An Investigation of Wild Bee Diversity and Abundance in Plots Managed by The Nature Conservancy in South-Central Nebraska and of Beneficial Arthropods Associated with Native Nebraska Flora

Insect pollination is an essential ecosystem service, and bees are the principal pollinators of wild and cultivated plants. Habitat management and enhancement are a proven way to encourage wild bee populations, providing them with food and nesting resources. I examined bee diversity and abundance in plots managed by The Nature Conservancy near Wood River, NE. The plots were seeded with 2 seed mixes at 2 seeding rates: high diversity mix at the recommended rate, high diversity mix double the recommended rate, Natural Resources Conservation Service (NRCS) conservation planting (CP) 25 mix at one-half the recommended rate, and NRCS CP25 mix at the recommended rate. I measured wild bee abundance and diversity, and established a database of wild bees associated with the plots. I also compared genus richness and abundance among the plots using and aerial net and blue vane traps to collect bees. Significant differences were not observed in genus richness and diversity among the plots; however, plot size and the ability of blue vane traps to draw bees from a long distance may have influenced my results. In 2008, 15 genera and 95 individual bees were collected using an aerial net and in 2009, 32 genera and 6,103 individual bees were collected using blue vane traps. I also studied the beneficial insects associated with native Nebraska flora. Seventeen species of native, perennial flora were established in 3 separate plots located in eastern Nebraska. I transplanted four plants of each species in randomized 0.61 m x 0.61 m squares of a 3.05 m x 9.14 m plot. Arthropods were sampled using a modified leaf blower/vacuum. Insects and other arthropods were identified to family and organized into groups of predators, parasites, pollinators, herbivores, and miscellaneous. Associations between plant species and families of beneficial arthropods (predators, parasites, and pollinators) were made. Pycnanthemum flexuosum Walter attracted significantly more beneficial arthropod families than 7 other species of plants tested. Dalea purpurea Vent and Liatris punctata Hook also attracted significantly fewer beneficial arthropod families than 4 other species of plants tested. In total, 31 predator, 11 parasitic, 4 pollinator, 31 herbivore, and 10 miscellaneous families of arthropods were recorded.

I. Development of the In Situ Reductive Ozonolysis of Alkenes with Tertiary Amine N-Oxides. II. Progress toward the Asymmetric Synthesis of Peroxyplakoric Acid A3.

Ozone, first discovered in the mid 1800’s, is a triatomic allotrope of oxygen that is a powerful oxidant. For over a century, research has been conducted into the synthetic application and mechanism of reactions of ozone with organic compounds. One of the major areas of interest has been the ozonolysis of alkenes. The production of carbonyl compounds is the most common synthetic application of ozonolysis. The generally accepted mechanism developed by Rudolf Criegee for this reaction involves the 1,3-electrocyclic addition of ozone to the π bond of the alkene to form a 1,2,3-trioxolane or primary ozonide. The primary ozonide is unstable at temperatures above -100 °C and undergoes cycloreversion to produce the carbonyl oxide and carbonyl intermediates. These intermediates then recombine in another 1,3-electrocyclic addition step to form the 1,2,4-trioxolane or final ozonide. While the final ozonide is often isolable, most synthetic applications of ozonolysis require a subsequent reductive or oxidative step to form the desired carbonyl compound. During investigations into the nucleophilic trapping of the reactive carbonyl oxide, it was discovered that when amines were used as additives, an increased amount of reaction time was required in order to consume all of the starting material. Surprisingly, significant amounts of aldehydes and a suppression of ozonide formation also occurred which led to the discovery that amine N-oxides formed by the ozonation of the amine additives in the reaction were intercepting the carbonyl oxide. From the observed production of aldehydes, our proposed mechanism for the in situ reductive ozonolysis reaction with amine N-oxides involves the nucleophilic trapping of the carbonyl oxide intermediate to produce a zwitterionic adduct that fragments into 1O2, amine and the carbonyl thereby avoiding the formation of peroxidic intermediates. With the successful total syntheses of peroxyacarnoates A and D by Dr. Chunping Xu, the asymmetric total synthesis of peroxyplakorate A3 was investigated. The peroxyplakoric acids are cyclic peroxide natural products isolated from the Plakortis species of marine sponge that have been found to exhibit activity against malaria, cancer and fungi. Even though the peroxyplakorates differ from the peroxyacarnoates in the polyunsaturated tail and the head group, the lessons learned from the syntheses of the peroxyacarnoates have proven to be valuable in the asymmetric synthesis of peroxyplakorate A3. The challenges for the asymmetric synthesis of peroxyplakorate A3 include the stereospecific formation of the 3-methoxy-1,2-dioxane core with a propionate head group and the introduction of oxidation sensitive dienyl tail in the presence of a reduction sensitive 1,2-dioxane core. It was found that the stereochemistry of two of the chiral centers could be controlled by an anti-aldol reaction of a chiral propionate followed by the stereospecific intramolecular cyclization of a hydroperoxyacetal. The regioselective ozonolysis of a 1,2-disubstituted alkene in the presence of a terminal alkyne forms the required hydroperoxyacetal as a mixture of diastereomers. Finally, the dienyl tail is introduced by a hydrometallation/iodination of the alkyne to produce a vinyl iodide followed by a palladium catalyzed coupling reaction. While the coupling reaction was unsuccessful in these attempts, it is still believed that the intramolecular cyclization to introduce the 1,2-dioxane core could prove to be a general solution to many other cyclic peroxides natural products.