One great issue of reforestation is the infestation of pest insects. The pine weevil (Hylobius abietis L.) is one of the economically most important pest insects in Europe and Asia. When insects feed on the trees the plants emit compounds that repel the insects. Methyl salicylate (MeSA) is one substance known to be emitted by conifer seedlings after herbivore feeding. Similar compounds are emitted by fungus isolated from pine weevil frass. Female pine weevils add frass to the egg laying site to protect the eggs from other pine weevils. The goal of the project was to cultivate the fungi Ophiostoma pluriannulatum and analyze the volatile substances. The fungus was cultivated using natural pine weevil frass (NF) as main substrate. Later new batches were prepared using lignin and potato dextrose broth (PDB), as feeding media to compare the results. Two sampling methods were used, SPME and adsorption with Porapak™ polymer column packing material. These samples were analyzed using GC-MS. Methyl salicylate was found in NF fungi cultures, peaking after ten days. Another, unexpected, product of the fungi was a sesquiterpene hydrocarbon. The lignin and the PDB samples did not produce MeSA. However, the sesquiterpene could be found in the lignin samples.

The green production of formic acid and utilization of methanol over heterogeneous catalysis system were investigated in this study. The heterogeneous catalysts are widely used in the chemical industry. They offer high stability and reusability which can enhance the production ability and lower the production cost, it can be considered as the sustainable energy solution for the future. In this work, we demonstrated several different heterogeneous catalysts for sustainable formic acid production and methanol utilization, including the heteropoly acid supported mesoporous silica catalysts and multi-function mixed metal oxide catalysts. Detailed characterizations of the final products were carried out by N2 adsorption and desorption, XRD, HR-TEM, SEM, ICP-OES, XANES, NH3- TPD, Raman spectroscopy, and FTIR to identify the chemical properties and physical properties of the catalysts. We obtained 60 % glycerol conversion and 30 % formic acid selectivity with at least 3 rounds of usages in batch system over PV1Mo/SBA-15-p-DS catalyst. Moreover, the continuous methyl formate production with significantly high formation rate (16.7) has been achieved via our CuMgO-based catalysts, and the best Cu5MgO5 catalyst gives more than 80 % methanol conversion with constant selectivity to methyl formate even after 4 catalytic test (more than 200 h), revealing their potential for industrialization. For the methanol utilization reaction, the methanol homocoupling to form dimethoxymethane (DMM) has been investigated. The redox and acidic properties of catalysts both play a critical role in this reaction and the related to different product. The supported V2O5 catalyst achieves the best catalytic performance (62.1 % conversion and 85.6 % DMM selectivity) with a Ce/Al specific ratio of 1. This research not only provided the efficient catalysts for numerous application with high activity, but also discovered the relation between the catalytic performance and the nature of the materials. These findings might further help the researcher to solve the global environmental and energy issues in the near future.

Chapter 1 provides some background information on the disease area of cancer and current modes of treatment. Chemotherapy treatment is discussed with a focus on the major cellular targets for these drugs: DNA and microtubules. For each target, classes of active compounds are described along with their mode of action. The microtubule stabilizing agent laulimalide is introduced and a case is made for analogue synthesis. Chapter 2 describes our first generation efforts toward synthesis of des-methyl laulimalide. The target compound is divided into a northern and southern fragment with the synthesis of each fragment described. The preparation of landmark intermediates along the synthetic route is also described. Chapter 3 presents our ongoing efforts toward a second generation synthesis of des-methyl laulimalide. Our progress toward a des-methyl,des-pyran analogue is covered as well. Chapter 4 reviews progress in the area of laulimalide analogue development. Biological assay results and the first insights into structure-activity-relationships are described.

The photolytic reaction of 0-methyl podocarpinitrile oxide to yield the δ-lactam (shown below) was studied under various conditions such as: solvent (hexane, methanol), mercury lamp wattage (lOOW, 450W), filter (Pyrex, Corex, Vycor), and additives (dichloromethane, hexafluorobenzene). The reactions were analyzed with IR, NMR and HPLC. Preparative medium pressure liquid chromatography and TLC were used in the δ-lactam isolation. The conditions resulting in the optimum yield of δ-lactam were determined. The photolytic stability of the δ-lactam under the conditions in which it was formed indicated that it was relatively stable only in hexane.

Leptinotarsa decemlineata (Say) is the most important defoliating pest of potato Solanum tuberosum L., in North America and Europe.  Management of this pest relies heavily on chemical control and insecticide resistance is a persistent problem.  This phenomenon has increased the need for developing novel insecticides, resistance evaluation, and the development of alternative control strategies regarding this insect pest.  From 2010 to 2013, field and lab experiments were conducted to evaluate the efficacy of a novel insecticide tolfenpyrad on L. decemlineata.  In leaf-dip assays, tolfenpyrad was highly toxic to L. decemlineata with LC50 values of 0.013 and 0.164 g ai/L for larvae and adults, respectively.  Tolfenpyrad was also toxic to eggs with 0% hatching after being dipped in a field rate concentration.  In field efficacy trials, potato plots treated with tolfenpyrad at rates as low as 153 g ai/ha effectively controlled L. decemlineata. In 2012, populations of L. decemlineata were collected from the Eastern Shore of VA and subjected to toxicity assays to determine current susceptibility to permethrin and oxamyl.  The toxicity assays indicated an increase in toxicity to permethrin in L. decemlineata larvae (LC50 = 3.931 g ai/L) and an increase in toxicity to oxamyl in adult beetles (LC50 = 9.695 g ai/L) compared with LC50 values previously reported in 1990.  In 2012, populations of L. decemlineata from Cheriton, VA, New Church, VA, Painter, VA, and Plymouth, NC were also evaluated for enzyme activity after exposure to sub-lethal concentrations of permethrin, oxamyl, and tolfenpyrad.  Adult beetles were subjected to enzyme assays to measure the activity of cytochrome P450 mono-oxygenase (P450), glutathione-S-transferase (GST), general esterases, and protein content.  Results from the enzyme assays indicated significantly greater esterase activity in beetles from Painter, VA exposed to permethrin [±-naphthol (F= 11.66, df= 4, 20, P<0.0001) and "-naphthol (F= 11.86, df= 4, 20, P<0.0001)], oxamyl [±- naphthol (F= 10.64, df= 4, 20, P<0.0001) and "-naphthol (F= 6.94, df= 4, 20, P=0.0011)], tolfenpyrad [±- naphthol (F= 407.62, df= 1, 8, P<0.0001) and "- naphthol (F= 28.15, df= 1, 8, P= 0.0007)], and the untreated control [±- naphthol (F= 28.14, df= 3, 16, P<0.0001) and "- naphthol (F= 28.86; df= 3, 16, P<0.0001)] compared to most of the other populations tested.  GST activity was significantly greater in tolfenpyrad exposed beetles compared to the non-treated beetles from Painter VA (F= 17.66, df= 5, 24, P< 0.0001). Through laboratory assays and field experiments in potato, the efficacy of a new bio-pesticide derived from the bacterium Chromobacterium subtsugae was evaluated for the control of L. decemlineata.  Results from the laboratory assays showed L. decemlineata feeding was inhibited by the bio-pesticide derived from C. subtsugae.  However, field efficacy trials in 2010, 2011, and 2012, indicated no control of L. decemlineata. Methyl salicylate is an organic compound produced by potato and other plants in response to insect herbivory.  Abundance of predatory arthropods and L. decemlineata life stages were measured in plots treated with and without 5 g slow-release packets of methyl salicylate (95% methyl salicylate (Predalure")).  Methyl salicylate treatment had no impact on predator recruitment or cumulative mortality of L. decemlineata in potatoes. This research has provided us with a new tool for L. decemlineata management, as well as more information about resistance trends and alternative control strategies from which we can build on to reduce resistance development in L. decemlineata and ultimately formulate a stronger integrated pest management strategy for this insect pest. / Ph. D.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第17886号 / 工博第3795号 / 新制||工||1580(附属図書館) / 30706 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 杉村 博之, 教授 酒井 明, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21363号 / 工博第4522号 / 新制||工||1704(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 高岡 昌輝, 教授 米田 稔, 准教授 大下 和徹 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

No description available.

The growth of Rhodotorula glutinis in sweet sorghum juice in three levels of three factors of temperature, carbon to nitrogen ratio and pH was evaluated. Accompanying of this growth was the generation of lipids converted to fatty acid methyl ester (FAMEs) and carotenoids. The optimized condition for maximum biomass and carotenoid accumulation was determined to be at 25C, pH of 5.5 and carbon to nitrogen ratio of 10. This condition yielded 22.7 g/L biomass with specific growth rate of 0.213 hr-1. At this condition the carotenoids generation was also maximum with 2.6 mg/gram biomass, comprising of torularhodin, beta-carotene and torulene. The accumulation of lipids following generation of biodiesel was highest at same temperature and pH but carbon to nitrogen ratio of 70, generating 96.3 mg of FAMEs/gram of biomass containing methyl ester of oleic acid, linoleic acid, palmitic acid, stearic acid and linolenic acid.

No description available.