Development of a high performance parallel computing platform and its use in the study of nanostructures : clusters, sheets and tubes .

Small clusters of gallium oxide, technologically important high temperature ceramic, together with interaction of nucleic acid bases with graphene and small-diameter carbon nanotube are focus of first principles calculations in this work. A high performance parallel computing platform is also developed to perform these calculations at Michigan Tech. First principles calculations are based on density functional theory employing either local density or gradient-corrected approximation together with plane wave and gaussian basis sets. The bulk Ga2O3 is known to be a very good candidate for fabricating electronic devices that operate at high temperatures. To explore the properties of Ga2O3 at nonoscale, we have performed a systematic theoretical study on the small polyatomic gallium oxide clusters. The calculated results find that all lowest energy isomers of GamOn clusters are dominated by the Ga-O bonds over the metal-metal or the oxygen-oxygen bonds. Analysis of atomic charges suggest the clusters to be highly ionic similar to the case of bulk Ga2O3. In the study of sequential oxidation of these slusters starting from Ga2O, it is found that the most stable isomers display up to four different backbones of constituent atoms. Furthermore, the predicted configuration of the ground state of Ga2O is recently confirmed by the experimental result of Neumark's group. Guided by the results of calculations the study of gallium oxide clusters, performance related challenge of computational simulations, of producing high performance computers/platforms, has been addressed. Several engineering aspects were thoroughly studied during the design, development and implementation of the high performance parallel computing platform, rama, at Michigan Tech. In an attempt to stay true to the principles of Beowulf revolutioni, the rama cluster was extensively customized to make it easy to understand, and use - for administrators as well as end-users. Following the results of benchmark calculations and to keep up with the complexity of systems under study, rama has been expanded to a total of sixty four processors. Interest in the non-covalent intereaction of DNA with carbon nanotubes has steadily increased during past several years. This hybrid system, at the junction of the biological regime and the nanomaterials world, possesses features which make it very attractive for a wide range of applicatioins. Using the in-house computational power available, we have studied details of the interaction between nucleic acid bases with graphene sheet as well as high-curvature small-diameter carbon nanotube. The calculated trend in the binding energies strongly suggests that the polarizability of the base molecules determines the interaction strength of the nucleic acid bases with graphene. When comparing the results obtained here for physisorption on the small diameter nanotube considered with those from the study on graphene, it is observed that the interaction strength of nucleic acid bases is smaller for the tube. Thus, these results show that the effect of introducing curvature is to reduce the binding energy. The binding energies for the two extreme cases of negligible curvature (i.e. flat graphene sheet) and of very high curvature (i.e. small diameter nanotube) may be considered as upper and lower bounds. This finding represents an important step towards a better understanding of experimentally observed sequence-dependent interaction of DNA with Carbon nanotubes.

Development of a wireless platform to generate nitric oxide for implanted biomedical devices

The perturbation of homeostatic mechanisms caused by interactions between any indwelling biomedical device and the biological medium into which it is implanted initiates a dynamic wound healing response from the host which can be rigorous and ongoing. The typical result of this response is a severe degradation in the performance and safety of the device, often to the extent of precluding their clinical use. Nitric oxide (NO) is an endogenously produced biomolecule capable of mediating many of the cellular processes leveraged against implanted devices. The in vivo performance of indwelling devices prepared with NO release coatings has recently been evaluated with very encouraging results. This work developed a platform capable of both generating programmable fluxes of NO and directly evaluating the performance of indwelling probes under different profiles of NO generation. This platform can be used to improve the efficacy of NO release materials in mitigating the host response.

CHARACTERIZATION OF ELECTRODEPOSITED POLYANILINE BIOSENSOR PLATFORM FOR ESCHERICHIA COLI O157:H7 DETECTION

Amperometric electrodeposition has been used to obtain uniform, conductive, and repeatable polyaniline (PANi) thin films for use in nano scaled biochemical sensors. This report describes the characterization of these films. Techniques such as ellipsometry were used to test repeatability of the deposition and the uniformity of the deposited thin films. Raman spectroscopy was utilized to confirm the composition of the deposited PANi thin films. Fluorescence microscopy was used to determine the immobilization of antibodies to the PANi thin films using biotin-avidin interactions, as well as the density of active binding sites. Ellipsometry results demonstrated that biomolecules could be immobilized on PANi films as thin as 9nm. Evidence from the Raman spectroscopy demonstrated the conductive nature of the PANi films. The fluorescence microscopy demonstrated that antibodies could be immobilized on PANi films, although the experiment also demonstrated a low density of binding sites. The characterization demonstrates the utility of the PANi thin films as a conductive interface between the inorganic sensor platform and biochemical molecules.

INTEGRATED ASSESSMENT OF ANTHROPOGENIC, CLIMATE, AND POLICY INDUCED CHANGES OF PHOSPHORUS EXPORT IN THE UNITED STATES LAURENTIAN GREAT LAKES WATERSHEDS

Anthropogenic activities have increased phosphorus (P) loading in tributaries to the Laurentian Great Lakes resulting in eutrophication in small bays to most notably, Lake Erie. Changes to surface water quality from P loading have resulted in billions of dollars in damage and threaten the health of the world’s largest freshwater resource. To understand the factors affecting P delivery with projected increasing urban lands and biofuels expansion, two spatially explicit models were coupled. The coupled models predict that the majority of the basin will experience a significant increase in urban area P sources while the agriculture intensity and forest sources of P will decrease. Changes in P loading across the basin will be highly variable spatially. Additionally, the impacts of climate change on high precipitation events across the Great Lakes were examined. Using historical regression relationships on phosphorus concentrations, key Great Lakes tributaries were found to have future changes including decreasing total loads and increases to high-flow loading events. The urbanized Cuyahoga watersheds exhibits the most vulnerability to these climate-induced changes with increases in total loading and storm loading , while the forested Au Sable watershed exhibits greater resilience. Finally, the monitoring network currently in place for sampling the amount of phosphorus entering the U.S. Great Lakes was examined with a focus on the challenges to monitoring. Based on these interviews, the research identified three issues that policy makers interested in maintaining an effective phosphorus monitoring network in the Great Lakes should consider: first, that the policy objectives driving different monitoring programs vary, which results in different patterns of sampling design and frequency; second, that these differences complicate efforts to encourage collaboration; and third, that methods of funding sampling programs vary from agency to agency, further complicating efforts to generate sufficient long-term data to improve our understanding of phosphorus into the Great Lakes. The dissertation combines these three areas of research to present the potential future impacts of P loading in the Great Lakes as anthropogenic activities, climate and monitoring changes. These manuscripts report new experimental data for future sources, loading and climate impacts on phosphorus.