>Magister Scientiae - MSc / Most of the world's energy production is still mainly achieved by the combustion of coal in power stations. Coal fly ash is the inevitable waste product that accumulates to metric ton volumes each year. These vast volumes pose a problem in the disposal of the coal fly ash which conventionally is loaded onto ash dumps located near the coal power stations. Alternatives need to be investigated for the use of the coal fly ash in applications that would make the coal fly ash useful and thereby help to mitigate the environmental strain imposed by conventional ash dump disposal. This study focussed on investigating the extraction of Si and Al from CFA. The investigation into the removal of the magnetic iron oxide content and calcium content from coal fly ash was also carried out to enhance the extraction of the Si and Al from CFA e.g. the removal of calcium was attempted to promote the leaching of aluminium from the ash. The rationale for this process was that by removing and recovering these major constituent elements from the ash, it would be easier to concentrate and isolate the trace elements especially the rare earth elements that are present in the CFA. Coal fly ash sourced from Matla coal power station was characterised using x-ray diffraction to determine the mineral phases present in the raw coal fly ash and elemental composition determined by x-ray fluorescence and laser ablation ICP-MS. The main mineral phases in coal fly ash were determined to be quartz, mullite, magnetite and lime (CaO). Magnetic extraction was initially carried out on the coal fly ash to remove the iron rich magnetic material. Extraction tests were then performed on the coal fly ash using alkaline and acidic media namely; NaOH, HCl and H₂SO₄. The extraction tests were assessed and a sequential extraction experimental procedure developed to achieve the highest extraction yield for Si, Al, Fe, Ca, and Mg from the coal fly ash. Lastly the rare earth element content in coal fly ash was tracked from the beginning till the end of the sequential extraction procedure to ascertain whether the rare earth elements partitioned to the leachates or the solid residues. The total element recoveries for Al, Si, Ca Fe, Mg were 53.36 %, 39.96 %, 93.8 %, 25.6 % and 67.3 % respectively using the sequential extraction procedure developed in this study. The rare earth elements contents were not affected by the sequential extraction procedure and on the whole remained in the solid residues at the completion of the sequential extraction, resulting in a residue with enriched levels of recoverable or extractable REE content after the removal of the major oxides from the CFA. The lowest enrichment being approximately 5 % for Thulium and the highest being approximately 76 % for Erbium.

Radioimmunotherapy (RIT) and radioimmunolocalisation (RIL) are developing and promising technologies to diagnose and treat tumours by use of radiolabelled antibodies targeting tumour specific antigens. The major reason why RIL and RIT not are efficient enough, is the comparatively low accumulation of radiolabelled antibodies in the tumours. Irrespective of the antigen - antibody system used, the maximal tumour uptake in humans is often limited to below 0.1 % of the total injected dose, with significant radionuclide remaining in the blood pool and extravascular fluid. In the present thesis, the following putative improvement techniques for radioimmunotargeting have been evaluated in an experimental model using HeLa cell-xenografted nude mice: 1) Repetitive, simultaneous targeting of different antigens, 2) Removal of non-targeting antibodies using secondary antiidiotypic antibodies, 3) Preinjection of unlabelled antibody to remove shedded antigen and 4) Use of fractionated antibody administration. By use of multiple injections of mixtures of two different 131I-labelled monoclonal antibodies targeting placental alkaline phosphatase (H7) and cytokeratin 8 (TS1), respectively, a significant tumour growth inhibition compared to controls, was obtained. In the treated group, a negligible increase in tumour volume was seen compared to the control group, in which a 20-fold increase was observed. Quantitative determinations of volume densities of viable tumour cells, necrotic cells and connective tissue demonstrated no significant differences in the relative proportions between the groups, indicating that the irradiation caused decelerated growth. Using hybridoma technology, monoclonal antiidiotypic antibodies were generated against both TS1 and H7. The in vitro and in vivo effects of these antibodies, aH7 and aTSl, were investigated. Both these antiidiotypes were found to generate stable complexes with the radiolabelled idiotypic antibody, as revealed by gel-electrophoresis and autoradiography. Using biosensor technology (BIAcore, Pharmacia) the interactions were followed in real time and the association rate-, dissociation rate-, and affinity constants between the reactants were determined. In vivo, the antiidiotypes promoted a rapid dose dependent clearance of the 125I-labelled idiotypes with a decrease in total body radioactivity and concomitant dramatic increase in non-protein bound 125I excreted in the urine. The syngeneic monoclonal antiidiotypic antibody αTSl, was furthermore evaluated as a secondary clearing antibody at radioimmunolocalisation. Injection of αTSl in a molar ratio of 0.5-0.75:1 to TS1, 24 hours after the 125I-labelled TS1 improved the tumour to normal tissue ratio 2-3 fold. This was due to a decreased level of total body radioactivity as well as a slight decrease in tumour-radioactivity. A model describing the kinetics of the involved components, i.e. the antigen, the idiotype and the antiidiotype was presented. It is concluded that high affinity monoclonal antiidiotypes can be used as tools to regulate the levels of idiotypic antibodies in vivo. This strategy, combined with preinjection of non­labelled idiotypic antibodies, caused accumulated doses of 3 Gy to the tumour and 0.9 Gy to non tumour tissues as calculated for 125I-labelled antibodies (80 MBq/mg) by MIRD formalism based on repetitive quantitative radioimmunoscintigraphies. By approaching the maximal tolerated whole body radiation dose for mice (i.e. 6 Gy), it can be estimated that doses up to 20 Gy are possible to obtain following one single injection of labelled antibody. It was furthermore demonstrated that a single bolus injection of antibody is to be preferred, compared to exactly the same dose divided into three or ten fractions. Thus, not only the dose of radioactivity, but also the amount of antibody should be considered for fractionated RIT. In summary, the thesis demonstrates that several techniques can be used to improve radioimmunolocalisation and to approach the proposed 70 Gy required to sterilise tumours at radioimmunotherapy. / digitalisering@umu.se

There is an increasing demand for DNA analysis because of the sensitivity of the method and the ability to uniquely identify and distinguish individuals with a high degree of certainty. But this demand has led to huge backlogs in evidence lockers since the current DNA extraction protocols require long processing time. The DNA analysis procedure becomes more complicated when analyzing sexual assault casework samples where the evidence contains more than one contributor. Additional processing to separate different cell types in order to simplify the final data interpretation further contributes to the existing cumbersome protocols. The goal of the present project is to develop a rapid and efficient extraction method that permits selective digestion of mixtures. Selective recovery of male DNA was achieved with as little as 15 minutes lysis time upon exposure to high pressure under alkaline conditions. Pressure cycling technology (PCT) is carried out in a barocycler that has a small footprint and is semi-automated. Typically less than 10% male DNA is recovered using the standard extraction protocol for rape kits, almost seven times more male DNA was recovered from swabs using this novel method. Various parameters including instrument setting and buffer composition were optimized to achieve selective recovery of sperm DNA. Some developmental validation studies were also done to determine the efficiency of this method in processing samples exposed to various conditions that can affect the quality of the extraction and the final DNA profile. Easy to use interface, minimal manual interference and the ability to achieve high yields with simple reagents in a relatively short time make this an ideal method for potential application in analyzing sexual assault samples.

In the past decade, the field of NMR spectroscopy has seen the emergence of ever more powerful superconducting magnets, which has opened the door for the observation of many traditionally challenging or non-receptive nuclei. In this dissertation, a variety of ionic solids with organic coordination environments are investigated using quadrupolar solid-state NMR experiments with an ultrahigh-field magnet (21.1 T). Two general research directions are presented including a 79/81Br solid-state NMR study of a series of 6 triphenylphosphonium bromides for which single-crystal X-ray structures are reported herein. A second research direction is also presented wherein alkaline-earth metal (25Mg, 43Ca, and 87Sr) solid-state NMR is used to characterize a systematic series of 16 aryl and alkyl carboxylates. In both studies, the quadrupolar nuclei studied are deemed “exotic” due to their unreceptive nature to NMR spectroscopic analysis including low natural abundances, large quadrupole moments, or low resonance frequencies. A variety of coordination modes to alkaline-earth metals, including N-atom coordination, are characterized herein for the first time using alkaline-earth metal solid-state NMR. In all cases, the electric field gradient (EFG) and chemical shift (CS) tensors are characterized and correlated to structural features such as interatomic distances measured from the crystal structure of the compound under study. In all of the projects undertaken herein, the gauge-including projector-augmented-wave density functional theory (GIPAW DFT) method is used, which allows for the prediction and rationalization of the experimental EFG and CS tensor parameters based on the input crystal structure. In the case of 43Ca solid-state NMR experiments reported in this dissertation, a linear correlation between the calculated and experimental 43Ca quadrupolar coupling constants, CQ, is used as a calibration curve for GIPAW DFT calculations performed on the 18 structural models currently available for the vaterite polymorph of CaCO3. Vaterite cannot be fully characterized by X-ray diffraction alone; therefore an NMR crystallography protocol is used in order to identify the model that best accounts for 43Ca solid-state NMR experiments performed on vaterite. It is expected that the conclusions from this dissertation can be used for future studies involving structural refinement and elucidation of solid materials containing challenging quadrupolar nuclei.

Fuel cells represent a promising technology for clean power generation because they convert chemical energy (fuel) into electrical energy with high efficiency and low-to-none emission of pollutants. Direct ethanol fuel cells (DEFCs) have several advantages compared to the most studied hydrogen and methanol fuel cells. First and foremost, ethanol is a non-toxic liquid, which lowers the investment of handling facilities because the current infrastructure for gasoline can be largely used. Second, ethanol can be conveniently produced from biomass, hence is carbon neutral which mitigates increasing atmospheric CO2. Last but not least, if completely oxidized to CO2, ethanol has a higher energy density than methanol since it can deliver 12 electrons per molecule. The almost exclusive oxidation to acetic acid overshadows the attractiveness of DEFCs considerably, as the energy density is divided by 3. The standard potential of acetic acid formation indicates that a reaction path including acetic acid, leads to inevitable potential losses of about 0.4 V (difference between ideal potential for CO2 and acetic acid "production"). The development of alkaline DEFCs had also been hampered by the lack of stable and efficient anion exchange membranes. Fortunately, this challenge has been well tackled in recent years,8,9 making the development of alkaline fuel cells (AFCs) which are of particular technological interest due to their simple designs and ability to operate at low temperatures (25-100 °C). In alkaline conditions, the kinetic of both the cathodic oxygen reduction and the anodic ethanol oxidation is facilitated. Furthermore, the expensive Pt catalyst can be replaced by the lower-cost and more active transition metals such as Pd. The main objectives of this project are: i) to provide detailed fundamental understanding of ethanol oxidation reaction on transition metal surfaces in alkaline media, ii) to propose the best rational catalyst design strategies to cleave the C–C bond during ethanol electrooxidation. To achieve these goals two methodologies are used, i.e., in-situ identification of ethanol electrooxidation products using polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) and mechanistic investigation using computational studies in the framework of density functional theory (DFT). The PM-IRRAS technique was advanced in this project to the level of distinguishing electrooxidation products at the surface of the nanoparticles (electrode) and in the bulk-phase of the electrolyte. This new PM-IRRAS utility makes it possible to detect molecules such as CO2 which desorbs from the catalyst surface as soon as they are formed. The DFT insights in this project, provides an explanation as to why it is difficult to break the C–C bond in ethanol and is used for screening the top candidate metals for further studies.

La chimie des métaux alcalino-terreux lourds (calcium, strontium et baryum) a longtemps été décrite comme difficile et imprévisible contrairement à la chimie du magnésium, leur plus léger congénère. Cependant, au cours des dernières décennies, de nombreux complexes basés sur ce type de métaux ont émergés en tant que précatalyseurs efficaces pour un grand nombre de transformations organiques (polymérisation, hydroélémentation, couplage déshydrogénants, etc..). Cette thèse décrit la synthèse et l’étude (expérimentale et théorique) de nouveaux complexes de baryum de basse coordinance basée sur l’utilisation de ligands alcoolates pauvres en électrons. L’étude de ces composés a permis d’améliorer notre compréhension des différents phénomènes nécessaires à la stabilisation de tels composés. Dans un second temps, deux nouveaux systèmes de couplages déshydrogénants BO‒H/H‒Si et SiO‒H/H‒Si ont été développés et étudiés. Ces systèmes ont permis la formation catalytique de borasiloxanes et de siloxanes dissymétriques de façon sélective. Enfin, ces travaux montrent la synthèse et l’utilisation de nouveaux ligands ancillaires pour la formation de complexes hétéroleptiques de baryum stables. Ces derniers ont démontré une forte activité catalytique en hydrophosphination intermoléculaire avec des TOF pouvant atteindre 200 h-1 pour l’hydrophosphination du styrène par la HPPh2. / Heavy alkaline earth metals chemistry (calcium, strontium and barium) has been described as difficult and unpredictable for a long time, unlike the chemistry of magnesium, their lightest congener. However, in the last decades, many complexes based heavy alkaline earth metals have emerged as effective precatalysts for many applications and organic transformations (polymerization, hydroelementation, dehydrogenating coupling, etc.). This thesis describes the synthesis and study (experimental and theoretical) of new low-coordinate barium complexes based on electron-poor alkoxide ligands. The study of these compounds has improved our understanding of the different phenomena required to stabilize such compounds. Then, two new dehydrocoupling systems BO-H/H-Si and SiO-H/H-Si were developed and studied. These systems have allowed the catalytic formation of borasiloxanes and asymmetric siloxanes in a selective manner. Finally, this work shows the synthesis and use of new ancillary ligands for the formation of stable heteroleptic barium complexes. The latter have demonstrated strong catalytic activity in hydrophosphination with TOFs up to 200 h-1 for the intermolecular hydrophosphination of styrene by HPPh2.

>Magister Scientiae - MSc / Palladium can be used as an anodic catalyst for the alkaline direct alcohol fuel cells (ADAFCs). Palladium has displayed high tolerance towards carbon monoxide (CO) poisoning and high catalytic activity for alcohol oxidation reaction in alkaline medium. Palladium-based catalysts have arisen as an alternative to performing alcohol oxidation reaction, especially when combined with other transition metals and multi walled carbon nanotubes (MWCNT) as a support, which induces changes in the palladium electronic structure, and thus, increasing its activity. This research is focused on the development of palladium catalysts incorporated with nickel and tin (transitional metals) on multi walled carbon nanotubes for alkaline direct glycerol fuel cells.

This diploma thesis is focused on the use of wheat bran as a raw material for extraction of arabinoxylans. Wheat bran is a waste product of mill processing of wheat into flour and is mainly used as a livestock feed. However, the amount of bran produced significantly exceeds its consumption as feed, which opens up space for research into their further use. Polysaccharides such as cellulose, hemicelluloses and lignin are mainly present in the bran. The most common type of hemicelluloses are arabinoxylans, which form the main structural component of wheat bran. Alkaline extraction disrupts hydrogen and covalent bonds and releases polysaccharides of various molar weights from the crosslinked cell wall structure. Hydrolysis is required to obtain arabinose and xylose. Trifluoroacetic acid was chosen for the hydrolysis. The acid breaks down glycosidic bonds of the poly- and oligosaccharides to give the corresponding monosaccharides. The experiments made during this thesis have shown that the yield of multi stage extraction is twice as high as the yield of single stage extraction. Hydrolysis of the solid fractions after alkaline extraction revealed that a relatively large amount of arabinoxylans and other carbohydrates still remain bound in the complex matrix of the bran cell wall. Thus, alkaline extraction alone may not be the best option for obtaining arabinoxylans on a larger scale, or process optimization must be considered. Extraction with the addition of hydrogen peroxide appears to be effective for large-scale extraction processes.

Předložená diplomová práce se zabývá přípravou hydrogelů odvozených od polyakrylonitrilu a charakterizací jejich fyzikálních a chemických vlastností. Teoretická část shrnuje základní poznatky z oblasti hydrogelů, a také o polyakrylonitrilu. Dále se zabývá možností zpracování polyakrylonitrilu do reaktivní formy, takzvaného aquagelu a jeho zásadité hydrolýzy za účelem přípravy multi-blokových kopolymerů schopných tvořit 3D síť (gel). Experimentální část prezentuje výsledky charakterizace hydrogelů z polyakrylonitrilu neboli HYPANů, které byly připraveny bazicky katalyzovanou hydrolýzou aquagelu. Aquagel byl připraven rozpuštěním a následnou extruzí polyakrylonitrilu. Vzniklé vlákno bylo zpracováno do formy pelet, které byly dále užity pro zmiňovanou hydrolýzu. Hydrolýza byla prováděna za různých podmínek (teplota, NaOH koncentrace, reakční čas) za účelem přípravy produktů s různým stupněm konverze -CN skupiny. Hydrolýzou vytvořené hydrofóbní a hydrofilní bloky, mohou zformovat 3D síť o různých vlastnostech, závisejících na poměru mezi počtem a délkou bloků. Z hydrolyzátů byly připraveny hydrogely jejichž visko-elastické a optické vlastnosti byly dále charakterizovány. Optimalizací přípravy bylo dozaženo multi-blokového kopolymeru schopného vytvořit gel s vhodnými fyzikálními vlastnostmi. Tento gel může najít uplatnění v medicíně, například jako implantáty v oftamologii.

In this work the influence of alkaline activator on immobilization of lead and copper in alkali-activated blast furnace slag was investigated. A total of five activators were used; sodium water glass, potassium water glass, sodium hydroxide, potassium hydroxide and sodium carbonate. The leaching test according to ČSN EN 12457-4 was used to evaluate the level of immobilization of heavy metals, the leached solutions were analyzed by ICP-OES. For a better understanding of immobilization, the selected samples were characterized by analytical methods (FTIR, XRD, SEM, XPS). It was found that the degree of immobilization Pb2+ and Cu2+ in AAS was very high, regardless of the type of alkaline activator used.