17 research outputs found
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Studies Toward the Synthesis of Natural Product Scaffolds
Part 1: A Diels-Alder Approach to the Synthesis of Novel Analogues of the Natural
Product Siamenol
Due to the prevalence of biaryl motifs in natural product synthesis, the Carter
research group has been exploring the utility of a Diels-Alder approach to biaryl
synthesis. The Diels-Alder approach involves a [4+2] cycloaddition between an
acetylene dienophile and a cyclohexadiene, followed by subsequent [4+2]
cycloreversion. This method of biaryl synthesis introduces numerous advantages
compared to the traditional metal-mediated biaryl synthesis procedures, including a lack
of environmentally hazardous transition metals.
The Diels-Alder approach has been used by the Carter group to synthesize the
natural product siamenol. This carbazole alkaloid, isolated from the Murraya siamensis
shrub, has been found to possess moderate activity in the inhibition of the human
immunodeficiency virus (HIV). Previously, synthesis of siamenol had been based on the
traditional metal-mediated cross-coupling approach. Based on this initial synthesis, a
series of novel analogues of siamenol have been synthesized using the Diels-Alder
approach to biaryl synthesis. This project focuses on the synthesis of four such
analogues of siamenol.
Part 2: Advances in Proline-Based Enantioselective Organocatalysis and its Application
to a Novel Synthesis of the Natural Product Aconitine
Organocatalysis, while not a novel concept, has made significant strides in the
last decade with the advent of improved methods of enantioselective organocatalysis.
Particular advances have been made in the use of proline-based organocatalysts in
catalyzing such reactions as aldol, Mannich and Michael reactions in a highly
enantioselective fashion. The Carter Group has utilized Hua Cat, a proline-based
sulfonamide, to catalyze a series of [2.2.2] bicyclizations based on a Mannich reactionrelated
mechanism. This approach has been utilized to form a precursor to the natural
product aconitine, a known analgesic and antipyretic. The key [2.2.2] bicyclization step
proceeded in a high-concentration (1.0 M), room temperature reaction that produced the
target [2.2.2] octane with a 57% yield and 99% e.e. Further considerations toward the
synthesis of aconitine are also discussed
Using Coupled Eulerian and Lagrangian Grids to Model Explosive Interactions with Buildings
This paper presents the development of a computational model that can be used to study the interactions between structures and detonating explosives contained within them. This model was developed as part of an effort to develop a rubble characterization model for use in AmmoSIM, an agent based urban tactical decision aid (UTDA) software for weapon-target pairing. The rubble pile created following the collapse of a building in a combat situation can significantly impact mission accomplishment, particularly in the area of movement and maneuver. The information provided by AmmoSIM will enable both platoon level and command center staff to make informed decisions concerning urban attack tactics.
Computational models were created using a combination of AUTODYN 2D and 3D. The detonation was modeled using a 2D wedge, which is a common method used in AUTODYN. The information obtained from the wedge calculation was then written to a data file and subsequently remapped into a larger 3D Euler air grid. The air grid loaded with blast pressure information was coupled to interact with the Lagrangian building parts. The Riedel, Hiermaier and Thoma (RHT) Concrete Model from the AUTODYN material library was utilized to create the components of the building. Results of the latest models will be given. Additionally, the paper details the development of the model at length including topics such as grid sizing, computational cost comparisons, grid interactions, multi-solver coupling, strain erosion, and material parameters and selections
Neurofunctional Correlates of Ethical, Food-Related Decision-Making
A grant from the One-University Open Access Fund at the University of Kansas was used to defray the authorās publication fees in this Open Access journal. The Open Access Fund, administered by librarians from the KU, KU Law, and KUMC libraries, is made possible by contributions from the offices of KU Provost, KU Vice Chancellor for Research & Graduate Studies, and KUMC Vice Chancellor for Research. For more information about the Open Access Fund, please see http://library.kumc.edu/authors-fund.xml.For consumers today, the perceived ethicality of a foodās production method can be as important a purchasing consideration as its price. Still, few studies have examined how, neurofunctionally, consumers are making ethical, food-related decisions. We examined how consumersā ethical concern about a foodās production method may relate to how, neurofunctionally, they make decisions whether to purchase that food. Forty-six participants completed a measure of the extent to which they took ethical concern into consideration when making food-related decisions. They then underwent a series of functional magnetic resonance imaging (fMRI) scans while performing a food-related decision-making (FRDM) task. During this task, they made 56 decisions whether to purchase a food based on either its price (i.e., high or low, the āprice conditionā) or production method (i.e., with or without the use of cages, the āproduction method conditionā), but not both. For 23 randomly selected participants, we performed an exploratory, whole-brain correlation between ethical concern and differential neurofunctional activity in the price and production method conditions. Ethical concern correlated negatively and significantly with differential neurofunctional activity in the left dorsolateral prefrontal cortex (dlPFC). For the remaining 23 participants, we performed a confirmatory, region-of-interest (ROI) correlation between the same variables, using an 8-mm3 volume situated in the left dlPFC. Again, the variables correlated negatively and significantly. This suggests, when making ethical, food-related decisions, the more consumers take ethical concern into consideration, the less they may rely on neurofunctional activity in the left dlPFC, possibly because making these decisions is more routine for them, and therefore a more perfunctory process requiring fewer cognitive resources
Rubble Pile Characterization Model
Rubble piles created following the collapse of a building in a combat situation can significantly impact mission accomplishment, particularly in the area of movement and maneuver. Rubble characteristics must be known, for example, in order to predict the ability of a vehicle to override the collateral damage from weapon effects in urban areas. Two types of models are developed: a first-order model and a first-principles-based model. In both models, we assume complete rubblization of the building and develop a rubble profile model using the size and composition of the collapsed structure to predict the rubble volume. In both cases, this profile model includes the size of the footprint area surrounding the original building assuming that the rubble is free to expand horizontally as well as the resulting height of such a rubble pile. Empirical data is now needed to verify the predictive capabilities of these models
Cdk Phosphorylation of a Nucleoporin Controls Localization of Active Genes through the Cell Cycle
The localization of active genes to the nuclear periphery is regulated through the cell cycle by Cdk1 phosphorylation of a single nuclear pore protein