45° reciprocal polarization rotator that is part of the optical isolator’s design, along with a polarization splitter and a Faraday rotator. We choose to use a field-assisted ion-exchange technique (FAIE). The implementation of the polarization rotator requires managing the side effects of the electrical field lines occurring during a FAIE. It allows controlling the waveguide core’s shape and thus the eigen axes tilt. It was obtained thanks to two cascaded FAIE. The first one, an Ag+/Na+ ion exchange, creates a high refractive index waveguide while the second one, a Na+/Na+ ion exchange, modifies the shape of the waveguide’s core. Measurements of the experimental polarization behavior are a first proof of a controlled tilt of eigen axes in this technology. Indeed, the waveguide exhibits a tilt of its eigen axes of (46.6 ± 0.1)° at the input and (42.3 ± 0.1)° at the output.The numerical study of the reciprocal rotator’s process has also been proposed and the adiabaticity of the design analytically validated. The first realization highlights high propagation losses that can linked to the degassing of the nitrate salts occurring during the FAIE. Possible improvements are thus suggested in the document.An enhancement of the Faraday rotator’s design is also proposed. It is obtained thanks to the fabrication of a waveguide exhibiting a negative birefringence whose design exploits the progress achieved in term of FAIE control. Eventually, a complete fabrication of the integrated isolator is proposed, taking into account the thermal budget of the various processes.

Le présent travail est dédié à l’étude d’un procédé hybride couplant l’électrodialyse à membrane bipolaire et l’échange d’ions. Cette étude est appliquée au traitement de solutions diluées d’acide acétique. L’objectif est double : acquérir une compréhension théorique des processus de transfert et des mécanismes qui impactent la consommation énergétique de ce système hybride et, de façon plus appliquée, proposer une configuration de cellule qui permette d’éliminer l’acide de la solution traitée en la transférant vers un compartiment de concentration. Cette configuration doit permettre d’obtenir le taux de purification le plus élevé possible tout en minimisant la consommation d’énergie. Des critères visant à optimiser le choix des résines échangeuses d’ions (fortes ou faibles) dans les compartiments de dilution sont proposés. L’intérêt de l’utilisation d’une résine cationique forte sous forme H+ dans le compartiment de concentration est par ailleurs mise en évidence, conduisant à une diminution de la résistance du compartiment et de ce fait de la consommation d’énergie. Une étude réalisée sur des systèmes « couplés » et « découplés » a permis d’identifier les contributions résistives des différents éléments de l’empilement. Cette approche a conduit à la détermination des paramètres d’un modèle qui permet de prévoir la résistance électrique d’un lit de résine dans une solution donnée. Les consommations spécifiques d’énergie (kWh/kg d’acide transféré) ont été évaluées en fonction du taux de purification souhaité. L’ensemble de l’étude a permis d’établir des recommandations pour la conception de la cellule et pour le choix des paramètres opératoires. / This work is dedicated to the study of a hybrid separation process involving bipolar membrane electrodialysis and ion exchange. This study is applied to the treatment of diluted effluents. The aim is first to acquire a theoretical understanding of transfer processes and mechanisms that affect energy consumption of this hybrid system. Then, in a more applied way, the objective is to be able to propose a cell configuration that allows to remove the acid from the treated solution by transferring it to a concentration compartment. This configuration must allow to obtain the highest purification rates as possible while minimizing energy consumption. Criteria aiming at optimizing ion exchange resins (strong or weak) in dilution compartment are proposed. The interest of the introduction of strong cationic resin under H+ form in the concentrated compartment is highlighted, as it enables reducing compartment resistance and hence energy consumption. Furthermore, experimental measurements successively conducted with “decoupled” and “coupled” systems identified resistive contributions of the different elements of the stack. This approach led to the determination of parameters of a model which predicts the resin bed electrical resistance in a given solution. Specific energy consumption (kWh/Kg transferred acid) was evaluated as a function of the desired purification rate. All the work led to recommendations for the cell design and for the choice of operating parameters.