Chemistry Commons^™

Gas-Surface Interactions: Reactive And Non-Reactive Scattering, Azar Farjamnia

Doctoral Dissertations

The adsorption and dissociation of small molecules on metal surfaces are key steps in many industrial reactions. A detailed understanding of the dynamics of these reactions provides us with the ability to control the outcome and efficacy of the reactions. The molecule-metal interactions will lead to reorientation, energy redistribution, or bond dissociation in the molecule. The process is strongly depending upon the initial conditions, i. e. the incident energy and vibrational state of the molecule, and the surface temperature. We use a fully quantum approach to compute the dissociative sticking probability of the molecules at zero overage, on the surface …

Understanding The Surface Fouling Mechanism Of Ultrananocrystalline Diamond Microelectrodes Using Microfluidics For Neurochemical Detection, An-Yi Chang

Doctoral Dissertations

Electrochemical methods are widely used for chronic neurochemical sensing, but thus far, the organic solution redox reactions fouled the electrodes' surface. It caused the reduction of sensitivity and the electrodes' lifetime.

Here, we present the boron-doped nanocrystalline diamond microelectrodes (BDUNCD) as the next generation electrode material for neurochemical sensor development. To aid in long-term chronic monitoring of neurochemicals, they have a wide window of electrochemical potential, extremely low background current, and excellent chemical inertness. The main research goal is to reduce the rate of electrode fouling due to the reaction by-products, and significantly extend their useful lifetime.

We systematically characterize …

Electrochemical Behavior Of Dense Electrodes For Impedancemetric Nox Sensors, Nabamita Pal

Doctoral Dissertations

NOx (NO and NO2) exhaust gas sensors for diesel powered vehicles have traditionally consisted of porous platinum (Pt) electrodes along with a dense ZrO2 based electrolyte. Advancement in diesel engine technology results in lower NOx emissions. Although Pt is chemically and mechanically tolerant to the extreme exhaust gas environment, it is also a strong catalyst for oxygen reduction, which can interfere with the detection of NOx at concentrations below 100 ppm. Countering this behavior can add to the complexity and cost of the conventional NO x sensor design. Recent studies have shown that dense electrodes are less prone to heterogeneous …

Synthesis, Characterization, And Activity Of Co/Fe Alumina/Silica Supported Ft Catalysts And The Study Of Promoter Effect Of Ruthenium, Sunday Azubike Esumike

Doctoral Dissertations

The alumina and hybrid alumina-silica FT catalyst were prepared by one-step solgel/oil-drop methods using metal-nitrate-solutions (method-I), and nanoparticle-metaloxides (method-2). The nanoparticle-metal-oxides did not participate in solubility equilibria in contrast to metal nitrate in method-1 causing no metal ion seepage; therefore, method-2 yields higher XRF metal loading efficiency than method-1. The thermal analysis confirmed that the metal loading by method-1 and method-2 involved two different pathways. Method-1 involves solubility equilibria in the conversion of metal-nitrate to metal- hydroxide and finally to metal-oxide, while in method-2 nanoparticle-metal-oxide remained intact during sol-gel-oil-drop and calcination steps.

The alumina supported catalysts were dominated by γ-alumina …

Cell Modulation Using Functionalized Nanoparticles, Rui Tang

Doctoral Dissertations

Monolayer functionalized ultra-small gold nanoparticles (AuNPs) provide a versatile platform for applications in cell research. Through rational design of surface ligands, the chemistry of AuNPs are precisely regulated at atomic level. In this dissertation, applications of AuNPs in cell modulation are discussed. The topics are split into two categories. In the first category, functionalized AuNPs are harnessed to generate a robust monolayer on cell culture surface for cell modulation. The proliferation and behavior of different types of cancer cells and normal cells are modulated by tuning the surface ligands of AuNPs. Fate decision of mesenchymal stem cells are also modulated …

Evidence Of Late Quaternary Fires From Charcoal And Siliceous Aggregates In Lake Sediments In The Eastern U.S.A., Joanne P. Ballard

Doctoral Dissertations

The late-glacial transition to the Holocene, 15,000–11,600 cal yr BP, is an enigmatic period of dynamic global changes and a major extinction event in North America. Fire is an agent of disturbance that transforms the environment physically and chemically, and affects plant community composition. To improve understanding of the linkages between fire, vegetation, and climate over the late glacial and Holocene in the eastern U.S., I analyzed lake-sediment cores for charcoal and indicators of wood ash, and compared results to existing pollen records. A new microscopic charcoal record from Anderson Pond, Tennessee revealed high fire activity from 23,000–15,000 cal yr …

Engineered Nanoparticles For Detection And Treatment Of Bacteria And Biofilms, Xiaoning Li

Doctoral Dissertations

Rapid and sensitive detection and identification of bacteria woud control and prevent bacterial infection and disease, enhancing the likelihood of early diagnosis and treatment. Especially developing effective biosensor for identification of bacteria species involved in formation of biofilms, which cause chronic and persistent diseases, would promote diagnostic and therapeutic efficiency. Conventional detection methods are limited by sensitivity and required time. First part of my research has been focused on developing a rapid, simple, and sensitive biosensor aiming at portable device application for detection of bacteria in water samples. This sensor is able to detect bacteria at low concentration and generate …

Developing Spatial Reasoning Skills In General Chemistry Students, Deborah L. Carlisle

Doctoral Dissertations

The study of organic chemistry requires the understanding and use of spatial relationships, which can be challenging for many students. Prior research has shown that there is a need to develop students’ spatial reasoning skills. To that end, this study implemented guided activities designed to strengthen students’ spatial skills, with the aim of preparing students for organic chemistry and other future STEM courses. Students, taking the second semester of a two-semester general chemistry course, engaged in these activities. This study followed a quasi experimental design, in which the experimental (n = 209) and the control group (n = 212) were …

Developing 16- And 18-Atom Ringed Macrocyclic Tetracarbene Complexes, Heather Marie Bass

Doctoral Dissertations

Stabilizing metal-ligand multiple bonds is important for the understanding of biological intermediates, as well as, for their use in group transfer reactions. Two considerations to make when developing a ligand system to support metal-ligand multiple bonds are the strength of the ligand and the symmetry of the ligand. Herein, our group has proposed a class of four-coordinate, strong σ-donor ligands by synthesizing macrocyclic tetraimidazoliums that form tetracarbenes upon deprotonation. By examining group theory, these systems should allow for the formation of complexes with metal-ligand multiple bonds in a bent square pyramidal geometry that exhibit high oxidation states and novel spin …

Exploring Computational Chemistry On Emerging Architectures, David Dewayne Jenkins

Doctoral Dissertations

Emerging architectures, such as next generation microprocessors, graphics processing units, and Intel MIC cards, are being used with increased popularity in high performance computing. Each of these architectures has advantages over previous generations of architectures including performance, programmability, and power efficiency. With the ever-increasing performance of these architectures, scientific computing applications are able to attack larger, more complicated problems. However, since applications perform differently on each of the architectures, it is difficult to determine the best tool for the job. This dissertation makes the following contributions to computer engineering and computational science. First, this work implements the computational chemistry variational …

Improving Analytical Utility Of Surface Enhanced Raman Spectroscopy Through Unique Lithographic Substrate Development, Sabrina Marie Wells

Doctoral Dissertations

Surface enhanced Raman spectroscopy (SERS) has the potential to be a useful analytical technique due to large signal enhancements. Unfortunately, SERS has several drawbacks, including a lack of reproducibility, which inhibits it from being a practical option. These large signals often arise from “hot spots” of extremely high enhancement on nanofeatured metallic substrates, the most common being comprised of aggregated silver colloid. It is difficult to reproducibly create these hot spots due to the randomness of the colloid substrates. However, through controlled substrate fabrication, many problems associated with SERS analysis can be overcome. Electron beam lithography (EBL) combined with reactive-ion …