Abstract 2-Methoxy- and 2-trimethylsilyloxyfuran undergo facile ring opening reaction upon treatment with metal carbeniod. Treatment of 2-methoxy-furan with ethyl diazoacetate and aryl-£\-diazocarbonyl compounds under metal catalysis afford (Z,E)-2,4-hexadienedioate and aryl-6-oxo-2,4-hexadienoates respectively. When 2- trimethylsilyloxyfuran was used, desilylation occurred to give directly the monoprotected (Z,E)-muconic acid and 6-aryl-6-oxo-2,4-hexadienoic acids. We have synthesized aromatic dienyl diketone using the method of Wenkert from aromatic diazo ketone and 2-methylfuran. This method was found to give a mixture of (Z,E)/(E,E)-dienyl diketones. The anticancer, antibacterial and vasorelaxing activities are evaluated. All the aromatic dienyl diketones synthesized exhibit strong in vitro inhibition of tumor cell and micro0organisms growth respectively, and three of these compounds exhibit strong vasorelaxing effect. Reaction of 1,6-dioxo-2,4-diene with P2S5 and Lawesson¡¦s reagent affords the 2,5-disubstituted thiophene. This reaction can take place regioselectively in the presence of BF3-etherate catalysis, useful for the synthesis of arylthiophene. We have demonstrated a new methodology for the facile synthesis of arylthiophene.

The indeterminate nature of lentil (Lens culinaris Medik), in conjunction with adverse field conditions, can lead to varying degrees of maturity among plants at harvest. This variable maturity may have a negative influence on lentil production and can delay harvest. Desiccants are currently used to improve lentil crop dry-down. However, applying desiccants too early may result in reduced crop yield and quality, and also leave unacceptable herbicide residues in lentil seeds. In addition, only four herbicides (glyphosate, diquat, saflufenacil, and glufosinate) are registered as desiccants for lentil desiccation in Canada, which limits options for growers. Therefore, the objectives of this thesis were i) to determine the importance of desiccant application timing in affecting crop yield and quality, as well as herbicide residues and ii) to determine whether additional desiccants applied alone or tank-mixed with glyphosate provide better crop desiccation. Field trials were conducted at Saskatoon and Scott, Saskatchewan, from 2012 to 2014. In the application timing trial, glyphosate or saflufenacil alone, or glyphosate+saflufenacil generally decreased seed yield, thousand seed weight, and crop dry-down, and increased herbicide residue levels at earlier application timings. For example, when applied at 60% seed moisture, saflufenacil reduced yield and thousand seed weight by 22% and 10%, respectively, and resulted in glyphosate and saflufenacil residues greater than 2.0 and 0.03 ppm, respectively. Although there were no reductions in yield and thousand seed weight when desiccants were applied at 50% or 40% seed moisture, glyphosate residue exceeded 2.0 ppm. Application of desiccants at 20 or 30% seed moisture content had no effect on yield, thousand seed weight, or herbicide residues. These results indicate that desiccant application timing is critical, and should not be made before 30% seed moisture. In a second study, glufosinate and diquat tank mixed with glyphosate were the most consistent desiccants and provided optimal crop dry-down without reducing yield and thousand seed weight, and effectively reduced glyphosate residue. The other herbicides tested (pyraflufen-ethyl and flumioxazin) were found to be poor options for growers as they had sub-optimal crop desiccation and did not affect glyphosate residue.

Bermudagrass (Cynodon dactylon L.) is often used for athletic fields due to its wear tolerance and recuperative ability. Studies were conducted May 2007 through November 2008 in Lexington, Kentucky. The cultivars ‘Quickstand’, ‘Tifway’, ‘Riviera’, and ‘Yukon’ grown in a sand-based medium were used to investigate differences in wear tolerance and shear strength. Trinexapac-ethyl (TE) was applied at label rates and frequencies or untreated. Overseeding treatments were perennial ryegrass (Lolium perenne L.) at 0, 612, and 1225 kg PLS ha-1. Traffic treatments were applied with a Brinkman traffic simulator 3 d wk-1 August through October. Shear tests were conducted using the Clegg shear tester once wk-1 for the same period. The main effect of cultivar was significant (p Quickstand=Yukon) and overseeding at the medium and high rates. Significant differences (p Tifway =Yukon (2007) and with Riviera ≥ Quickstand > Tifway = Yukon (2008). Significant differences (p0.05) in either year for traffic tolerance or shear strength.

Magnetic particles have attracted increasing attention in fields ranging from separation processes to electromagnetic information storage an medical application. Various approaches for their synthesis have been developed and studied to satisfy the criteria of production. Improvement and optimization of size, stability, and functionality is of vital importance in biological applications. The main aspect of project, initially, was to study the application of aqueous functionalized magnetic nanoparticles coupled with high gradient magnetic separation technique for the removal of trace residue of organic contaminants from drinking water. However, the importance of synthesizing stable ferrofluid for this purpose became clear later and took precedence over the initial objective. Different approaches were adopted, such as the incorporation of poly(ethylene glycol) methacrylate, ethylenediamine, and chitosan, to enhance the stability of magnetic particles. However, these surface modifications had unfavorable effect on the stability of initial particles. In accord with the initial objective of the project, the possibility of utilization of β-cyclodextrin, as organic pollutant entrapment agent, was investigated in preliminary studies conducted on its interaction with a model compound, procaine hydrochloride. The outcomes of these experiments suggest its potential as a biocompatible removal agent for the elimination of organic pollutant in drinking water system, or other applications that require selective separation of organic compounds.

Ethyl lactate is a promising, and environmentally benign chemical, which requires efficient separation techniques to overcome the equilibrium limitations in its production. Pervaporation based hybrid systems are successful in these type of equilibrium limited reactions, where product and/or by-product are removed from reaction medium by pervaporation unit(s) so as to drive reaction to completion. For the production of ethyl lactate four possible semi-batch hybrid systems were previously proposed. However, in order to select the suitable hybrid system within the proposed layouts phase equilibrium and reaction kinetics of the system must be well defined in addition to the performance data of the pervaporation membranes. Therefore, vapor pressure curve of ethyl lactate, VLE curves of ethanol-ethyl lactate and ethyl lactate-water were determined and performances of commercial hydrophobic membranes were investigated experimentally for the separation of ethanol-ethyl lactate mixtures. As a result of vapor pressure and VLE experiments, azeotrope was observed at 71wt% of water for ethyl lactate-water binary mixture at 80mmHg pressure. Furthermore, dependence of vapor composition on pressure was found to be slight for ethanol-ethyl lactate mixtures. Two commercial hydrophobic membranes, and an organoselective one were used in the separation of ethyl lactate-ethanol mixtures. It is found that hydrophobic membranes have sufficient fluxes and reasonable selectivities. Moreover, it is observed that as temperature increase flux increases and selectivity decreases. Finally, it is concluded that it would be possible to produce ethyl lactate by using the previously proposed integrated PV-esterification reactor systems.

Pervaporation is a selective membrane technique in which a liquid feed mixture is separated by means of partial vaporization through a non-porous perm-selective membrane. This method can be used for the recovery of heat sensitive aroma compounds to avoid them from thermal damage in beverage industries. The main objective of this study was to determine the effects of feed temperature (30, 40, 50&deg / C), composition (different model solutions, strawberry essence), concentration (50, 100, 150 ppm) and permeate pressure (4, 8 mbar) on the recovery of aroma compounds of strawberry by pervaporation in terms of mass flux and selectivity. In addition, it was aimed to optimize the extraction conditions (extraction time, temperature, agitation speed, strawberry matrix) of Solid-phase microextraction (SPME), which is used for the analysis of strawberry aroma compounds. Optimum results for SPME were obtained at 40&deg / C, 700 rpm for 30 min and no matrix effect was observed. Pervaporation experiments were performed using a hydrophobic membrane, PERVAP 1070 (PDMS). As the feed temperature increased, the mass flux and selectivity increased and the total mass flux followed an Arrhenius type relation. Decreasing downstream pressure increased both total flux and selectivity, while increase in feed concentration led to higher organic fluxes but lower selectivities. In general, PERVAP 1070 showed a higher selectivity towards Methyl butyrate (MTB) than Ethyl butyrate (ETB) and MTB flux was affected negatively by the presence of ETB in the feed solution. Pervaporation experiments were also performed with a strawberry essence and strawberry model solution. The selectivities of MTB and ETB were negatively affected by the presence of other aroma compounds.

In einer Vielzahl von Arbeiten konnten anti-inflammatorische Eigenschaften von Ethylpyruvat (EP) aufgezeigt werden. An verschiedenen Modellen der Sepsis, des hämorrhagischen Schocks, von Verbrennungsschäden, des Apoplex oder der Ischämie und Reperfusion wurde bei der Behandlung mit EP ein protektiver Effekt sowie eine verminderte Produktion von pro-inflammatorischen Zytokinen nachgewiesen. Als biochemische Grundlage wurde die Interaktion von EP mit dem Transkriptionsfaktor NF-κB identifiziert, die spezifischen Regulationsmechanismen konnten bisher allerdings nicht zufriedenstellend aufgeklärt werden. In dieser Arbeit wurde als eine neue mögliche Erklärung für die anti-inflammatorischen Eigenschaften des EP und weiterer α-oxo-Karbonsäureester die Inhibierung der Glyoxalase I (Glo-I) aufgezeigt. In vitro-Experimente zur Enzymaktivität belegten die Hemmung der Glo-I durch EP, während α-Hydroxy-Karbonsäureester wie L-Ethyllaktat (EL) keine inhibierenden Eigenschaften aufwiesen. Dennoch waren sowohl EP als auch EL und weitere Laktatester in der Lage, die LPS-induzierte Produktion von pro-inflammatorischen Zytokinen wie IL-1β, IL-6, IL-8 und TNF-α von humanen immunkompetenten Zellen zu supprimieren und die Expression von Immunrezeptoren wie HLA-DR, CD14 und CD91 zu modulieren. Somit konnten erstmals anti-inflammatorische Eigenschaften von Laktatestern nachgewiesen sowie eine Verbindung zwischen den Glyoxalase-Enzymen und dem Immunsystem etabliert werden. Diese und weitere Ergebnisse zur Einflussnahme der Karbonsäureester auf die Zellvitalität präsentieren das Glyoxalasesystem als mögliches Ziel neuer Therapiekonzepte für die Immunsuppression und bestätigen dessen Bedeutung für die Entwicklung von Anti-Tumor-Agenzien.

Poly(2-ethyl-2-oxazoline) (PEOX) is a nonionic, synthetic polymer which is soluble in both a variety organic solvents and water. The negative entropy of mixing of this polymer in aqueous solution suggested that it adopts a rigid conformation such as a helix in aqueous solution. Hydrogen bonding between PEOX and water molecules is thought to facilitate a special conformation that is specific to aqueous solution. The intent of this work is to investigate the conformation of PEOX in aqueous solution and consequently propose the mechanism by which it would adsorb onto cellulose and make it a valuable additive in paper processing. This work ultimately contributes to the greater matter of understanding the mechanisms by which water solvates nonionic polymers. Viscometry measurements of PEOX in water show that its shape scales similar to a random coil and that its molecules collapse in the presence of sodium chloride. Investigation into the molecular structure of PEOX through molecular scale simulations have revealed that although a rigid helical conformation does not exist, the potential exists for PEOX to have secondary helical structure in both water and other solvents. Without the rigid predicted structure, however, it is not surprising that PEOX does not adsorb well on cellulose. Comparing this folded helical conformation to a random coil conformation reveals that the random coil produces a lower energy system in water.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1939. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaf [15]).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1962. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 131-135).