We have two topics, In the first study, we synthesized three low-molecular-weight poly(glutamate)s¡Xpoly( £^-methyl l-glutamate) (PMLG), poly( £^-ethyl l-glutamate) (PELG), and poly( £^-benzyl l-glutamate) (PBLG)¡Xthrough living ring-opening polymerization of their £\-amino acid-N-carboxyanhydride derivatives and then blended them with phenolic resin to control the secondary structures of these polypeptides. Each of the three binary blends exhibited a single glass transition temperature (differential scanning calorimetry) and solid state nuclear magnetic resonance (NMR) spectroscopy], characteristic of a miscible system. The strength of the inter-associative interactions depended on the nature of the hydrogen bond acceptor groups, increasing in the order phenolic/PELG > phenolic/PMLG > phenolic/PBLG, as evidenced through analyses using Fourier transform infrared (FTIR) spectroscopy and the Painter¡VColeman association model. The fractions of £\-helical conformations (measured using FTIR and solid state NMR spectroscopy) of PMLG and PELG decreased initially upon increasing the phenolic content, but increased thereafter; in contrast, the fraction of £\-helical conformations of PBLG increased continuously upon increasing the phenolic contents. Using variable-temperature infrared spectroscopy to investigate the changes in the conformations of the secondary structures of the peptide segments in these three binary blends, we found that the £\-helical conformation in these three blend systems correlated strongly with the rigidity of side chain groups, the strength of the intermolecular hydrogen bonding with the phenolic resin, the compositions of phenolic resin, and the temperature. More interestingly, the content of £\-helical conformations of the polypeptides in these phenolic/PBLG blends increased upon increasing the temperature. The second topic is synthesized low-molecular-weight poly( £^-benzyl l-glutamate) (PBLG) through living ring-opening polymerization of their £\-amino acid-N-carboxyanhydride derivatives and blended them with poly( styrene¡^(PS), poly (acetoxystyrene) (PAS) and poly(vinyl phenol) (PVPh) to control the secondary structures of these polypeptides. DSC have been used to investigate the miscibility of. FTIR spectroscopies and wide-angle X-ray diffraction (WXRD) spectroscopic analyses provided evidence for the change and specific interactions between (PS, PAS and PVPh) and PBLG. That the secondary structures of polypeptides can be altered through blending with other different Specific Interactions, mediated by hydrogen bonding, dipole¡Vdipole, and £k¡X£k Interaction, we investigate strong Specific interactions was found between the side-chain esters of PAS, PVPh, but not found between PBLG and PS, because more weakly with the aromatic rings of PS through intermolecular £k¡X£k interactions, so that this latter system is phase separated.

The objective of this study is to extract phenolic compounds from nettle and melissa by using microwave and ultrasound and to compare these methods with conventional extraction and maceration, respectively. Extraction of melissa essential oil was also studied. In extraction of phenolics, effects of extraction time (5-20 min for microwave / 5-30 min for ultrasound) and solid to solvent ratio (1:10, 1:20, 1:30 g/ml) on total phenolic content (TPC) were investigated for microwave and ultrasound extractions. Different powers were also studied for ultrasound extraction. In addition, effect of solvent type (water, ethanol, ethanol-water mixture at 50:50 v/v) was analyzed and water was found as better solvent. Optimum conditions for microwave extraction of phenolics were determined as 10 min and 1:30 solid to solvent ratio for nettle, and as 5 min and 1:30 solid to solvent ratio for melissa. TPC at these conditions for nettle and melissa extracts were 24.6 and 145.8 mg GAE/g dry material, respectively. Optimum conditions for ultrasound extraction was 30 min, 1:30 solid to solvent ratio, and 80% power for nettle and 20 min, 1:30 solid to solvent ratio, and 50% power for melissa. TPC at these conditions for nettle and melissa were 23.9 and 105.5 mg GAE/g dry material, respectively. Major phenolic acids were determined as naringenin in nettle and rosmarinic acid in melissa. Major aromatic compounds in melissa essential oil were found as limonene, citral, and caryophyllene oxide. Yields of essential oil obtained by microwave and hydrodistillation were 4.1 and 1.8 mg oil/g dry sample, respectively.

Past research conducted by our lab demonstrated that potatoes contain significant levels of phytochemicals important to human health. However, since potatoes are not consumed raw, it is important to determine the effects of processing on these levels. Therefore, the changes in carotenoid content, antioxidant activity, and phenolic content were investigated using combinations of cultivars, cooking methods, storage treatments, and low-dose ionizing irradiation. Carotenoid content was measured via absorbance at 445 nm, 450 nm, and HPLC identification. Antioxidant activity was measured initially and at stabilization via the DPPH method and phenolic content was measured via the Folin method and HPLC identification. Microwaved, baked, fried, and raw potato samples contained more carotenoids than boiled samples. The samples microwaved, baked, and fried contained higher antioxidant activity and phenolics than the boiled or raw samples. However, the compound quercetin dihydrate appeared to decrease with cooking. Carotenoids, antioxidant activity, and phenolics appeared to decrease with storage; however, high storage temperatures and long storage times were believed to cause a dehydration and concentration of compounds, which caused levels to be equal to or greater than before storage. However, this decreasing trend was not linear and there were multiple significant interactions. The compound chlorogenic acid appeared to be quite sensitive to high temperature storage. Irradiation dose appeared to have only a minor, if any, effect on carotenoid levels. The interaction between storage time and irradiation dose was very influential on antioxidant activity. In early stages of storage, higher doses of irradiation had greater antioxidant activity, while, with continued storage, low doses had higher antioxidant activity. Exposure to irradiation appeared to cause an increase in phenolic content, determined by the Folin method. There may be a stimulation, induction, or release of some compounds due to processing; however, its magnitude is not believed to be as great as genetic control. The effects of processing can not be denied and should continue to be investigated. Future studies investigating the health properties of fruits and vegetables, particularly potatoes should include processing effects.

(-) Codeine, (-) morphine, and their semi-synthetic derivatives play an integral role in medicinal analgesia. Due to a complex list of undesirable side effects, their effective use is often complicated and troublesome giving cause for the investigation of novel semi-synthetic analogs for efficacy and side-effect profile. It was envisioned that new and interesting codeine analogs could be synthesized via an opening of a hindered 7,8-[alpha]-epoxide. Classically, hindered epoxides are formed via halohydrin formation and subsequent closure. Interestingly, the 7,8-epoxide formed via bromohydrin closure was resistant to reaction with small nucleophiles, such as oxygen and hydride, but reactive towards large and nucleophilic atoms, such as sulfur and bromide. It was discovered that the epoxide was in fact the less hindered 7,8-[Beta] epoxide via x-ray analysis of various compounds. This hinted at an unexpected rearrangement which most likely occurred during the bromohydrin formation due to the severe steric interactions present in the core structure of codeine. Due to the reversibility of bromonium ion formation, a highly hindered double bond can produce the opposite configuration of what is expected when subjected to aqueous brominating conditions. Many popular alkaloids, including codeine and galanthamine, are biosynthetically formed via a spirocyclic dienone intermediate. In nature these intermediates are formed via an enzymatically driven phenolic oxidation; however in the lab this reaction has proven difficult to reproduce. In a previous Magnus publication, (±) codeine and (-) galanthamine, were synthesized via a common spirocyclic cross-conjugated dienone intermediate similar to the intermediate found in nature. Most importantly, this intermediate was formed without a phenolic oxidation. Instead, a para-alkylation of an appropriately substituted phenol efficiently created the key intermediate. Expanding on this phenolic alkylation strategy, various biaryl systems were built in order to investigate the scope and limitations of this reaction. Multiple para- alkylations proved successful while ortho- alkylations unveiled an interesting rearrangement which occurs during the reaction. Lastly, it was determined that a 7-membered ring could not be set using a phenolic alkylation strategy. / text

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Currently, creosote-treated wood waste is mainly landfilled but the Province of Nova Scotia would prefer to see the waste converted to a valuable product. Bioremediation provides a treatment option for creosote-treated wood waste and the production of a value-added product that would have economic and environmental benefits. Composting technique can be used to degrade the contaminants and convert wood waste into humus and nutrients rich product and reduces the waste volume. The aim of this study was, therefore, to test the efficiency of the composting process in degrading the creosote in the contaminated wood waste. A laboratory scale bioremediation process was carried out in three specially designed in-vessel bioreactors equipped with thermo-insulating outer layer, mixing units, controlled aeration units, thermocouples a data logger and a computer. The three bioreactors were used as replicates. The ability of three thermophilic and cellulolytic microorganisms (T. curvata, T. aurantiacus and T. fusca) to degrade lignocellulose substrate was tested.

The total phenolic content (TPC) of common vegetables grown in Ontario was determined by the Folin-Ciocalteu method, and it was found that the broccoli inflorescence had an exceptionally high TPC on average value, followed by cabbage, onion, potato and carrot. The TPC values of darkpurple potatoes and carrots were higher than the common potatoes and carrots. Positive correlations between the TPC and TAA were observed with varied degrees in all vegetables. Choice of cultivar and production practices can be used to increase TPC and TAA in a wide range of vegetables. Insecticide application did not influence the TPC and TAA of broccoli leaves and flowers. Higher N rate decreased the TPC and TAA of cabbage cultivar ‘Huron’ and of carrot. Fungicide and biofungicide applications did not influence TAA in carrots. Fertilizer applications did not influence the TAA of onions, but there was a decrease in TPC. The rate of MAP (mono ammonium phosphate 52% P2O5) affected the TAA of onions, but the influence was inconsistent between two antioxidant assays. High temperature with possibly high rainfall capacity occurred in the year increased the TPC and TAA of most studied vegetable crops. / Ontario Ministry of Agriculture, Food and Rural Affairs/University of Guelph Sustainable Production Systems Program

This thesis is an investigation of the effects of whole beans, with different levels of phenolics level, on colonic inflammation in mice. C57BL/6 male mice were fed a basal diet (BD) supplemented with or without 20% bean flour for 3 weeks. Colitis was induced by 2% dextran sulphate sodium (DSS) in mice drinking water. Phenolic determinations of the bean flours revealed that within each pair of beans, the darker bean had higher phenolic content and antioxidant activity compared to the lighter one. In addition, only coloured beans had anthocyanin. When bean were consumed both prior to and during DSS cycle, the mice experienced both disease attention and aggravation. However, when bean consumption was limited to prior to DSS induction only, mice had reduced colitis upon later DSS induction. Overall, findings suggest that the effects of bean may differ depending on the timing of consumption. / Agriculture and Agri-Food of Canada, Ontario Ministry of Agriculture and Rural Affairs

Fragaria ananassa, generally known as strawberry is a nutritious fruit that is rich in polyphenols and widely consumed as part of a healthy diet. Anthocyanins have been found to be the main group of phenolic components present in strawberry with pelargonidin-3-glucoside as the major component in all strawberry cultivars studied. The main volatile component has been identified as caryophyllene oxide, a sesquiterpene compound that was present abundantly in all cultivars. The effect of preharvest spray applications of a formulation containing hexanal which is known to enhance membrane preservation, was evaluated using two strawberry cultivars, ‘Jewel’ and ‘Mira’. Our results suggest that preharvest spray application of hexanal formulation results in biochemical changes that alter the profile of phenolic compounds and the volatiles of the fruit. An osmotic infusion treatment was implemented to generate an intermediate moisture food product with high quality and enhanced storage life that can be potentially used in processed food. Infusing strawberry with other functional ingredients such as fructoligosaccharides, lecithin, and ascorbic acid showed that the infused strawberry produced by this technique was structurally and organoleptically similar to fresh strawberry, and visually similar to the intial fruits. Drying of infused fruits could extend their shelf life up to several months, while providing fruit products with superior nutritional qualities. Subjecting strawberry fruit extract to a simulated in vitro digestion of strawberry greatly affected the polyphenol composition and concentrations during different stages of digestion. The concentrations of most polyphenols increased during gastric digestion suggesting that the acidic environment of the stomach may help to release polyphenols that are bound to the strawberry matrix. Following incubation of the IN and the OUT fractions with colonic bacteria, the presence of urolithin B glucunoride in the IN fraction and the increase of ellagic acid deoxyhexoside in both the IN and OUT fractions after fermentation process, suggest that the polyphenols are catabolized into simple phenolic compounds in the colon. The remaining polyphenols as well as the catabolites in the gut, could potentially have a beneficial effect in enhancing colonial health. / Ministry of Higher Education Malaysia, Universiti Putra Malaysia

As sessile organisms, plants are unable to escape from attack by herbivorous insects. To cope with this pressure, plants have evolved several defense strategies, including the production of secondary metabolites, specialized chemicals with ecological functions. Most studies have focused on the role of secondary metabolites in plant defense against chewing insects. Little is known about what compounds are present in phloem sap and how they affect phloem feeding insects. Therefore, I investigated the effects of phenolic compounds on phloem feeders, using Chaitophorus aphids in bioassays with wildtype and transgenic poplar overexpressing the transcription factor MYB 134, which results in elevated levels of tannins and reduced levels of phenolic glycosides. Aphids produced significantly more offspring on MYB 134 plants but showed a significant preference for lower tannin leaf tissue. Analysis of poplar phloem exudates and aphid extracts provides direct evidence that the phenolic glycosides salicin, salicortin and tremulacin are present in poplar phloem and are ingested by aphids. These results are discussed in relation to what is driving the differences in aphid fecundity and choice between plant types. / Graduate / 0309 / 0307 / 0329 / alphareghanwong@gmail.com