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Thesis (Ph. D.)--University of Wisconsin--Madison, 1953. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 74-78).

Simultaneous electrosynthesis of alkaline hydrogen peroxide and sodium chlorate in the same cell was investigated. The alkaline hydrogen peroxide was obtained by the electroreduction of oxygen in NaOH on a fixed carbon bed while the chlorate was obtained by the reaction of anodic electrogenerated hypochlorite and hypochlorous acid in an external reactor. An anion membrane, protected on the anode side with an asbestos diaphragm was used as the separator between the two chambers of the cell. The effects of superficial current density (1.2 - 2.4 kA m⁻²), sodium hydroxide concentration (0.5 - 2.0 M) and catholyte flow (0.1 x 10⁻⁶ - 0.5 x 10⁻⁶ m³ s⁻¹) on the chlorate and peroxide current efficiencies were measured. The effect of peroxy to hydroxy mole ratio on the chlorate current efficiency was measured too. The cell was operated at fixed anolyte flow of 2.0 x 10⁻⁶ m³ s⁻¹, inlet and outlet temperatures of 27/33°C (anode side), 20/29°C (cathode side), cell voltages of 3.0 - 4.2 V (current density of 1.2 - 2.4 kA -m⁻²) and a fixed temperature of 70°C in the anolyte tank. Depending on the conditions, alkaline peroxide solution and sodium chlorate were cogenerated at peroxide current efficiency between 20% and 86%, chlorate current efficiency between 51.0% and 80.6% and peroxide concentration ranging from 0.069 M to 0.80 M. The cogeneration of the two chemicals was carried out at both concentrated (2.4 - 2.8 M) and dilute (0 - 0.5 M) chlorate solutions. A relative improvement on the current efficiencies at concentrated chlorate was observed. A chloride balance indicated negligible chloride loss to the catholyte. The results are interpreted in terms of the electrochemical and chemical kinetics and the hydrodynamics of the cell . / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

This master thesis project was carried out as a part of the chlorate research conducted at the Process RD&I department for bleaching chemicals at AkzoNobel Pulp and Performance Chemicals AB in Bohus. During the project already implemented filter cloths as well as new types of filters were studied and compared by experimental trials. The results were then examined in an attempt to evaluate existing filtration systems as well as investigate if there are other, better alternatives. The impurities found in a chlorate plant account for an efficiency loss in the process and a reduction of impurities would hence result in an energy reduction and a cleaner product. The trials were conducted at one of AkzoNobel’s chlorate plants. Six filters were studied and evaluated by measuring turbidity of the electrolyte and pressure over the filter during the experiments. Samples of the electrolyte were analyzed to obtain the metal content, and thereby the impurity content, of the electrolyte. The structures of the filters were studied by optical microscopy. The results from the trials show that all filter types except one, a needle felt filter, seem to be suitable for chlorate electrolyte filtration (including the filter types already used in the plants). The other filters all reach turbidity values below 0.1 FNU immediately or within 90 minutes of filtration, which is considered good enough. The results from the metal content analysis show a similar trend where the metal concentrations decrease to levels below the detection limits immediately or within 90 minutes of filtration. Apart from the lab trials performed some measurements were made on the existing filtration equipment in the chlorate plant. The measurements show varying results, partly similar to those achieved during the lab filter trials but also results showing a higher turbidity value and metal content, indicating that full scale operation are more complicated than lab scale operation. The lab trial results obtained with the filter types already used in the plants show that lower impurity content is possible to achieve. However, this would require closer monitoring of the filtration systems in the plants. Apart from the filtration trials, an attempt to determine the sizes of the particles present in the electrolyte using laser diffraction was performed. However, too little was known of the chlorate electrolyte’s optical data for the measurements to be reliable. Further work is needed before a method for size determination of the particles in a chlorate electrolyte can be achieved. Also, an Optical Filtration Test was tried on the electrolyte but was not sensitive enough for utilization on electrolyte with low (below 1 FNU) turbidity values.  The project concluded that a switch to another filtration system is unmotivated, unless a change in the product requirements would occur. Since the impurities have proven to affect the efficiency of the process, it is recommended to make an effort into utilizing the filtration system to its full extent.

14th International Summer School on Crystal Growth ( 1–7 August 2010, Dalian (China))

<p>An essential ingredient in the generation of environmentally compatible pulp bleaching chemicals is sodium chlorate. Chlorate is produced in electrochemical cells, where the electrodes are the key components. In Sweden the so-called DSA !R electrodes with catalytic coatings have been produced for more than 35 years. The production of chlorate uses a large amount of electric energy, and a decrease of just five percent of this consumption would, globally, decrease the consumption of electrical energy corresponding to half a nuclear power reactor. The aim of this project is to improve the electrode design on the nanoscale to decrease the energy consumption. The success of the DSA!R depends on the large catalytic area of the coating, however, little is known about the actual structure at the nanometer level. To increase the understanding of the nanostructure of these coatings, we used a number of methods, including atomic force microscopy, transmission electron microscopy, X-ray diffraction, porosimetry, and voltammetric charge. We found that the entire coating is built up of loosely packed rutile mono-crystalline 20 − 30 nm sized grains. The small grain sizes give a the large area, and consequently, lower cell-voltage and reduced energy consumption. A method to control the grain size would thus be a way to control the electrode efficiency. To alter the catalytically active area, we made changes in the coating process parameters. We found a dependency of the crystal-grain sizes on the choice of ruthenium precursor and processing temperature. The use of ruthenium nitrosyl nitrate resulted in smaller grains than ruthenium chloride and lowering the temperature tended to favour smaller grains. A more radical way would be to create a totally different type of electrode, manufactured in another way than using the 1965 DSA !R recipe. Such new types of electrodes based on, for example, nanowires or nanoimprint lithography, are discussed as future directions.</p>

An essential ingredient in the generation of environmentally compatible pulp bleaching chemicals is sodium chlorate. Chlorate is produced in electrochemical cells, where the electrodes are the key components. In Sweden the so-called DSA !R electrodes with catalytic coatings have been produced for more than 35 years. The production of chlorate uses a large amount of electric energy, and a decrease of just five percent of this consumption would, globally, decrease the consumption of electrical energy corresponding to half a nuclear power reactor. The aim of this project is to improve the electrode design on the nanoscale to decrease the energy consumption. The success of the DSA!R depends on the large catalytic area of the coating, however, little is known about the actual structure at the nanometer level. To increase the understanding of the nanostructure of these coatings, we used a number of methods, including atomic force microscopy, transmission electron microscopy, X-ray diffraction, porosimetry, and voltammetric charge. We found that the entire coating is built up of loosely packed rutile mono-crystalline 20 − 30 nm sized grains. The small grain sizes give a the large area, and consequently, lower cell-voltage and reduced energy consumption. A method to control the grain size would thus be a way to control the electrode efficiency. To alter the catalytically active area, we made changes in the coating process parameters. We found a dependency of the crystal-grain sizes on the choice of ruthenium precursor and processing temperature. The use of ruthenium nitrosyl nitrate resulted in smaller grains than ruthenium chloride and lowering the temperature tended to favour smaller grains. A more radical way would be to create a totally different type of electrode, manufactured in another way than using the 1965 DSA !R recipe. Such new types of electrodes based on, for example, nanowires or nanoimprint lithography, are discussed as future directions.

Actuellement le polyéthylènimine (PEI) est l’agent de transfection transitoire le plus utilisé par l’industrie pharmaceutique pour la production de protéines recombinantes à grande échelle par les cellules de mammifères. Il permet la condensation de l’ADN plasmidique (ADNp) en formant spontanément des nanoparticules positives appelées polyplexes, lui procurant la possibilité de s’attacher sur la membrane cellulaire afin d’être internalisé, ainsi qu’une protection face aux nucléases intracellulaires. Cependant, alors que les polyplexes s’attachent sur la quasi-totalité des cellules seulement 5 à 10 % de l’ADNp internalisé atteint leur noyau, ce qui indique que la majorité des polyplexes ne participent pas à l’expression du transgène. Ceci contraste avec l’efficacité des vecteurs viraux où une seule particule virale par cellule peut être suffisante. Les virus ont évolués afin d’exploiter les voies d’internalisation et de routage cellulaire pour exprimer efficacement leur matériel génétique. Nous avons donc supposé que l’exploitation des voies d’internalisation et de routage cellulaire d’un récepteur pourrait, de façon similaire à plusieurs virus, permettre d’optimiser le processus de transfection en réduisant les quantités d’ADNp et d’agent de transfection nécessaires. Une alternative au PEI pour transfecter les cellules de mammifèreest l’utilisation de protéines possédant un domaine de liaison à l’ADNp. Toutefois, leur utilisation reste marginale à cause de la grande quantité requise pour atteindre l’expression du transgène. Dans cette étude, nous avons utilisé le système E/Kcoil afin de cibler un récepteur membranaire dans le but de délivrer l’ADNp dans des cellules de mammifères. Le Ecoil et le Kcoil sont des heptapeptides répétés qui peuvent interagir ensemble avec une grande affinité et spécificité afin de former des structures coiled-coil. Nous avons fusionné le Ecoil avec des protéines capables d’interagir avec l’ADNp et le Kcoil avec un récepteur membranaire que nous avons surexprimé dans les cellules HEK293 de manière stable. Nous avons découvert que la réduction de la sulfatation de la surface cellulaire permettait l’attachement ciblé sur les cellules par l’intermédiaire du système E/Kcoil. Nous démontrons dans cette étude comment utiliser le système E/Kcoil et une protéine interagissant avec l’ADNp pour délivrer un transgène de manière ciblée. Cette nouvelle méthode de transfection permet de réduire les quantités de protéines nécessaires pour l’expression du transgène. / Pharmaceutical industry often employs polyethylenimine (PEI) for large scale protein production processes by transient transfection of mammalian cells. PEI condenses plasmid DNA (pDNA) by spontaneously forming positive nanoparticles known as polyplexes. Condensed pDNA is favoured for cell surface binding, internalization and protection from intracellular nucleases. While most of the cells efficiently uptake polyplexes, only 5 to 10% of captured pDNA reaches the nucleus for transgene expression. This suggests that polyplexes are hampered in their ability to route and to translocate to the nucleus necessitating large amounts of polyplexes to achieve high expression levels. By contrast, many viruses can efficiently transduce cells with only one or a few viral genome copies. Viruses have evolved to exploit cellular internalization and routing properties to express their own genetic material. We hypothesized that less pDNA would be used in an optimized transfection process if we exploited the internalization and routing properties that viruses use. DNA binding proteins could be used as an alternative to PEI to transfect mammalian cells. However, their usage is marginal due to the large protein quantities required to bind pDNA for transgene expression. If less pDNA is used less binding protein is needed. In this study, we used the E/Kcoil system to target a membrane receptor to deliver pDNA in mammalian cells. The Ecoil and Kcoil are two repeated heptapeptides which interact with a high affinity and specificity to form coiled-coil structures. We fused the Ecoil with a recombinant pDNA-binding protein. The Kcoil was fused to a stably-expressed membrane receptor in HEK293 cells. We discovered that low sulfation of the cell surface reduced non-specific binding of the pDNA:protein complex and permitted targeted binding via the E/Kcoil interaction. We demonstrate how to use recombinant pDNA-binding protein and the E/Kcoil system for targeted transgene delivery. This newly developed system provides a new transfection method, with reduced pDNA-binding protein quantities needed to achieve transgene expression.