Methane activation with bromine followed by the condensation of the methyl bromide into higher hydrocarbons or oxygenates is a novel route. However, the selective production of monobrominated methane (CH3Br) at high conversions is a crucial prerequisite. A reaction model was developed according to the kinetic data available in the literature and thoroughly studied to investigate the optimum reactor conditions for selective methane bromination in gas phase. It was concluded that at high methane (&gt / 90%) conversions dibromomethane synthesis was favored at high selectivity (~90%) under the following conditions: T=330 &deg / C, Br:CH4 = 3. Sulfated zirconia included SBA-15 catalysts were prepared and characterized for the catalytic methane activation via bromination. The SBA-15 sol-gel preparation technique was followed and the zirconium was added during the preparation in the form of ZrOCl2&middot / 8H2O with 5-30 mol % ZrO2 with respect to the SiO2 content simultaneously with the silicon source (TEOS). The catalysts were sulfated in 0.25 M H2SO4 solution. The zirconium contents of the catalysts were determined by elemental analysis and 15 wt. % Zr was determined as the highest amount. XRD analysis showed the crystalline zirconia peaks only for high zirconia loadings (&gt / 25 mol % ZrO2) indicating the good distribution of Zr in silica framework at lower loadings. BET surface areas of the sulfated catalysts are in the range of 313-246 m2/g. The porous structures of the catalysts were determined by TEM pictures, which revealed that the increase in Zr content decreased the long range order of pore structure of SBA-15 in agreement with XRD results. The acidities of the catalysts were determined by 1H MAS NMR experiments. Br&oslash / nsted acidity was identified by a sharp 1H MAS NMR line at 10.6 ppm. The highest acidity was observed at 5.2 wt. % Zr loading according to 1H MAS NMR experiments. 29Si MAS NMR analysis showed the formation of Si-O-X linkages (X=H, Zr). Further characterization of Br&oslash / nsted acidity was performed by FT-IR spectroscopy of adsorbed CO at 82 K. The analysis revealed that the Br&oslash / nsted acidity of sulfated catalysts were similar to the acid strength of the conventional sulfated zirconia. In TPD experiments, the basic molecule isopropylamine (IPAm) was adsorbed and decomposition temperature of IPAm was monitored. The temperature decreased from 340 &deg / C to 310 &deg / C in sulfated catalysts, indicating the acidic character of these samples. Catalytic methane bromination reaction tests were performed in a quartz tubular reactor. The results showed that 69% methane conversion was attainable over SZr(25)SBA-15 catalyst at 340 &deg / C. The liquid 1H NMR measurements of the products revealed that &gt / 99% methyl bromide selectivity was achieved.

<p> <p>&nbsp / </p> </p> <p align="left">Retinoblastoma binding protein 6 (RBBP6) is a 250 kDa human splicing-associated protein that is also known to interact with tumour suppressor proteins p53 and pRb and to mediate ubiquitination of p53 via its interaction with Hdm2. RBBP6 is highly up regulated in oesophageal cancer, and has been shown to be a promising target for immunotherapy against the disease. RBBP6 is also known to play a role in mRNA splicing, cell cycle control and apoptosis.</p>

Woodchucks are the preferred animal model to study chronic viral hepatitis and the development of hepatocellular carcinoma (HCC), which occurs as a result of infection with woodchuck hepatitis virus. Significant elevations in the phosphomonoester peak in 31P-MRS spectrum correlated to the presence of HCC. Ex vivo 31P-NMR determined that HCC tissue had significantly elevated concentrations of PC compared to uninfected control tissues, confirming that PME is specific to the tumour’s growth. Finally, a recombinant vaccinia virus was constructed to stimulate the immune systems of infected woodchucks against cells expressing core antigens. Despite reductions in surface antigen expression and viral load, elevations in serum GGT and the PME in 31P-MRS indicated that there was tumour growth in treated woodchucks. In conclusion, the PME peak represents a potential biomarker of cancerous growth when used in conjunction with serological tests to detect HCC in the liver due to chronic hepatitis virus infection.

Woodchucks are the preferred animal model to study chronic viral hepatitis and the development of hepatocellular carcinoma (HCC), which occurs as a result of infection with woodchuck hepatitis virus. Significant elevations in the phosphomonoester peak in 31P-MRS spectrum correlated to the presence of HCC. Ex vivo 31P-NMR determined that HCC tissue had significantly elevated concentrations of PC compared to uninfected control tissues, confirming that PME is specific to the tumour’s growth. Finally, a recombinant vaccinia virus was constructed to stimulate the immune systems of infected woodchucks against cells expressing core antigens. Despite reductions in surface antigen expression and viral load, elevations in serum GGT and the PME in 31P-MRS indicated that there was tumour growth in treated woodchucks. In conclusion, the PME peak represents a potential biomarker of cancerous growth when used in conjunction with serological tests to detect HCC in the liver due to chronic hepatitis virus infection.

Master of Science / Department of Grain Science and Industry / Yong Cheng Shi / Waxy wheat starch (WWS) containing little or no amylose has unique properties for food and industrial uses. Hydroxypropylation, a widely used means for modifying starches, could enhance functionalities of starch by substituting hydroxyl groups in starch. There are limited numbers of literatures regarding hydroxypropylation of WWS. WWS hydroxypropylated with 3.0-9.0% propylene oxide (PO) were prepared and compared to hydroxypropylated normal wheat starch (NWS) and hydroxypropylated waxy maize starch (WMS). The molar substitution (MS) of the resulting hydroxypropylated NWS, WWS and WMS was 0.055-0.151, 0.048-0.133, and 0.049-0.139, respectively. Gelatinization temperatures and enthalpy of hydroxypropylated starches were significantly lower than those of their unmodified counterparts and the extent of decrease was positively correlated to the MS. Differential scanning colorimetry (DSC) results showed that hydroxypropylation reduced the retrogradation of the starches during the storage after gelatinization but there were differences between the starches. For the same level of PO reaction (3 and 5% PO), hydroxypropylated WWS retrogradated less than hydroxypropylated WMS, suggesting that for the same level of cold storage stability, less PO is needed for WWS. After reacted with 6% PO, MS was 0.092 and 0.094, respectively, for WWS and WMS, and no retrogradation was observed for those hydroxypropylated starches, indicating that at MS ~0.094, hydroxypropyl groups prevents amylopectin chains from re-associating and forming crystalline structures. In contrast, a higher level of PO (9%) was needed to react with NWS to achieve the hydroxypropylated starch with an MS of 0.151 that gave no retrogradation. Consistent with microscopic observation results, Micro-Visco-Amylograph (MVA) analysis showed hydroxypropylated starches developed viscosity at lower temperatures and had improved hot and cold viscosities. The specific characteristics of hydroxypropylated starches are related to the degree of hydroxypropylation. Therefore, it is critical to determine the level of hydroxypropylation in modified starches. 1H NMR is a simple and rapid means of determining hydroxypropyl (HP) group in modified starches. In this study, a method to prepare a HP starch for NMR analysis was improved. The optimum parameters proposed to hydrolyze HP starches were 10% starch solid content, 3.5% (wt.%) DCl in D2O as the solvent, sodium acetate as an internal standard, heating at 90oC for 1 h. Optionally, 6% (v/v) trifluoroacetic acid-d as the water-peak shifting reagent. Six hydroxypropylated starch samples and two commercial cross-linked and hydroxypropylated starch samples were hydrolyzed with this modified method before 1H NMR analysis, and the results of HP group content in the samples were in agreement with the results from an enzyme-catalyzed method, which indicate that the improved acid hydrolysis method is applicable for both hydroxypropylated starch and cross-linked and hydroxypropylated starch.

Magister Scientiae - MSc / Retinoblastoma binding prot ein 6 (RBBP6) is a 250 kDa human splicing-associated protein that is also known to interact with tumour suppresso r proteins p53 and pRb and to mediate ubiquitination of p53 via its intera ction with Hdm2. RBBP6 is highly up regulated in oesophageal cancer, and has been shown to be a promising target for immunotherapy against the disease. RBBP6 is also known to play a role in mRNA splicing, cell cycle control and apoptosis. / South Africa

Since their discovery in the 1930s, polymeric foams have been widely used in the industry for a variety of applications such as acoustical and thermal insulation, filters, absorbents etc. The reason for this ascending trend can be attributed to factors such as cost, ease of processing and a high strength to weight ratio compared to non-foamed polymers. The purpose of this project was to develop an “indestructible” material made of polycarbonate (PC) for industrial applications. Due to the high price of polycarbonate, two foaming methods were investigated to reduce the amount of material used. Samples were foamed physically in supercritical CO2 or chemically with 5-phenyl-1H-tetrazole. After thermal characterization of the foams in differential scanning calorimetry (DSC), we saw that none of the foaming methods had an influence on the glass transition of polycarbonate. Micrographs taken in scanning electron microscopy (SEM) showed that foams obtained in physical and chemical foaming had different structures. Indeed, samples foamed in supercritical CO2 exhibited a microcellular opened-cell structure with a high cell density and a homogeneous cell distribution. On the other hand, samples foamed with 5-phenyl-1H-tetrazole had a macrocellular closed-cell structure with a much smaller cell density and a random cell distribution. Compression testing showed that polycarbonate foamed physically had a compression modulus a lot greater. Then, XLPE mesh 35 or 50 and wollastonite were added to the polymeric matrices to enhance the foaming process and the mechanical properties. DSC experiments showed that the addition of fillers changed the thermal properties of polycarbonate for both foaming methods by inducing a shift in glass transition. SEM revealed that fillers lowered the average cell diameter and increased the cell density. This phenomenon increased the compression modulus for polycarbonate foamed in supercritical CO2. However, mechanical properties decreased for samples foamed with 5-phenyl-1H-tetrazole due to their relative brittleness and the propagation of microcracks.

The expected outcome of this project is to develop a general strategy to functionalize dispersions, by noncovalent adsorption of HMW surfactants, ultimately for applications such as hydrophobic coatings with high hiding power and hardness, improved mechanical properties via pigment-latex interactions, improved substrate adhesion or improved freeze-thaw stability. So far, we have produced poly (methyl methacrylate-co-butyl acrylate) latexes in the presence of HMW surfactants via emulsion polymerization and demonstrated stronger adsorption of HMW surfactants on particle surface than sodium dodecyl sulfate (SDS). In addition, we have developed surfactant-free latexes, poly (methyl methacrylate-co-butyl acrylate-co-methacrylic acid), as models for post functionalization with high molecular weight surfactants. The successful transfer of surfactants onto particle surface from liquid crystals was indicated by the increase in zeta potential and confirmed via chemical shifts variation in 1H NMR spectra. Additionally, the HMW surfactants were used for dispersing hydrophobic inorganic particles, such as hydrophobic carbon black, in aqueous phase, providing an indication of the general applicability and versatility of our approach.

Topical treatment containing undeclared corticosteroids and illegal topical treatment with corticosteroid content have been seen on the Swedish market. In creams and ointments corticosteroids in the category of glucocorticosteroids are used to reduce inflammatory reactions and itchiness in the skin. If the inflammation is due to bacterial infection or fungus, complementary treatment is necessary. Side effects of corticosteroids are skin reactions and if used in excess suppression of the adrenal gland function. Therefore the Swedish Medical Products Agency has published related warnings to make the public aware. There are many similar structures of corticosteroids where the anti-inflammatory effect is depending on substitutions on the corticosteroid molecular skeleton. In legal creams and ointments they can be found at concentrations of 0.025 ‑ 1.0 %, where corticosteroids with fluorine substitutions usually are found at concentrations up to 0.1 % due to increased potency. At the Medical Products Agency 19F-NMR and 1H-NMR have been used to detect and quantify corticosteroid content in creams and ointments. Nuclear Magnetic Resonance, NMR, is an analytical technique which is quite sensitive and can have a relative short experimental time. The low concentration of corticosteroids makes the signals detected in NMR small and in 1H‑NMR the signals are often overlapped by signals from the matrix. With 1H‑NMR characteristic signals could be detected in a less crowded spectral window between 5.96 ‑ 6.40 ppm where overlapping signals from the matrix often are absent. Since fluorine is less common in molecules, the option of using 19F‑NMR increases the possibility of finding fluorine-containing corticosteroids in creams and ointments. The corticosteroid signals in 19F‑NMR are detected at -165 ppm and -187 ppm, depending on where fluorine is located on the structure. Quantifying with 1H-NMR and 19F-NMR gave similar result with an accuracy of 98‑116 % and 89-106 % respectively, and RSD values between 2‑35 %, depending on the kind and amount of corticosteroid. Relations between the structure and some signals in 1H‑NMR were found, making it easier to determine the basic structure of unknown corticosteroids in creams and ointments. Screening experiments were performed on creams and ointments with known concentration corticosteroid in order to find minimum NS for analyzing products which might contain corticosteroids. In order to detect a corticosteroid concentration of 0.05 % 19F‑NMR needed 64 NS with an experimental time of 2 min and 1H-NMR needed 160 NS with an experimental time of 17 min. Concentrations of 0.025 % could for some corticosteroids be detected with these parameters. The possibility of spiking samples in order to discriminate between corticosteroids was also investigated. The corticosteroids available at the MPA could be discriminated from each other with at least one of the methods 1H‑NMR or 19F-NMR, and in most cases with both. A market research was done in order to search for counterfeits and salespersons in different health food stores were asked to recommend the best product to treat eczema or psoriasis. Nine recommended products were bought where one was found illegally containing a corticosteroid. In previous experiments at the MPA there had been occurrences of a split signal in 19F-NMR when analyzing creams. The split 19F‑NMR signal was shown to be related both to the presence of water and structural effects of the corticosteroid

No description available.