No description available.

No description available.

Measurement of soil phytase activity (PA) and delineation of the impact of this important phosphomonoesterase on the P-cycling process in soil and sediments suffer from the lack of a reliable assay. A method for measuring PA in soil that promises to be accurate and reliable has been recently published. The method involves the use of a novel chromophoric analog of phytic acid, referred to as T(tethered)InsP5 (5-O-[6-(benzoylamino)hexyl]-D-myo-inositol-1,2,3,4,6-pentakisphosphate). This study was conducted to measure PA in a Clymer forest soil, which contained over twice the amount of soil organic C as previously tested soils, using the TInsP5 PA assay. This investigation specifically addresses: (1) the development of a soil dilution technique for determining maximal PA, (2) identification of previously unsubstantiated soil-produced dephosphorylated intermediate probe species, (3) the impact of increasing assay buffer pH on soil PA and (4) testing stability of the probe's amide bond in a highly (bio)active forest soil. PA assays were conducted by measuring dephosphorylation of TInsP5 in citrate-acetate buffered (pH 4.2) active and autoclaved (Control) soil suspensions. Phosphorylated probe intermediates (i.e., TInsP4, TInsP3, TInsP2 and TInsP1) and T-myo-inositol were extracted from samples of soil suspension following incubation. Probe species were quantified using reversed phase high-performance liquid chromatography (RPHPLC) with UV detection. PA was calculated based on a mass balance approach. A soil dilution technique was developed to address the challenge of determining maximal PA in soils containing higher organic matter content. In the initial report on use of the TInsP5 method for measuring PA in soil, two "soil-generated" UV-adsorbing compounds (designated Y and Z) were observed, but never confirmed as probe species. The experimental evidence presented in this report supports inclusion of compound Y as a phosphorylated probe intermediate species (i.e. TInsPy), based primarily on its UV adsorption spectra (diode-array detection analysis). Compound Z could not be substantiated as a probe species based on the evidence presented in this study. PA of Claymer forest soil decreased with an increase in assay buffer pH. Further, the probe's amide bond linkage was stable in a forest soil exhibiting high PA. / Master of Science

Sampling small scale ocean turbulence is one of the most important problems in oceanography. The turbulence can be near the noise level of current microscale profiling techniques and these techniques do not provide spatially and temporally dense measurements and can be labor intensive. A 5 beam acoustic Doppler current profiler (VADCP) can more accurately measure three components of fluid velocity in a column. By towing such a device in a sensor platform, called a towfish, one may measure turbulent mixing in a vertical swath of the ocean. If the towfish attitude is not precisely regulated, however, the turbulence measurements can be irreversibly corrupted. A two-part tow that includes a depressor weight between the towing vessel and the towfish can provide some degree of disturbance rejection. Passive devices alone, however, can not meet the performance requirements for measuring ocean turbulence. This thesis presents a design for a two-stage towing system which will be used to measure ocean turbulence. The focus is on the towfish, which includes independently actuated stern planes for pitch and roll disturbance rejection. The thesis also describes design and analysis of an active control system to precisely regulate the pitch and roll attitude of a streamlined towfish. A three dimensional numerical model is presented and a PID controller is developed to provide active attitude stabilization. The effect of random depressor motions on the towfish dynamics is assessed for both the uncontrolled and the feedback-controlled case. The numerical investigation also considers variations in parameters such as tether length and CG location. / Master of Science

This thesis describes the development of new osmium-mediated methodologies providing novel applications through the use of a third generation of reoxidant for osmium. Chapter 1, The introduction: Summary of past and present methodologies towards the synthesis of the 1,2 amino alcohol motif. Chapter 2, Intramolecular processes: The studies of the tethered aminohydroxylation (TA) of amide and urea derivatives are being investigated. Chapter 3, Investigations towards an intermolecular process: The transposition of the TA methodology to an intermolecular process and the requirements involved are discussed. The role of acetamide is being investigated. Chapter 4, Successful transition to an intermolecular process: Amino acid derivatives became for the first time possible nitrogen sources and were efficiently employed through osmium-mediated reaction to afford interesting biological scaffolds. Chapter 5, Experimental: Full experimental procedures and characterisation of compounds are reported. References: A complete list of citations employed in the previous five chapters is provided. Appendix: Full documentation of X-ray crystal structures, key NMR spectra and HPLC traces is provided.

The fragmentation of γ-silyloxy-β-hydroxy-α-diazoesters to provide tethered aldehyde ynoates was discovered and developed in Prof. Brewer's laboratory. This reaction is a Lewis acid mediated heterolytic cleavage of the Cβ-γ bond of a γ-silyloxy-β-hydroxy-α-diazocarbonyl functional group array contained in a ring compound. This dissertation describes a further study of this ring fragmentation reaction and application of this fragmentation to the preparation of synthetically useful organic molecules. The purpose of this dissertation work was three fold. The first objective was to extend this ring fragmentation reaction to the synthesis of tethered aldehyde ynones by fragmenting various γ-silyloxy-β-hydroxy-α-diazo ketone compounds. The second objective was to develop a new way to make medium size rings by fragmenting fused bicyclic γ-silyloxy-β-hydroxy-α-diazo ketones. The final goal was to use this reaction to make medium size ynolides by fragmentation of fused bicyclic γ-silyloxy-β-hydroxy-α-diazo esters to provide core structures for medium-size lactones which are synthetically challenging to make using other available methods.

N-heterocyclic carbenes (NHCs) can be used as ligands for organometallics complexes, which can then facilitate numerous catalytic applications, such as, C-H activation, small molecule activation and numerous materials applications. The use of anionically-tethered NHCs for usage with electropositive metals has been pioneered by the Arnold group within the last decade. This thesis describes the synthesis of both aryloxide- and amide-tethered NHC organometallic complexes of s-, p-, d- and f-block metals to provide a platform for small molecule activation. Once synthesised, the reactivity of some of these complexes were tested by reaction with CO2 with the aim of turning a molecule considered a harmful (environmentally), waste product into value added products, potentially providing an alternative fuel source. Chapter One introduces the use of anionically-tethered NHCs for use in a number of organometallic complexes as well as their current potential as catalysts for a number of important small molecules. This chapter focuses upon the differences between complexes tethered with anionic O, N, P, S elements, f-element NHC complexes and the use of d-block NHC complexes for catalysis. Chapter Two contains the synthesis and characterisation of a number of aryloxy-tethered NHC p-, d- and f-block organometallic complexes using the ligand H2(LArO R)2. The synthesis of SnII complexes including the synthesis of new ‘normal’ ‘abnormal’ complexes given enough steric bulk around the Sn centre due to the lone pair present in Sn complexes, preventing one of the ligands binding through the classical carbene position and therefore binding through the backbone C4 carbon. The synthesis of MII (Zn, Co and Fe) complexes to compare the solid-state structure and binding mode of the carbenes. The synthesis and characterisation of MIII (Ce and Eu) complexes to assess the solid-state structure and binding modes within f-bock complexes. Chapter Three investigates the reactivity of the MII complexes (Sn, Zn, and Fe) with CO2. Successful reactions were characterised using NMR and further treated with alkynes to target catalytic reactions. Chapter Four contains reactions to target a number of amide-tethered bis (NHC) s-, p-, d- and f-block organometallic complexes using the proligand, H4(LN Mes)Cl3. Deprotonation studies undertaken with a number of bases to give the MI (Li and K) salts and MII (Mg) salts and proved to be unsuccessful upon isolation. Reactions to synthesise the p-, d- and f-block complexes were then undertaken using in situ free carbene production as well as the attempted isolation of the free carbene, both of which also proved unsuccessful. Chapter Five provides an overall conclusion to the work presented in Chapters Two, Three and Four within this thesis. Chapter Six gives the experimental and characterising data for the complexes and reactions.

The major goals of this work were to: develop a new methodology for the preparation of site-isolated catalytic sites on a silica surface, prepare the first truly single-site supported metallocene/CGC polymerization catalyst, and develop structure-reactivity relationships for these new systems. To synthesize these novel catalysts, the approach taken was to develop a protocol which allows for the synthesis of an aminosilica material with isolated, uniform amine sites. This patterned aminosilica was then used as a scaffold to support a constrained geometry catalyst. These functionalizations occurred at essentially a quantitative level, in stark contrast to previous literature reports. The patterned catalysts were evaluated in the polymerization of ethylene and compared to densely loaded literature materials. Overall, it was found the patterned materials were 5-10 times more active than traditional immobilized CGC catalysts. The patterned catalysts were also found to be effective catalysts for the copolymerization of norbornenes (including functionalized norbornenes) and ethylene, the first reported use of a tethered CGC for the production of ethylene-norbornene copolymers. The control materials were inactive in these polymerizations, providing further evidence that the patterning protocol allows for the synthesis of unique highly active, isolated catalytic sites. Various structural components of the immobilized CGC developed in this work were tested for their impact on catalyst synthesis and reactivity in ethylene polymerizations. The results showed the patterned materials in general behaved according to the trends seen in homogeneous CGC polymerizations. These results, while congruent with similar homogeneous CGC studies, are in direct conflict with previous work on supported CGCs reported in the literature. This discrepancy is likely the result of the difference between the isolated, possibly single-site patterned catalysts developed in the course of this work and the multi-sited catalysts prepared by traditional supporting protocols. This also further illustrates the difficulty in developing structure-reactivity relationships when ill-defined solid catalysts are used.

Command generation is a process by which input commands are constructed or modified such that the system's response adheres to a set of desired performance specifications. Previously, a variety of command generation techniques such as input shaping have been used to reduce residual vibration, limit transient deflection, conserve fuel or adhere to numerous other performance specifications or performance measures. This dissertation addresses key issues regarding the application of command generation techniques to tethered satellite systems. The three primary objectives of this research are as follows: 1) create analytically commands that will limit the deflection of flexible systems 2) combine command generation and feedback control to reduce the retrieval time of tethered satellites, and 3) develop command generation techniques for spinning tether systems. More specifically, the proposed research addresses six specific aspects of command generation for tethered satellites systems: 1) create command shapers that can limit the trajectory tracking for a mass under PD control to a pre-specified limit in real time 2) create commands analytically that can limit the transient deflection of a model with one rigid-body and one flexible mode during rest-to-rest maneuvers 3) command generation for a 2-D model of earth-pointing tethered satellites without tether flexibility, 4) command generation for a 2-D model of earth-pointing tethered satellites to reduce tether retrieval time and reduce swing angle, 5) command generation for a 3-D model of earth-pointing tethered satellites without tether flexibility, and 6) command generation for improved spin-up of spinning tethered satellite systems. The proposed research is anticipated to advance the state-of-the-art in the field of command generation for tethered satellite systems and will potentially yield improvements in a number of practical satellite and tether applications.

Interactions between the aerodynamics and dynamics of bluff bodies are important in many engineering applications, including suspension bridges, tall buildings, oil platforms, wind turbine towers, air drops, and construction with cranes. In the rotorcraft field, bluff bodies are commonly suspended underneath the vehicle by tethers. This approach is often the only practical way to deliver a payload in a reasonable amount of time in disaster relief efforts, search-and-rescue operations, and military operations. However, currently a fundamental understanding of the aerodynamics of these bluff bodies is lacking, and accurate dynamic simulation models for predicting the safe flying speed are not available. In order to address these shortcomings, two main advancements are presented in this thesis. The aerodynamics of several three-dimensional canonical bluff bodies are examined over a range of Reynolds numbers representative of wind-tunnel-scale to full-scale models. Numerical experiments are utilized, with a focus on uncertainty analysis and validation of the computations. Mean and unsteady forces and moments for these bluff bodies have been evaluated, and empirical models of the shear layer characteristics have been extracted to quantify the behaviors and provide predictive capability. In addition, a physics-based reduced-order simulation model has been developed for bluff bodies. The physics-based approach is necessary to ensure that the predicted behavior of new configurations is accurate, and it is made possible by the breakthroughs in three-dimensional bluff body aerodynamics presented in this thesis. The integrated aerodynamic forces and moments and dynamic behavior predicted by model are extensively validated with data from wind tunnels, flight tests, and high-fidelity computations. Furthermore, successful stability predictions for tethered loads are demonstrated. The model is applicable to the simulation of any generic bluff body configuration, is readily extensible, and has low computational cost.