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First studies of electron transfer in [N]phenylenes were performed in bimolecular quenching reactions of angular [3]- and triangular [4]phenylene with various electron acceptors. The relation between the quenching rate constants kq and the free energy change of the electron transfer (ΔG0CS ) could be described by the Rehm-Weller equation. From the experimental results, a reorganization energy λ of 0.7 eV was derived. Intramolecular electron transfer reactions were studied in an [N]phenylene bichomophore and a corresponding reference compound. Fluorescence lifetime and quantum yield of the bichromophor display a characteristic dependence on the solvent polarity, whereas the corresponding values of the reference compound remain constant. From the results, a nearly isoenergonic ΔG0CS can be determined. As the triplet quantum yield is nearly independent of the polarity, charge recombination leads to the population of the triplet state.

Heparan sulfate (HS) is a glycosaminoglycan present in all cell types covalently attached to core proteins forming proteoglycans. HS interacts with different proteins and thereby affects a variety of processes. The biosynthesis of HS takes place in the Golgi network where a complex of the enzymes EXT1 and EXT2 adds N-acetyl glucosamine and glucuronic acid units to the growing chain. The HS chain is N-sulfated by the enzyme N-deacetylase N-sulfotransferase (NDST). N-Sulfation occurs in domains where further modifications (including O-sulfations) take place, giving the chain a complex sulfation pattern. In this thesis, new data about the regulation of NDST enzyme activity is presented. By studying NDST1 with active site mutations overexpressed in HEK 293 cells we show that N-deacetylation is the rate-limiting step in HS N-sulfation and that two different NDST molecules can work on the same GlcN unit. By analyzing recombinant forms of NDST1 and NDST2 we determined the smallest substrate for N-deacetylation to be an octasaccharide. Importantly, the sulfate donor PAPS was shown to regulate the NDST enzymes to modify the HS chain in domains and that binding of PAPS had a stimulating effect on N-deacetylase activity. We could also show that increased levels of NDST1 were obtained when NDST1 was coexpressed with EXT2, while coexpression with EXT1 had the opposite effect. We suggest that EXT2 binds to NDST1, promoting the transport of functional NDST1 to the Golgi network and that EXT1 competes for binding to EXT2. Using cell lines overexpressing EXT proteins, it was demonstrated that overexpression of EXT1 increases HS chain length and coexpression of EXT2 results in even longer chains. The enhancing effect of EXT2 was lost when EXT2 was carrying mutations identical to those found in patients with hereditary multiple exostoses, a syndrome characterized by cartilage-capped bony outgrowths at the long bones. .

There is a demand for new recommendations for pulse seeding rates that will meet the needs of organic farmers. This study was conducted to determine the impact of seeding rate on N2 fixation and N accumulation in lentil and pea and to examine the impact of different seeding rates of lentil and pea on the productivity and N-uptake (i.e., N benefit) in a subsequent wheat crop.<p> The study was performed between 2005 and 2007. Two sites were selected each year of the two-year experiment on certified organic farms in central Saskatchewan. At each location, lentil (<i>Lens culinaris</i> L.) cultivar CDC Sovereign and field pea (<i>Pisum sativum</i> L.) cultivar CDC Mozart were each seeded at five different rates. Wheat (<i>Triticum aestivum</i> L.) cultivar AC Elsa was sown as a non-fixing reference crop at a plant population density of 250 seeds m-2. In the following year, wheat was sown to assess the effect of the pulse seeding rate treatments on the succeeding crop.<p> The pulse crop seeding rates significantly affected the quantity of N2 fixed of lentil and field pea, although %Ndfa (80 to 88% and 79 to 85% for lentil and pea, respectively) typically was unaffected by seeding rate. Yield parameters of following wheat crop were not affected by the seeding rates of the previous pulses. Typically, N contributions increased with increasing seeding rates of both lentil and pea, but there was no detectable difference in N uptake by the following wheat grown on the both pulse stubble. The different seeding rates of organically grown lentil and field pea have impacts on the amount of N2 fixed and N contribution to the soil. However, the differences in N remaining in the soil at different seeding rates of the pulse crops were not detectable in the following wheat crop and the soil N in the following year.

UDP-galactopyranose mutase (EC 5.4.99.9; UGM), the product of the glf gene, is an enzyme that catalyzes the conversion of uridine diphosphate galactopyranose (UDP-Galp) to UDP-galactofuranose (UDP-Galf). UGM activity is found in bacteria, parasites and fungi, however is absent in higher eukaryotes. This enzyme is essential for the viability of many pathogenic organisms, such as Mycobacterium tuberculosis and Escherichia coli, due to the broad distribution of Galf in crucial structures such as the cell wall or capsular polysaccharide. Not surprisingly, galactofuranose biosynthesis has become an attractive antimicrobial target due to the absence of these sugars in higher eukaryotes. The UGM homologue, UDP-Nacetylgalactopyranose mutase (UNGM), was identified in Campylobacter jejuni 11168, encoded for by the cj1439c gene. UNGM is known to function as a bifunctional mutase, which catalyzes the reversible ring contraction between the pyranose-furanose forms of UDPgalactose (UDP-Gal) and UDP-N-acetylgalactosamine (UDP-GalNAc). UNGM is essential for the virulence of C. jejuni, due to the incorporation of UDP-N-acetylgalactofuranose into the capsular polysaccharide. We report the first structure of UNGM determined by X-ray crystallography, to a resolution of 1.9 Å. Analysis of the dimeric, holoenzyme structure of UNGM has identified that the cofactor flavin adenine dinucleotide is bound within each monomer of the enzyme. Comparative analysis with UGM homologues has confirmed the conserved active site residues involved in the binding of various substrates. Docking studies suggest that UNGM binds its natural substrates in a productive binding mode for catalysis with the flavin cofactor, which is consistent with the proposed mechanism for UNGM. The mobile loops are essential for substrate binding, and we have identified that the conserved arginine residue, Arg169, and the neighboring Arg168, function to stabilize the diphosphate region of UDP, although not concurrently. The non-conserved arginine residue, Arg168, appeared to favor the stabilization of N-acetylated sugars, which is in agreement with the enzyme’s higher binding affinity for UDP-GalNAc over UDP-Gal by a factor of 0.9. We have also identified that the active site Arg59 exists in two conformations in the structure of UNGM, with one conformation directed toward the active site. Arg59 is 2.5 to 3.0 Å from the acetamido moiety of GalNAc, which is favorable for stabilization and is believed to confer specificity for this substrate.

Design of new chiral ligands for asymmetric synthesis is important. The ligand should be economical and efficient in enantioselective transformations. For the synthesis of some natural products and biologically active compounds, optically active amines are used as important intermediates. For this reason, it is significant to develop new catalyst system which can produce optically active amines in an economical and efficient way. Our group developed PFAM ligands and used successfully for the enantioselective synthesis of organic compounds. In this work, these ligands were tested as chiral catalysts for enantioselective synthesis of amines. N-sulphonyl and N-phosphinoyl imines synthesized from aromatic aldehydes were used as the starting material for enantioselective diethylzinc addition reaction in the presence of copper salt and PFAM ligands. By improving the known procedure, N-benzylidine sulphonylaldimine was obtained in excellent yield (98%). Asymmetric diethylzinc addition reaction to N-sulphonyl and N-phosphinoyl aryaldimines provided chiral amines in up to 81% enantioselectivity and 99% yield.

A quitting game is an undiscounted sequential stochastic game, with finitely many players. At any stage each player has only two possible actions, continue and quit. The game ends as soon as at least one player chooses to quit. The players then receive a payoff, which depends only on the set of players that did choose to quit. If the game never ends, the payoff to each player is zero. In this thesis we give a detailed introduction to quitting games. We examine the existing results for the existence of equilibria and improve an important result from Solan and Vieille stated in their article “Quitting Games” (2001). Since there is no software for the analysis of quitting games, or for stochastic games with more than two players, we provide algorithms and programs for symmetric quitting games, for a reduction by dominance and for the detection of a pure, instant and stationary epsilon-equilibrium.

There is a demand for new recommendations for pulse seeding rates that will meet the needs of organic farmers. This study was conducted to determine the impact of seeding rate on N2 fixation and N accumulation in lentil and pea and to examine the impact of different seeding rates of lentil and pea on the productivity and N-uptake (i.e., N benefit) in a subsequent wheat crop.<p> The study was performed between 2005 and 2007. Two sites were selected each year of the two-year experiment on certified organic farms in central Saskatchewan. At each location, lentil (<i>Lens culinaris</i> L.) cultivar CDC Sovereign and field pea (<i>Pisum sativum</i> L.) cultivar CDC Mozart were each seeded at five different rates. Wheat (<i>Triticum aestivum</i> L.) cultivar AC Elsa was sown as a non-fixing reference crop at a plant population density of 250 seeds m-2. In the following year, wheat was sown to assess the effect of the pulse seeding rate treatments on the succeeding crop.<p> The pulse crop seeding rates significantly affected the quantity of N2 fixed of lentil and field pea, although %Ndfa (80 to 88% and 79 to 85% for lentil and pea, respectively) typically was unaffected by seeding rate. Yield parameters of following wheat crop were not affected by the seeding rates of the previous pulses. Typically, N contributions increased with increasing seeding rates of both lentil and pea, but there was no detectable difference in N uptake by the following wheat grown on the both pulse stubble. The different seeding rates of organically grown lentil and field pea have impacts on the amount of N2 fixed and N contribution to the soil. However, the differences in N remaining in the soil at different seeding rates of the pulse crops were not detectable in the following wheat crop and the soil N in the following year.

In this study, two regenerative thermal oxidizers (RTO) were used to test the thermal destruction, thermal recovery efficiency and the gas pressure drop over the beds characteristics when burning, respectively, airborne chlorine- and nitrogen-containing volatile organic compounds (VOCs). First, an electrically-heated RTO containing two 0.5 m ¡Ñ 0.5 m ¡Ñ 2.0 m (L ¡Ñ W ¡Ñ H) beds, both packed with gravel particles with an average diameter of around 0.0116 m and a height of up to 1.48 m with a void fraction of 0.41 in the packed section was used to study the destruction characteristics of chlorine-containing VOCs (trichloroethane, TCE and dichloromethane, DCM). With a valve switch time (ts) of 1.5 min, preset maximum destruction temperatures (TS) of 500-800 oC and superficial gas velocity (Ug) of 0.17-0.33 m/s (evaluated at an influent air temperature of around 27 ¢J), tests on the thermal recovery efficiency (TRE) and the pressure drop for the air stream without VOC in the influent air stream have been performed. With a ts of 1.5 min, Ts of 500-800 oC and Ug of 0.17-0.24 m/s (evaluated at an influent air temperature of around 27 ¢J), tests on the degree thermal destruction of VOCs with influent air streams containing one of the two VOCs: trichloroethylene (TCE) and dichloromethane (DCM) have been done. Second, an electrically-heated RTO containing two 0.152 m ¡Ñ 0.14 m ¡Ñ 1.0 m (L ¡Ñ W ¡Ñ H) beds, both packed with gravel particles with an average diameter of around 0.0111 m and a height of up to 1.0 m with a void fraction of 0.42 in the packed section was used to study the destruction and NOx formation characteristics of DMF (N, N-dimethylformamide). With a ts of 1.5 min, Ts of 750-850 ¢Jand Ug of 0.39-0.78 m/s (evaluated at an influent air temperature of around 30 ¢J), TRE and the pressure drop for the air stream without VOC in the influent air stream have been tested. With a ts of 1.5 min, a Ug of 0.39 m/s (evaluated at an influent air temperature of around 30 ¢J), and Ts of 750-950 ¢J and, thermal destruction efficiencies and nitrogen oxides (NOx) formation characteristics in burning air streams containing either DMF or DMF mixed with methyl ethyl ketone (MEK) were performed. Results demonstrate that: (1) a RTO is suitable for destruction of low concentrations (<1,000 ppm as methane) of airborne highly chlorinated VOCs such as TCE and DCM and the destructed products contain no chlorine and only trace of COCl2 (< 1% of the influent VOC); (2) for TS = 800 oC and Ug = 0.17-0.24 m/s, complete oxidation products of TCE and DCM are HCl, CO2, and H2O, and the main intermediates are CO and COCl2; (3) with ts of 1.5 min, a Ug of 0.39 m/s (evaluated at an influent air temperature of around 30 oC) and TS of 750-950 ¢J, no NOx was present in the effluent gas from the RTO when it was loaded with DMF-free air; (4) when only DMF was present in the influent air, the average destruction efficiencies exceeded 96%, and increased with the influent DMF concentration from 300 to 750 mg/Nm3. The ¡§NOx-N formation/DMF-N destruction¡¨ mass ratios were in the range 0.76-1.05, and decreased as the influent DMF concentration increased within the experimental range; (5) when both DMF and MEK were present in the influent gas, the NOx formation ratio was almost the same and the DMF destruction efficiency increased with the influent MEK/DMF ratio from 150/300 to 4500/300 (mg/mg) and in the preset temperature range. The NOx formation ratios were in the range 0.75-0.96; (6) the TRE decreased as Ug increased but was invariant with Ts; and (7) the Ergun equation was found to suffice in the estimation of the pressure drop when the gas flowed over the packing beds.

The linear relationship between a conservative element and salinity during mixing of water masses is widely used to study biogeochemistry in estuaries and the oceans. Even though nutrient ratios are widely used to determine the limiting nutrient in aquatic environments, the rules of nutrient ratios change through the mixing of freshwater and seawater are still unstudied. This study provides general rules for nutrient ratios change via mixing. A simple mixing model is developed with the aims to illustrate that nutrient ratio is a nonlinear function of salinity, thus, shift in limiting nutrient over the salinity gradient can be simply a result of river water and seawater mixing, albeit complicated by biological consumption or remineralization. This model explains a natural phenomenon that rivers contain relatively high dissolved inorganic nitrogen (DIN) to soluble reactive phosphorus (SRP) ratios start to decrease the ratios as salinity increases when seawater contains higher SRP:DIN ratios. Although additional sources of P have been implicated as the cause for such change, this change can be a result of riverine water and seawater mixing. Four mixing rules are presented here to explain the factors governing the change in nutrient ratios vs. salinity; thus, answering why in some cases variations in nutrient loading and in other cases mixing triggers changes to seasonal limitation status in some estuaries. Shift in nutrient ratios can be explained by the change in nutrient inventories via mixing. After the P-limited riverine water shifts in N limitation by mixing with N-limited seawater, new production of the estuary in general becomes limited by the amount of N inputs from the riverine water and the seawater. The result may help to explain a current consensus that N and not P riverine loadings lead to eutrophication in estuaries which are influenced by P-limited riverine waters. Further, new production which is generated by N-limited riverine input and N-limited seawater input mainly depends on the amount of N inputs from the riverine water and the seawater.