Synthetic Studies on Guaipyridine Alkaloids: Rupestines B and C

The rupestines, a family of guaipyridine alkaloids, are isolated from the plant Artemisia rupestris. Historically, this plant was used intraditional Chinese medicine due to its reported antitumor, antibacterial, and antiviral activities as well as reported protection of the liver. The rupestines can only be isolated from their parent plant in small quantities, making the total synthesis of these guaipyridine alkaloids of particular interest. Cananodine, anotherguaipyridine alkaloid, is a biologically active compound that can be isolated in small quantities from the fruits of Cananga odorata and displays activity against two types of hepatocellular carcinoma cell lines. It is hypothesized that the rupestines may also have anticancer activity. Synthesis of the rupestines would allow biological testing to determine if they, like cananodine, contain any activity against liver cancer or other types of cancer. In this project, the total synthesis of rupestines B and C was accomplished.The cyclic guaipyridine core in the synthesis of rupestines B and C was formed via intramolecular Mizoroki-Heck cyclization. In the first generation synthesis of rupestines B and C, a ketoester intermediate under went an undesired decarbonylation while producing only trace amounts of the desired product. To avoid the decarbonylation of the ketone, the starting material was changed such that a decarboxylation of anallylester would be favored. Alkylation of allyl 3-oxopentanoate with a substituted picolyl bromide provided the carbon-backboneof the target. Treatment ofadiallyl protected intermediate with palladium(0) in basic methanol resulted in the cleavage of both allyl groups and in situ decarboxylation of the intermediate keto acid. Triflation of the resulting phenolic hydroxyl gave the cyclization precursor. Exposureof the triflatetopalladium (0) in hot basic dioxane resulted in an intramolecular Mizoroki-Heck reaction that formed the seven-membered carbocycle of the guaipyridines. Finally, hydrogenation of the exocyclic alkene gave rupestines B and C in quantitative yield as a 1:2 mixture of diastereomers. While these diastereomers were not separable using flash column or radial chromatography, they were separableusing reverse phase MPLC. The 1H and 13C spectra for each diastereomer were assigned and matched the data reported in the isolation of the natural products

Marsbee - Swarm of Flapping Wing Flyers for Enhanced Mars Exploration

Mars exploration has received significant interest from academia, industry, government, and the general public. Despite continued interest, flying on Mars remains challenging, mainly due to the ultra-thin Martian atmospheric density. Although the gravitational acceleration on Mars is 38 percent of Earth's 9.8 meters per second squared, the Martian atmospheric density is only 1.3 percent of the air density on Earth. The aerodynamic forces are proportional to the ambient fluid density. Therefore, flying near the surface of Mars has been considered nearly impossible. The proposed mission architecture (Fig. 1) consists of a Mars rover (already existing) that serves as a mobile base for Marsbees - a deployable swarm of small bio-inspired flapping wing vehicles. In one ConOps scenario, each Marsbee would carry an integrated stereographic video camera and the swarm could construct a 3D topographic map of the local surface for rover path planning. These flying scouts would provide a "third-dimension" to the rover capabilities. In other scenarios, each part of the swarm of Marsbees could carry pressure and temperature sensors for atmospheric sampling, or small spectral analyzers for identification of mineral outcroppings. In each scenario, the rover acts as a recharging and deployment/return station and data and communication hub. Human exploration of Mars is one of the major objectives of NASA and commercial entities such as SpaceX and Boeing. The identified innovations unique to the bio-inspired flapping Marsbee provide viable multi-mode flying mobility for Martian atmospheric and terrain exploration. A swarm of Marsbees provides an enhanced reconfigurable Mars exploration system that is resilient to individual component failures. These Marsbees can carry sensors and wireless communication devices in combination with a Mars rover and helicopters. These enhanced sensing and information gathering abilities can contribute to the following NASA Mars mission objectives: i) "Determine the habitability of an environment", ii) "Obtain surface weather measurements to validate global atmospheric models", and iii) "Prepare for human exploration on Mars." Various commercial entities, e.g. SpaceX and Boeing, are investing in technologies to transport humans to Mars

Interventional suite and equipment management: cradle to grave

The acquisition process for interventional equipment and the care that this equipment receives constitute a comprehensive quality improvement program. This program strives to (a) achieve the production of good image quality that meets clinical needs, (b) reduce radiation doses to the patient and personnel to their lowest possible levels, and (c) provide overall good patient care at reduced cost. Interventional imaging equipment is only as effective and efficient as its supporting facility. The acquisition process of interventional equipment and the development of its environment demand a clinical project leader who can effectively coordinate the efforts of the many professionals who must communicate and work effectively on this type of project. The clinical project leader needs to understand (a) clinical needs of the end users, (b) how to justify the cost of the project, (c) the technical needs of the imaging and all associated equipment, (d) building and construction limitations, (e) how to effectively read construction drawings, and (f) how to negotiate and contract the imaging equipment from the appropriate vendor. After the initial commissioning of the equipment, it must not be forgotten. The capabilities designed into the imaging device can be properly utilized only by well-trained operators and staff who were initially properly trained and receive ongoing training concerning the latest clinical techniques throughout the equipment’s lifetime. A comprehensive, ongoing maintenance and repair program is paramount to reducing costly downtime of the imaging device. A planned periodic maintenance program can identify and eliminate problems with the imaging device before these problems negatively impact patient care

Preparation of Heterocycles by Gold Catalyzed Cyclizations of Propargyl Ethers and Sulfides

Oxygen heterocycles are synthesized by the intramolecular cyclization of substrates catalyzed by gold. One of the goals of this project was to also synthesize sulfur heterocycles. Many cyclization precursors have been formed from substituted aromatic thiols and alkynes. By investigating the effect of gold on intramolecular cyclizations, we can extend our studies to the varying substituents and their impact on the cyclization

Northside Boulevard Interchange Improvements, Nampa, Idaho

The Northside Boulevard Interchange serves the western Treasure Valley by providing interstate access to downtown Nampa, various agricultural and industrial zones, and a growing volume of commuter traffic. Interstate 84 is undergoing lane expansion projects to facilitate future traffic demands throughout the greater Treasure Valley. The expansion of the interstate corridor necessitates the following improvements to the Northside Boulevard Interchange: 1) the redesign and rebuilding of existing interstate overpass bridges to accommodate the interstate expansion, 2) the realignment and addition of lanes to existing on-ramps and off-ramps, 3) the addition of one lane to Northside Boulevard, for a total of six lanes, and 4) the redesign of existing intersections of Northside Boulevard and the interstate on-ramps and off-ramps. To meet the required levels of service D for design year 2030, capacity analyses were performed for all components of the interchange. A system was designed to collect and store stormwater resulting from these interchange improvements. The new bridges and appurtenant foundation and subsurface design were designed to adequately service the interchange and interchange components through 2030