Physical Sciences and Mathematics Commons^™

An Experimental And Computational Evaluation Of The Importance Of Molecular Diffusion In Gas Gravity Currents, Jeremy Jac Herman

Graduate Theses and Dissertations

The accidental release of hazardous, denser-than-air gases during their transport or manufacture is a vital area of study for process safety researchers. This project examines the importance of molecular diffusion on the developing concentration field of a gas gravity current released into a calm environment. Questions which arose from the unexpectedly severe explosion in 2005 at Buncefield, England were of particular interest. The accidental overfilling of a large tank with gasoline on a completely calm morning led to a massive open air explosion. Forensic evidence showed that at the time of ignition, a vapor cloud, most of which now appears …

Developing A Presumptive Test For Select Synthetic Cannabinoids, Carrie Snyder

Graduate Theses and Dissertations

Synthetic cannabinoids (SC's) began to gain popularity around the world in 2009. Since then, many of the compounds have been outlawed and methods developed to detect them and their metabolites using mass spectrometry. Our work investigated the possibility of developing a colorimetric presumptive test. The SC JWH-019 was synthesized and its ketone targeted as a possible reaction site. Many SC's contain ketones and thus a reaction at this site would be applicable to many of the compounds. Since JWH-019 is costly and time consuming to synthesize, much of the experimental work was done using benzophenone (BP). BP contains a diaryl …

Microfluidics Guided By Redox-Magnetohydrodynamics (Mhd) For Lab-On-A-Chip Applications, Vishal Sahore

Graduate Theses and Dissertations

Unique microfluidic control actuated by simply turning off and on microfabricated electrodes in a small-volume system was investigated for lab-on-a-chip applications. This was accomplished using a relatively new pumping technique of redox-magnetohydrodynamics (MHD), which as shown in this dissertation generated the important microfluidic features of flat flow profile and fluid circulation. MHD is driven by the body force, FB = j × B, which is the magnetic part of the Lorentz force equation, and its direction is given by the right hand rule. The ionic current density, j, was generated in an equimolar solution of potassium ferri/ferro cyanide by applying …

Towards The Total Synthesis Of Antascomicin B. Efforts To Construct The C1-C21 Fragment, Juliette Rivero-Castro

Graduate Theses and Dissertations

Antascomicin B is a macrolide isolated from a strain of Micromonospora. It possesses structural similarities to FK506 and rapamycin and exhibits potent binding ability to FKBP12. Recent reports suggest that small molecule ligands of FKBP12 possess potent neuroprotective and neurodegenerative properties in mouse models of Parkinson's disease. Our approach to the C1-21 fragment of antascomicin B involves an asymmetric amino-Claisen rearrangement originally developed by Tsunoda et al.35 report the scalability of the preparation and rearrangement of an allylic amide possessing a silyloxy group at the terminal position of the alkene. The Tsunoda-Claisen rearrangement uses inexpensive (S)-α-methylbenzylamine as the chiral …

Steady-State Switching And Dispersion/Absorption Spectroscopy Of Multistate Atoms Inside An Optical Ring Cavity, Jiteng Sheng

Graduate Theses and Dissertations

This thesis mainly focuses on the experimental investigations of electromagnetically induced transparency (EIT) related phenomena in various systems involving multilevel atoms inside an optical ring cavity. Semiclassical methods, e.g. density-matrix equations, are used through out this thesis to simulate the experimental results. First, the cavity transmission spectrum can be significantly modified when multilevel atoms are placed inside an optical ring cavity. Such coupled atom-cavity systems are well explained by the intracavity dispersion/absorption properties. Specifically, three-level lambda-type, four-level N-type and double-lambda-type atoms inside an optical ring cavity are investigated by examining their cavity transmission spectra. Second, optical multistability (OM) has been …

Monodentate, Bidentate And Photocrosslinkable Thiol Ligands For Improving Aqueous Biocompatible Quantum Dots, Hiroko Takeuchi

Graduate Theses and Dissertations

Water-soluble Quantum Dots (QDs) are highly sensitive fluorescent probes that are often used to study biological species. One of the most common ways to render QDs water-soluble for such applications is to apply hydrophilic thiolated ligands to the QD surface. However, these ligands are labile and can be easily exchanged on the QD surface, which can severely limit their application. As one way to overcome this limitation while maintaining a small colloidal size of QDs, we developed a method to stabilize hydrophilic thiolated ligands on the surface of QDs through the formation of a crosslinked shell using a photocrosslinking approach. …

Structural Properties Of Ferroelectric Lead (Zirconium0.5,Titanium0.5)Oxygen3 Nanotube Array And Electronic Structure Of Lao Delta-Doped Strontium Titanate, Rajendra Prasad Adhikari

Graduate Theses and Dissertations

In this Dissertation we begin with two introductions on: 1) ferroelectricity and related phenomena, and 2) novel properties of Oxide electronics and the generation of two dimensional electron gas. We then give theoretical background of density functional theory (including LDA+U) and pseudopotentials. The first part of research work is about structural, polarization, and dielectric properties of ferroelectric Lead Zirconate Titanate (PZT) solid solution in the form of a nanotube array, embedded in a matrix medium of different ferroelectric strengths. We use the effective Hamiltonian derived from first-principles and finite-temperature Monte Carlo methods to determine the various properties. We revealed different …

Design And Evaluation Of A Fiber Optic Probe As A Means Of Subsurface Planetary Exploration, Robert Paul Pilgrim

Graduate Theses and Dissertations

The Optical Probe for Regolith Analysis (OPRA) is an instrumentation concept designed to provide spectroscopic analysis of the near subsurface of unconsolidated regolith on bodies such as moons, asteroids and planets. Below a chemically altered surface may lay the geological history in the form of stratigraphy that is shielded from degradation due to harsh external environments. Most of what we know about our solar system comes from remote platforms, such as satellites that are deployed into orbit around the target body. In the case of Mars, we have had several successful landers and rovers however, with the exception of the …

The Word Problem For The Automorphism Groups Of Right-Angled Artin Groups Is In P, Carrie Anne Whittle

Graduate Theses and Dissertations

We provide an algorithm which takes any given automorphism f of any given right-angled Artin group G and determines whether or not f is the identity automorphism, thereby solving the word problem for the automorphism groups of right-angled Artin groups. We do this by solving the compressed word problem for right-angled Artin groups, a more general result. A key piece of this solution is the use of Plandowski's algorithm. We also demonstrate that our algorithm runs in polynomial time in the size of the given automorphism, written as a word in Laurence's generators of the automorphism group of the given …

Fabrication Of Tungsten Tips Suitable For Scanning Probe Microscopy By Electrochemical Etching Methods, Gobind Basnet

Graduate Theses and Dissertations

The fabrication of metal tips is becoming an interesting field for scientists who are working in spectroscopy measurements. A significant amount of work has already been done in the tips fabrication process. Metal tips used to analyze the surface of materials play a key role in the scanning tunneling microscope (STM) technique. It's remarkable quality that it is used to study the surface of material at the atomic level.

There are various methods used in the tips fabrication process. Of diverse methods, three different electrochemical etching methods: submerged method, single lamella drop-off method, and double lamella drop-off method are commonly …

Modeling Chemical Reactions In Aqueous Solutions, Osman Uner

Graduate Theses and Dissertations

The energy barriers for SN2 ligand exchange reactions between the chloride anion and para-substituted benzyl chlorides were investigated both in water solution and in the gas phase by using quantum chemical simulations at the DFT and Hartree-Fock levels. The question addressed was the effect of the solvent (water) and of the substituent on the barrier height. The para substitutient groups included NH2, OH, OCH3, CH3, C(CH3)3, H, F, Cl, Br, I, CF3, CN, NO2, and SO3- . The calculations in aqueous solution were carried out with the recently developed Ultrafast Monte Carlo method using the TIP3P explicit water model. The …

Synthesis Of Platinum And Platinum-Copper Branched Nanoparticles For Electrooxidation Of Methanol, Eric Courtland Taylor

Graduate Theses and Dissertations

Platinum and Pt alloys are among the most important heterogeneous catalysts for many organic reactions and electrochemical reactions associated with the fuel cell technologies. How to reduce Pt usage while maintaining the performance of the catalysts becomes a subject for intensive research in materials chemistry. For heterogeneous catalysis, the catalytic reactivity and selectivity are strongly correlated with different crystallographic facets exposed on the surface. The facets with high-index planes whose Miller indices with at one is larger than unity are generally more active than those with low-index planes (e.g., {100}, {111}, and {110}). Tuning the morphology of the nanoparticles to …

Multiscale Study Of Batio3 Nanostructures And Nanocomposites, Lydie Louis Louis

Graduate Theses and Dissertations

Advancements in integrated nanoelectronics will continue to require the use of unique materials or systems of materials with diverse functionalities in increasingly confined spaces.

Hence, research on finite-dimensional systems strive to unearth and expand the knowledge of fundamental physical properties in certain key materials which exhibit numerous concurrent and exploitable functions.

Correspondingly, ferroelectric nanostructures, which particularly display a plethora of complex phenomena, prevalent in countless fields of research, are noteworthy candidates. Presently, however, the assimilation of zero-(0D) and one-dimensional (1D) ferroelectric into micro- or nano-electronics has been lagging, in part due to a lack of applied and fundamental studies but …

Optimization Of Sample Preparation In Matrix-Assisted Laser Desorption/Ionization (Maldi) Mass Spectrometry Of Macromolecules, Evgenia Akhmetova

Graduate Theses and Dissertations

New method for the matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) and Fourier transform mass spectrometry (MALDI-FTMS) analysis of low molecular weight polyvinyl acetate (PVAc) was developed and then applied to the characterization of commercially available chewing gum. The optimization of MALDI analysis of PVAc was achieved by investigating the influence of sample preparation variables such as the choice of solvent and choice of matrix-analyte ratio. It was demonstrated that the use of ethyl acetate as a solvent and 2,5-Dihydroxybenzoic acid as a matrix yielded the highest signal intensity for the pure polymer sample. The application of TOF technique did not …

Biodiesel Transesterification Byproducts As Soil Amendments, Solomon Parker

Graduate Theses and Dissertations

For every ten kilograms of biodiesel that is produced from the transesterification of vegetable oil, approximately 1 kg of glycerol is produced as a byproduct. Also known as glycerin, it is a chemical used in many products including cosmetics, foods, and desiccants. However, the crude glycerol created during biodiesel production is tainted with potassium hydroxide and methanol making it unsuitable for commercial use without costly refinement. With increase in production of biodiesel driven by rising fuel prices, the market has become glutted with glycerol and it is on the threshold of becoming a waste product. Common methods for disposing glycerol …

Active Galactic Nuclei Mergers And Outflows: Observations From Optical And Ultraviolet Emission Lines, Robert Scott Barrows

Graduate Theses and Dissertations

I have investigated the nature of a subset of active galactic nuclei (AGN) which show double peaks in their characteristic optical and ultraviolet emission lines. I have performed this investigation through studies of the broad emission line regions (BLRs), which are produced less than 1 pc from the central supermassive black hole (SMBH), and the narrow emission line regions (NLRs), which originate at larger (kpc) distances. The BLR studies consist of detailed line modeling of two individual quasars with double-peaked broad emission line profiles. The modeling suggests there are two primary interpretations of the complex broad line profiles. The first …

Hardy Space Properties Of The Cauchy Kernel Function For A Strictly Convex Planar Domain, Belen Espinosa Lucio

Graduate Theses and Dissertations

This work is based on a paper by Edgar Lee Stout, where it is shown that for every strictly pseudoconvex domain $D$ of class $C^2$ in $\mathbb{C}^N$, the Henkin-Ram\'irez Kernel Function belongs to the Smirnov class, $E^q(D)$, for every $q\in(0,N)$.

The main objective of this dissertation is to show an analogous result for the Cauchy Kernel Function and for any strictly convex bounded domain in the complex plane. Namely, we show that for any strictly convex bounded $D\subset\mathbb{C}$ of class $C^2$ if we fix $\zeta$ in the boundary of $D$ and consider the Cauchy Kernel Function

\mathcal{K}(\zeta,z)=\frac{1}{2\pi i}\frac{1}{\zeta-z}

as a …

Interactions Between Ions And Lysenin Nanochannels And Their Potential Applications As Biosensors, Radwan Awwad Al Faouri

Graduate Theses and Dissertations

Lysenin is classified as a pore-forming toxin protein that is isolated from the earthworm Eisenia fetida and consists of 297 amino acids [1]. Lysenin inserts large conducting pores (3.0-4.7 nm in diameter) into artificial membranes (BLM) which include sphingomyelin. These pores (channels) are open and oriented upon insertion into the bilayer lipid membrane. Lysenin channels gate at positive voltages (voltage-induced gating), but not at negative voltages. Lysenin pores also exhibit activity modulation in response to changes in ionic strength and pH, indicating that electrostatic interaction is responsible for Lysenin conductance activities. In this line of inquiries, and by modulating Lysenin …

Quantum Resonant Beats And Revivals In The Morse Oscillators And Rotors, Zhenhua Li

Graduate Theses and Dissertations

Analytical eigenfunctions and eigenvalues for the Morse oscillator were applied to investigate the quantum resonant beats and revivals of wave packet propagation. A concise way for exact prediction of the complete revival period of the Morse oscillator was given for the first time. It was suggested that any complete period was made of integer numbers of the minimum or fundamental period. Within the fundamental period, the anharmonicity of this oscillator appeared to cause interesting space-time phenomena that include relatively simple Farey-sum revival structures. In addition, a simple sum of two Morse oscillators led to a double-Morse well whose geometric symmetry …

The Geometry And Sensitivity Of Ion-Beam Sculpted Nanopores For Single Molecule Dna Analysis, Ryan Connor Rollings

Graduate Theses and Dissertations

In this dissertation, the relationship between the geometry of ion-beam sculpted solid-state nanopores and their ability to analyze single DNA molecules using resistive pulse sensing is investigated. To accomplish this, the three dimensional shape of the nanopore is determined using energy filtered and tomographic transmission electron microscopy. It is shown that this information enables the prediction of the ionic current passing through a voltage biased nanopore and improves the prediction of the magnitude of current drop signals when the nanopore interacts with single DNA molecules. The dimensional stability of nanopores in solution is monitored using this information and is improved …

New Effects Of Aging And Lattice Intercalation On Surface Properties Of Titanate Nanobelts, Roger Williams

Graduate Theses and Dissertations

Titanate nanobelts (NBs) have structural characteristics beyond that of clays. Due to a negatively charged lattice matrix of edge-shared TiO6-octahedra, the location of intercalated cations within the interlayer space may dictate the charge-conductions. This environment may in turn govern the lattice-framework's stability and surface properties, based upon our preliminary

data.

On that basis, these nanomaterials have been found in our lab to possess superb biological compatibility that is closely related to the types of the intercalated cations. In addition, a prolonged agitation was proven to enable us to manipulate the titanate NBs' length. In a parallel study, a ripening was …

Plasmonic Nanostructures For The Absorption Enhancement Of Silicon Solar Cells, Nathan Matthias Burford

Graduate Theses and Dissertations

In this work, computational investigation of plasmonic nanostructures was conducted using the commercial finite element electromagnetics solver Ansys® HFSS. Arrays of silver toroid nanoparticles located on the surface of an amorphous silicon thin-film absorbing layer were studied for particle sizes ranging from 20 nm to 200 nm in outer diameter. Parametric optimization by calculating an approximation of the photocurrent enhancement due to the nanoparticles was performed to determine optimal surface coverage of the nanoparticles. A comparison was made between these optimized nanotoroid arrays and optimized nanosphere arrays based on spectral absorption enhancement and potential photocurrent enhancement in an amorphous silicon …

The Effect Of Symmetry On The Riemann Map, Jeanine Louise Myers

Graduate Theses and Dissertations

The Riemann mapping theorem guarantees the existence of a conformal mapping or Riemann map in the complex plane from the open unit disk onto an open simply-connected domain, which is not all of the complex plane. Although its existence is guaranteed, the Riemann map is rarely known except for special domains like half-planes, strips, etc. Therefore, any information we can determine about the Riemann map for any class of domains is interesting and useful.

This research investigates how symmetry affects the Riemann map. In particular, we define domains with symmetries called Rectangular Domains or RDs. The Riemann map of an …

Further Studies On The Allylic Diazene Rearrangement, Maha Laxmi Shrestha

Graduate Theses and Dissertations

Former graduate student Wei Qi and Professor Matt McIntosh have reported diastereoselective reductive 1,3-transpositions of acyclic alpha, beta-unsaturated tosyl hydrazones to afford substrates with a 1,4-syn or 1,4-anti relationship between alkoxy and methyl groups that proceed via an ADR (Qi, W.; McIntosh, M. C. Org. Lett. 2008, 10, 357; Qi, W.; McIntosh, M. C. Tetrahedron 2008, 64, 7021). In these reports, silica gel was employed to accelerate the reduction. We have found that acetic acid gives the same results with high diastereoselectivity in the reaction. We further optimized the reaction by lowering the amount of catecholborane to 3 eq. Effects …

On Chlorine Salts: Their Detection, Stability And Implications For Water On Mars And Europa, Jennifer Hanley

Graduate Theses and Dissertations

Chlorine salts (e.g. chlorides, chlorates and perchlorates) are an important factor in the stability of water on the surfaces of planetary bodies. Here we have shown that perchlorate and chlorate salts will lower the freezing point of water, allowing it to be liquid down to ~204 K. These salts will also slow down the evaporation rate, extending the lifetime of the liquid water solution. Chlorine salts have been detected on Mars, which has significant implications for the stability of water and hence its habitability. To study their effects on the stability of water on planetary surfaces, we need to first …

Design And Fabrication Of Nanofluidic Systems With Integrated Sensing Electrodes For Rapid Biomolecule Characterization, Taylor Bradley Busch

Graduate Theses and Dissertations

A transparent nanofluidic system with embedded sensing electrodes was designed and fabricated by integrating Atomic Force Microscopy (AFM) nanolithography, Focused Ion Beam (FIB) milling and metal deposition, and standard microfabrication processing. The fabrication process started with the evaporation of chrome/gold (Cr/Au) onto a Pyrex 7740 wafer followed by photolithography and wet etching of the microchannels. The wafer was patterned a second time to form Au microelectrodes with 15-45 micrometer separation gaps in the nanochannel region. Sensing electrodes (up to one micron wide) were then deposited using FIB to bridge the gaps. The nanochannels were realized through both AFM nanolithography and …

An Investigation Of The Electronic Coupling In Some Dimeric Ruthenium (Ii) Polypyridine Complexes, Roland Ngebichie Njabon

Graduate Theses and Dissertations

A detailed understanding of respiration at the molecular level requires an understanding of the many electron transfer steps involved in the process. These electron transfer processes are extremely fast and are impossible to measure by simple rapid mixing techniques. In order to get around this problem, scientists have used laser flash photolysis. This technique relies on the fact that under proper conditions, a reactant can be generated by a very short laser pulse. Once generated, the course of the reaction can be monitored by various techniques capable of very rapid time response. Many applications of this methodology rely on the …