Chlorine as a chemical is widespread in industry and found in a great variety of processes ranging from water purification to plastic production. In this thesis, a magnesium production factory was chosen as an example because it involved both chlorine - air separation and hydrogen –hydrogen chloride separation. Previously, various types of membrane materials have been tested out for their applicability in the chosen process. The materials previously tested either lacked sufficient membrane performance or sufficient membrane stability. As an attempt to improve both the membrane performance and stability, glass membranes are used in this thesis. Glass membranes are prepared from a borosilicate glass, via a phase separation followed by an acid leaching route. By choosing the appropriate phase separation temperature and acid to glass ratio, the membrane can be produced with an average pore diameter of 2 nm (or 4 nm). However, the 2 nm average pore size is still too large to separate gases with separation selectivities beyond the selectivities predicted from Knudsen diffusion theory. If the pores are narrowed, the selectivity may be raised while the flux hopefully is maintained. The narrowing of the pores was done by a silane coupling to the surface OH-groups on the glass. The silane coupling agent is of the dimethylacyl-chlorosilane type, where the length of the acyl chain varies from 1 carbon up to 18 carbons. Glass fibres are also tested in this work, which are produced without phase separation and their average pore size is smaller than the surface-modified glasses. To be able to compare the performance of the various membranes, permeance measurements are performed and these measurements are evaluated by the separation power (product of the selectivity and the permeability of the fastest permeating compound). Because of the harsh chlorine or hydrogen chloride environment, to which the membranes are exposed in this work, the membrane stability is at least as important s factor as the perm-selectivities. To evaluate this, both short- and longterm aggressive gas exposures are performed using a special designed durability chamber. From the combination of the perm-selectivities and the durability tests, the following conclusions may be drawn (evaluated at 30°C and 1 bar): Firstly, the pure glasses have a relatively poor stability (for chlorine gas) and the perm-selectivity is too low (for both separations in question). Secondly, the C8 and C12 modified glass membranes have a relatively satisfactory perm- selectivity for chlorine separation, but the durability in chlorine is poor. Thirdly, the long-chained C18 modified glass membrane has a relatively satisfactory perm-selectivity but a fair to low chlorine stability. If the C18 membrane is applied in the hydrogen chlorine separation the perm-selectivity is a bit low, but the stability is sufficient. However, this membrane is the best choice for a low temperature HCl selective membrane. Finally, to improve the chlorine stability, a perfluorinated version of a C1 modification is tried out. This membrane has excellent chlorine stability, and the perm-selectivity is fair. This membrane is the best choice for a chlorine selective membrane. The stability of the fibres is comparable to that found for the pure glass tubes. However, the permeabilities in the glass fibres are several orders of magnitude lower than for the glass tubes. The pore size in the fibre is so narrow that separation occurs according to a molecular sieving mechanism. The mounting of the fibres into a labsized module is tricky and the permeabilities are at the border of detection, so the results obtained here should only serve as trends.

Carbon nanofibers (CNFs) and carbon nanotubes (CNTs) have attracted intense research efforts with the expectation that these materials may have many unique properties and potential applications. The most promising way for large-scale synthesis of CNFs and CNTs is chemical vapor deposition (CVD). CNFs were synthesized on a series of hydrotalcite (HT) derived 77 wt.% Ni-Fe/Al2O3 catalysts in order to achieve the optimization of productivity and quality. It was found that only the Fe catalyst was active in CO disproportionation and only the Ni catalyst was active in ethylene decomposition, whereas all catalysts were active in ethylene decomposition when the reactants were a mixture of C2H4/CO. More control over the structure and diameter of the CNFs has been realized with the HT catalysts. At the same time, a high yield can be obtained. The synthesis process has been further studied as a function of various process parameters. It turned out that high hydrogen concentration, space velocity, and reaction temperature would enhance the production of CNFs. However, a slightly lower quality was associated with the higher productivity. The optimum CNF yield of 128 gCNF/gcat could be reached within 8 h on the HT catalyst with a Ni/Fe ratio of 6:1. Therefore, HT derived catalysts present a new promising route to large-scale controlled synthesis of CNFs. CNTs has been synthesized from CO disproportionation on Ni-Fe/Al2O3 supported catalysts with metal loadings of 20 and 40 wt.%. A high space velocity resulted in a high production rate but a short lifetime and a low carbon capacity. Increasing the metal loading to 40 wt.% significantly increased the reaction rate and productivity, and produced similarly uniform CNTs. Furthermore, H2 was found to be necessary for a high productivity, and the H2 partial pressure could be changed to adjust the orientation angle of the graphite sheets. The effects of catalyst particle size and catalyst support on the CNT growth rate during CO disproportionation were studied over SiO2 and Al2O3 supported Fe catalysts with varying particle sizes. It was found that there was an optimum particle size at around 13-15 nm for the maximum growth rate, and the growth rate was influenced both by the particle size and the support but the particle size was the dominating factor. The trends have been demonstrated at two different synthesis temperatures of 600 and 650°C. The effect of gas precursors on the yield and structure of carbon growth has been systematically investigated over powder Fe and Fe/Al2O3 catalysts. CO/H2, CO, CH4, and C2H6/H2 were the gas precursors studied. The carbon yield was higher on powder Fe from CO, but the yield was higher on Fe/Al2O3 from hydrocarbons. Completely different or similar carbon nanostructures were synthesized, depending on the gas precursors. It was suggested that the reactivity of gas precursors and the structures of carbon deposits are determined by the size and crystallographic faces of the catalyst particles, which are dictated by the interactions among metal particles, support, and the reactants. Controlled synthesis of CNT, platelet nanofiber, fishbone-tubular nanofiber, and onion-like carbon with high selectivity and yield was realized. A mechanism was proposed to illustrate the growth of different carbon nanostructures.

Diffusion into the rock matrix has been identified as one of the most important retention mechanisms for dissolved contaminants in fractured crystalline rock. In this thesis the diffusive properties of granitic rock, described by the formation factor, have been investigated by electrical methods. These methods are based on the Einstein relation between diffusivity and ionic mobility. Formation factors have been obtained both in the laboratory and in deep lying rock in-situ. At present, two locations in Sweden, Forsmark and Oskarshamn, are undergoing site investigations for the siting of a repository for spent nuclear fuel. As a part of these investigations, the formation factor of the rock surrounding five, 1000 m deep boreholes has been investigated. More than 250 rock samples, taken from the bore cores, have been investigated in the laboratory and around 50 000 formation factors have been obtained in-situ. The results have been treated statistically and it appears that the formation factor is lognormally distributed. The mean and standard deviation of the obtained log-normal distributions vary from site to site, depending on the geology. For intact granitic rock, the obtained formation factors range between 2.2·10-7 and 2.5·10-2. The results suggest that diffusion into open, but hydraulically non-conductive fractures may have a significant influence on radionuclide retention by way of increasing it. Therefore, the fractured rock formation factor was introduced in addition to the traditional rock matrix formation factor. The retardation capacity of crystalline rock is strongly associated with the pore connectivity. In this thesis, it is shown that the micropore network of granitic rock is connected on, at least, a metre scale in-situ. / QC 20101019

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QC 20110104

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<p><strong>Abstract</strong></p><p> </p><p>This exam project is an effort to derivatize one side of magnetic beads with one kind of molecule  , and another one on the opposite side. First the surface of the sphere is loaded with a suitable linker with, e.g. amino or hydroxyl groups. In the second step, these groups are derivatized with a photosensitive protecting group such as Nitroveratryloxycarbonyl. In the third step, the particles are placed on a surface and then irradiated with UltraViolet light (320 nm) from above, which will cleave off the Nitroveratryloxycarbonyl on the upper half, while leaving in place the ones at the lower half. The linker groups of the upper half can now be derivatized by other reagents of choice. The remaining Nitroveratryloxycarbonyl groups can be removed by suspending the particles in a solvent and then exposing them to UltraViolet light. Finally the linker groups on this half of the particles can be derivatized by a second reagent.</p><p>Magnetic particles were marked with FITC, two different kinds of magnetic particles were selected, sikastar-NH2 function and sikastar-COOH function. Five different solvents were used to wash the magnetic particles and remove the bounded FITC, solvents are Acetone, 1-butanol, DMSO, 4-propanol, and Urea. Magnetic particles sikastar-NH2 and sikastar-COOH were washed with Tween 20 and SDS to remove non-specific binding of FITC. Sikastar particles were treated with IgG*FITC in constant presence of the following solvents: PBS*10, Pluronic-F127, Tween 20. Pegylation of sikastar particles got done to reduce non-specific binding. Derivatisation of Nitroveratryloxycarbonyl got done and specific bindning of IgG*FITC to micromer particles got done by protein thiolation.</p><p>When a different concentration of FITC was tested to control specific and non-specific binding to sikastar functions, we observed that we had a specific binding to sikastar-NH2 in the lowest concentration. In choice of magnetic particles we had specific binding with sikastar-NH2.<strong> </strong>Using a different solvents Acetone, 1-butanol, 4-propanol, and Urea  to remove bounded FITC, sikastar-NH2 showed stronger fluoresence than sikastar-COOH after washing because of specific binding and it was difficult to remove FITC with Acetone, 1-butanol,  4-propanol,and Urea, on the other hand DMSO could remove bounded FITC from sikastar particles. When we washed magnetic particles sikastar-NH2 and sikastar-COOH with Tween 20 and SDS to remove non-specific binding of FITC, we could see that magnetic particles showed fluoresence in both functions due to non-specific binding. When sikastar particles got treated with IgG*FITC in constant presence of solvents PBS*10, Pluronic-F127, and Tween 20, we had a specific binding between sikastar particles and IgG*FITC in a presence of pluronic-F127. Pegylation of sikastar particles with a different kind of a PEG was possibl to reduce non-specific bindning. The derivatisation of Nitroveratryloxycarbonyl could be done in a N2 environment, and Nitroveratryloxycarbonyl-sikastar-NH2 could be radiated with UltraViolet light to remove Nitroveratryloxycarbonyl. Also thiolation method could be used to perform specific binding of IgG*FITC to micromer particles.<strong></strong></p>

Att ha en låg mätosäkerhet på en analysmetod är otroligt viktigt. Målet med den härstudien var därför att utveckla och förbättra den metod som BillerudKorsnäs AB använderidag för att bestämma kantinträngning av vätska i kartong. Det skulle utföras genom attse över de parametrar som finns i metoden och på så sätt försöka förbättra några av dessa.Först utfördes några försök med den metod som BillerudKorsnäs AB använder sig av föratt mäta kantinträngning och dessa resultat kunde användas som referensprover. Enparameter i taget varierades för att försöka minska mätosäkerheten. Det som bl.a.testades var att rengöra giljotinen oftare som användes för att skära ut proverna. En korgmed gummisnoddar istället för den nuvarande korgen med buntband samt en ny korgtestades. Kaffeblandningen som BillerudKorsnäs AB använder som testlösning testadesatt bytas ut mot tensid med ättiksyra i samt olika koncentrationer med diskmedel, och enkoncentration med diskmedel och karamellfärg. Slutligen plottades några andraegenskaper som mättes på kartongen mot kantinträngningen för att ta reda på om någotsamband kunde ses. Det visade sig att mätosäkerheten minskade när giljotinenrengjordes oftare samt när den nya korgen användes. Tensid med ättiksyra kunde inteersätta kaffeblandningen eftersom att lösningen behövde ett betydligt lägre pH änkaffeblandningen. Diskmedel med karamellfärg gav en väldigt låg mätosäkerhet ochskulle därför kunna ersätta kaffeblandningen om fler försök undersöks, i syfte att se omde korrelerar. Det kunde ses att ytvikten på 170 g/m2 stack ut något mot de övrigaytvikterna, annars kunde inget samband ses mellan andra egenskaper som mättes påkartongen och kantinträngningen.

Feruloyl esterases (FAEs, EC 3.1.1.73) represent a subclass of carboxylic acid esterases that under normal conditions catalyze the hydrolysis of the ester bond between hydroxycinnamic acids (ferulic acid, sinapic acid, caffeic acid, p-coumaric acid) and arabinose residues in plant cell walls. Based on their specificity towards monoferulates and diferulates, substitutions on the phenolic ring and on their amino acid sequence identity, they have been classified into four types (A-D). The use of FAEs as accessory enzymes for the degradation of lignocellulosic biomass and their synergism with other hemicellulases has been studied for application in many industries, such as the food, the biofuel and the paper pulp industry. In the recent years, the use of FAEs as biosynthetic tools has been underlined. Under low water content, these enzymes are able to catalyze the esterification of hydroxycinnamic acids or the transesterification of their esters resulting in compounds with altered lipophilicity, revealing a great potential for tailor-made modification of natural antioxidants for use in cosmetic, cosmeceutical and pharmaceutical industries. The first part of the thesis is focused on the optimization of reaction conditions for the synthesis of two bioactive esters: prenyl ferulate and L-arabinose ferulate using 5 FAEs (FaeA1, FaeA2, FaeB1, FaeB2 and MtFae1a) from Myceliophthora thermophila in detergentless microemulsions. Reaction conditions were optimized investigating parameters such as the medium composition, the substrate concentration, the enzyme load, the pH, the temperature and the agitation. Regarding the synthesis of prenyl ferulate, FaeB2 offered the highest transesterification yield (71.5±0.2%) after 24 h of incubation at 30oC using 60 mM vinyl ferulate (VFA), 1 M prenol and 0.02 mg FAE/mL in a mixture comprising of 53.4: 43.4: 3.2 v/v/v n-hexane: t-butanol: 100 mM MOPS-NaOH pH 6.0. At these conditions, the competitive hydrolysis was 4-7 fold minimized. Regarding the synthesis of L-arabinose ferulate, FaeA1 offered highest transesterification yield (35.9±2.96%) after 8 h of incubation at 50oC using 80 mM VFA, 55 mM L-arabinose and 0.02 mg FAE/mL in a mixture of 19.8: 74.7: 5.5 v/v/v n-hexane: t-butanol: 100 mM MOPS-NaOH pH 8.0. It was revealed that the type B FAEs from M. thermophila show higher preference to more lipophilic acceptors like prenol, while the type A FaeA1 was more efficient in the synthesis of the more hydrophilic L-arabinose ferulate. The second part of the thesis is focused on the investigation of the basis of the type A classification of a well-studied FAE from Aspergillus niger (AnFaeA) by comparing its activity towards methyl and arabinose hydroxycinnamate esters. For this purpose, L-arabinose ferulate and caffeate were synthesized enzymatically. kcat/Km ratios revealed that AnFaeA hydrolyzed arabinose ferulate 1600 times and arabinose caffeate 6.5 times more efficiently than methyl esters. This study demonstrated that short alkyl chain hydroxycinnamate esters which are used nowadays for FAE classification can lead to activity misclassification, while L-arabinose esters could potentially substitute synthetic esters in classification.