Physical Sciences and Mathematics Commons^™

The “Apparent” Diffusion Coefficient Of Electrons Through A Nafion Membrane, Marissa Kayle Reynolds

Graduate Theses and Dissertations

The hydrogen/oxygen fuel cell is a greener, more efficient energy solution. However, there are many problems with the fuel cell including storage, infrastructure, cost, the oxygen reduction reaction, and the durability of the proton exchange membrane (PEM). The PEM is not only used as the electrolyte for the cell but also as a physical barrier between the anode and the cathode. The integrity of this membrane is crucial to the functioning of the fuel cell. This thesis will examine using ferricyanide as a probe molecule for diagnostic experiment of Nafion membrane integrity. Using hydrodynamic voltammetry with a rotating disk electrode …

Morphology Controlled Synthesis Of Copper Based Multimetallic Nanostructures And Their Electrocatalytic Properties For Methanol Oxidation Reaction, Leanne Elizabeth Mathurin

Graduate Theses and Dissertations

This research focuses on the development of shape-controlled synthesis of Cu NM, Cu-based bimetallic and trimetallic nanostructures, and their electrocatalytic properties for methanol oxidation reaction (MOR). Copper nanomaterials (Cu NM) with specific surface facets can tailor their catalytic activity. Understanding reagents responsible for Cu NM growth is important for morphology-controlled synthesis of the nanostructures. This research studies the halide influence on Cu NM growth and morphology in an oil-based synthesis. The morphology of the Cu NM varies with the halide type (i.e., Cl-, Br-, I-), and the halide concentration. Additionally, the type of Cu precursor also influenced the morphology of …

Electrochemical Time Of Flight For Rapid And Direct Measurement Of Diffusion Coefficients, Jonathan C. Moldenhauer

Graduate Theses and Dissertations

The determination of diffusion coefficients is of fundamental importance to the understanding of electrochemistry and sensors. Developing a method by which diffusion coefficients of Red/ox active analytes can be determined quickly and elegantly, would be a great advancement over presently accepted methods. This dissertation reports the reviving electrochemical time of flight (ETOF), and developing a method that allows for empirical determination of diffusion coefficients from a single measurement. ETOF is a generate and detect experiment where the time an electrochemically generated species takes to transit a known distance is measured and related to the diffusion coefficient of the species. The …

Influence Of Histidine Residues, Ph And Charge Interactions On Membrane-Spanning Peptides, Ashley N. Henderson

Graduate Theses and Dissertations

Designed transmembrane peptides were employed for investigations of histidine residues within the hydrophobic environment of the lipid bilayer by means of oriented solid-state deuterium NMR spectroscopy. Using the model peptide GWALP23 sequence (GGALW(LA)6LWLAGA) as a host framework, the effects of single and double histidine mutations were explored. Replacement of leucine residue 12 to polar neutral histidine had little influence on the peptide average orientation, however under strongly acidic pH conditions in DOPC bilayers, the histidine becomes positively charged (pKa 2.5) and the GWALP23-H12 peptide exits the membrane and adopts a surface-bound orientation. Conversely, mutation of leucine 14 to neutral histidine …

3-Manifold Perspective On Surface Homeomorphisms For Surfaces With Very Negative Euler Characteristic, Michael Harris

Graduate Theses and Dissertations

The goal of this paper is to show for a compact triangulated 3-manifold M with boundary which fibers over the circle that whenever F is a fiber with sufficiently negative Euler characteristic the monodromymaps an essential simple closed curve or an essential simple arc in F to be disjoint from its image (possibly after isotopy). This is shown by applying the theorem of Ichihara, Kobayashi, and Rieck in [10] to the double of M to get a pair of pants. We then find an equivariant pair of pants and use it to find an essential simple closed curve or an …

Dpweka: Achieving Differential Privacy In Weka, Srinidhi Katla

Graduate Theses and Dissertations

Organizations belonging to the government, commercial, and non-profit industries collect and store large amounts of sensitive data, which include medical, financial, and personal information. They use data mining methods to formulate business strategies that yield high long-term and short-term financial benefits. While analyzing such data, the private information of the individuals present in the data must be protected for moral and legal reasons. Current practices such as redacting sensitive attributes, releasing only the aggregate values, and query auditing do not provide sufficient protection against an adversary armed with auxiliary information. In the presence of additional background information, the privacy protection …

A Bayesian Variable Selection Method With Applications To Spatial Data, Xiahan Tang

Graduate Theses and Dissertations

This thesis first describes the general idea behind Bayes Inference, various sampling methods based on Bayes theorem and many examples. Then a Bayes approach to model selection, called Stochastic Search Variable Selection (SSVS) is discussed. It was originally proposed by George and McCulloch (1993). In a normal regression model where the number of covariates is large, only a small subset tend to be significant most of the times. This Bayes procedure specifies a mixture prior for each of the unknown regression coefficient, the mixture prior was originally proposed by Geweke (1996). This mixture prior will be updated as data becomes …

Exploring Thermoresponsive Affinity Agents To Enhance Microdialysis Sampling Efficiency Of Proteins, Thaddeus Vasicek

Graduate Theses and Dissertations

Affinity agents increase microdialysis protein relative recovery, yet they have not seen widespread use within the microdialysis community due to their additional instrumentation requirements and prohibitive cost. This dissertation describes new affinity agents for microdialysis that require no additional instrumentation to use, have nearly 100% particle recovery, are 7 times more cost efficient than alternatives, and have low specificity enabling their use for a wide variety of proteins. Initially gold nanoparticles were chosen as an affinity ligand support due to their high surface area/volume ratio and colloidal stability. Poly (N-isopropylacrylamide) was immobilized to the gold nanoparticles, which served to sterically …

Infrared Energy Conversion In Plasmonic Fields At Two-Dimensional Semiconductors, Gregory Thomas Forcherio

Graduate Theses and Dissertations

Conversion of infrared energy within plasmonic fields at two-dimensional, semiconductive transition metal dichalcogenides (TMD) through plasmonic hot electron transport and nonlinear frequency mixing has important implications in next-generation optoelectronics. Drude-Lorentz theory and approximate discrete dipole (DDA) solutions to Maxwell’s equations guided metal nanoantenna design towards strong infrared localized surface plasmon resonance (LSPR). Excitation and damping dynamics of LSPR in heterostructures of noble metal nanoantennas and molybdenum- or tungsten-disulfide (MoS2; WS2) monolayers were examined by parallel synthesis of (i) DDA electrodynamic simulations and (ii) near-field electron energy loss (EELS) and far-field optical transmission UV-vis spectroscopic measurements. Susceptibility to second-order nonlinear frequency …

An Electrochemical Characterization Of A Vanadium-Based Deoxydehydration Catalyst, Joel Eric Baker

Graduate Theses and Dissertations

Alternative methods for the conversion of polyols into olefins, be it for carbon storage or hydrocarbon fuel production, have become prevalent in today’s chemical industry. One process in particular, deoxydehydration (DODH) has been proven effective in taking sustainable biomass derivatives and converting them through the utilization of various homogenous metal catalysts. While this process may show productive yields and material conversion, it is hindered by the need of a sacrificial reductant. This makes a novel process economically unviable and relatively unused outside of scientific research. That fact begs the question: Can the process be improved? It is proposed here that …

Characterization Of Coupled Gold Nanoparticles In A Sparsely Populated Square Lattice, Roy Truett French Iii

Graduate Theses and Dissertations

Metal nanoparticles deposited in regular arrays spaced at optical wavelengths support a resonance due to a coherent coupling between localized surface plasmon mode and lattice diffraction allowing for engineering of tunable devices for use in biological sensors, nanoantennae, and enhanced spectroscopy. Techniques such as electron beam lithography, focused ion beam lithography, nanosphere lithography, and nanoimprint lithography are used for fabrication but are limited by cost, device throughput, and small deposition. Polymer soft lithography and continuous dewetting of particles is a potentially viable alternative showing promise in all of those areas. This thesis developed the fabrication of a refined hydrophilic nanoimprinted …

Plasmon-Mediated Energy Conversion In Metal Nanoparticle-Doped Hybrid Nanomaterials, Jeremy Dunklin

Graduate Theses and Dissertations

Climate change and population growth demand long-term solutions for clean water and energy. Plasmon-active nanomaterials offer a promising route towards improved energetics for efficient chemical separation and light harvesting schemes. Two material platforms featuring highly absorptive plasmonic gold nanoparticles (AuNPs) are advanced herein to maximize photon conversion into thermal or electronic energy. Optical extinction, attributable to diffraction-induced internal reflection, was enhanced up to 1.5-fold in three-dimensional polymer films containing AuNPs at interparticle separations approaching the resonant wavelength. Comprehensive methods developed to characterize heat dissipation following plasmonic absorption was extended beyond conventional optical and heat transfer descriptions, where good agreement was …

Discord And Global Discord In Systems Of Coupled Quantum Dots In Driven Cavities With Dissipation, And A Method For The Calculation Of Global Discord, Willa Danielle Rawlinson

Graduate Theses and Dissertations

In the field of quantum information, which is subdivided into quantum computing and quantum cryptography, quantum correlations are essential for a performance or security boost not achievable with classical means. Various quantum correlation measures exist for evaluating a state’s potential to be a qubit (quantum bit). Entanglement, or nonseparability of quantum states, is the older, better known class of measures. However, for a mixed state, quantum entanglement is an incomplete measure of quantumness. Quantum discord, and its multibody extension global discord, encompass all quantum correlations. We study systems of coupled quantum dots using these measures.

We study the discord of …

Analysis Of Break-Points In Financial Time Series, Jean Remy Habimana

Graduate Theses and Dissertations

A time series is a set of random values collected at equal time intervals; this randomness makes these types of series not easy to predict because the structure of the series may change at any time. As discussed in previous research, the structure of time series may change at any time due to the change in mean and/or variance of the series. Consequently, based on this structure, it is wise not to assume that these series are stationary. This paper, discusses, a method of analyzing time series by considering the entire series non-stationary, assuming there is random change in unconditional …

Interactive Physics And Characteristics Of Photons And Photoelectrons In Hyperbranched Zinc Oxide Nanostructures, Garrett Edward Torix

Graduate Theses and Dissertations

As is commonly known, the world is full of technological wonders, where a multitude of electronic devices and instruments continuously help push the boundaries of scientific knowledge and discovery. These new devices and instruments of science must be utilized at peak efficiency in order to benefit humanity with the most advanced scientific knowledge. In order to attain this level of efficiency, the materials which make up these electronics, or possibly more important, the fundamental characteristics of these materials, must be fully understood. The following research attempted to uncover the properties and characteristics of a selected family of materials. Herein, zinc …

Artificial Quantum Many-Body States In Complex Oxide Heterostructures At Two-Dimensional Limit, Xiaoran Liu

Graduate Theses and Dissertations

As the representative family of complex oxides, transition metal oxides, where the lattice,

charge, orbital and spin degrees of freedom are tightly coupled, have been at the forefront

of condensed matter physics for decades. With the advancement of state-of-the-art heteroepitaxial deposition techniques, it has been recognized that combining these oxides on the atomic scale, the interfacial region offers great opportunities to discover emergent phenomena and tune materials' functionality. However, there still lacks general guiding principles for experimentalists, following which one can design and fabricate artificial systems on demand. The main theme of this dissertation is to devise and propose some …

Monte Carlo Methods In Bayesian Inference: Theory, Methods And Applications, Huarui Zhang

Graduate Theses and Dissertations

Monte Carlo methods are becoming more and more popular in statistics due to the fast development of efficient computing technologies. One of the major beneficiaries of this advent is the field of Bayesian inference. The aim of this thesis is two-fold: (i) to explain the theory justifying the validity of the simulation-based schemes in a Bayesian setting (why they should work) and (ii) to apply them in several different types of data analysis that a statistician has to routinely encounter. In Chapter 1, I introduce key concepts in Bayesian statistics. Then we discuss Monte Carlo Simulation methods in detail. Our …

Fabrication Of Infrared Photodetectors Utilizing Lead Selenide Nanocrystals, Justin Anthony Hill

Graduate Theses and Dissertations

Colloidal lead selenide and lead selenide / lead sulfide core/shell nanocrystals were grown using a wet chemical synthesis procedure. Absorbance and photoluminescence measurements were made to verify the quality of the produced nanocrystals. Absorbance spectra were measured at room temperature, while photoluminescence spectra were measured at 77 K. Organic ligands were exchanged for shorter ligands in order to increase the conductivity of the nanocrystals. Absorption and PL spectra for both core and core/shell nanocrystals were compared. Interdigital photodetector devices with varying channel widths were fabricated by depositing gold onto a glass substrate. Lead selenide nanocrystals were deposited onto these metallic …

Measuring Nonlinear Properties Of Graphene Thin Films Using Z-Scan Technique, Thekrayat Hassan Al Abdulaal

Graduate Theses and Dissertations

The nonlinear studies of two-dimensional (2D) nanomaterials, specifically graphene, are very significant since graphene is finding its usefulness in handling the enormous heat in nanoscale high-density power electronics. Graphene has emerged to be a promising nanomaterial as an excellent heat spreader due to its high thermal conductivity. However, the experimental nonlinear study of graphene materials and their application in developing future optoelectronic devices demands for more developed research.

The research objective is first to build a precise, and sensitive technique to investigate and understand the thermal nonlinear properties, including nonlinear refractive index (n2), nonlinear absorption coefficient (β), and thermo-optic coefficient …

Bioorthogonal Reactions: Synthesis And Evaluation Of Different Ligands In Copper Catalyzed Azide-Alkyne1,3-Dipolar Cycloaddition (Cuaac), Zainab Abdullah Almansaf

Graduate Theses and Dissertations

The Copper CatalyzedAzide-Alkyne1,3-Dipolar Cycloaddition (CuAAC) reaction has unique features that qualify it to be one of the best click reactions. Its applications have been shown in different aspects and for multiple purposes. The oxidative degradation of biological systems (labile proteins and live cells) is, however, generally recognized as the major problem when using this reaction in living systems. Reactive oxidation species can be easily produced in the presence of copper(II), ascorbate and air, and this is the main cause of toxicity. However, the uses of ligands have shown a major impact on reducing copper toxicity, protecting Cu(I) from the redox …

Direct Attachment Of 4-Hydroxybenzoic Acid Polymers And Capture Agents To Flat Sheet And Microdialysis Membranes For Improved Mass Transport, Sarah Jane Phillips

Graduate Theses and Dissertations

Microdialysis (MD) sampling is a diffusion-based separation method which has the ability to sample any analyte that can diffuse across the semi-permeable membrane. However one challenge for MD is that for soluble proteins greater than 10 kDa, the relative recovery (RR) using a 100 kDa MD probe is between 1-5%.1 There are two major barriers that lead to these low recovery values - nonspecific adsorption (NSA) and poor solute mass transport. To overcome these two barriers, the modification of PES-based MD membranes has been initiated by laccase. Previous researchers have used laccase to modify PES flat sheet and hollow fiber …

Synthesis, Characterization, And Fabrication Of All Inorganic Quantum Dot Leds, Haider Baqer Salman

Graduate Theses and Dissertations

Quantum Dot LEDs with all inorganic materials are investigated in this thesis. The research was motivated by the potential disruptive technology of core shell quantum dots in lighting and display applications. These devices consisted of three main layers: hole transport layer (HTL), electron transport layer (ETL), and emissive layer where the emission of photons occurs. The latter part was formed of CdSe / ZnS core-shell quantum dots, which were synthesized following hot injection method. The ETL and the HTL were formed of zinc oxide nanocrystals and nickel oxide, respectively. Motivated by the low cost synthesis and deposition, NiO and ZnO …

Investigation Of The Interaction Of Dimeric Ruthenium Complexes With Cytochrome B5, Christopher Dain Rupar

Graduate Theses and Dissertations

Photoreactive complexes to study the kinetics of electron transfer of proteins have been in use for a long time. It has always been speculated that complexes bind near the heme or the electron transfer reaction would not occur. But it is unkown exactly how the complex interacts with the protein. The structural, thermodynamic, and kinetic properties of rat liver microsomal cytochrome b5 were investigated when bound to ruthenium dimer complexes. Heteronuclear Single Quantum Coherence studies support a dynamic binding model of a dimer Ru complex bound near the protein’s heme involving residues H39, E44, G42, V61, G62, and H63. The …

Studies In The Asymmetric Synthesis Of The C21-C34 Fragment Of The Natural Product, Antascomicin B, Brian Lee Walker

Graduate Theses and Dissertations

This dissertation describes studies in the asymmetric synthesis of the C21 – C34 fragment of the natural product, antascomicin B. Antascomicin B is structurally related to FK506, binds strongly to FKBP12, yet does not shown immunosuppressive activity. Small ligand FKBP12 binding complexes were shown to have potent neuroprotective and neuroregenerative properties in mouse models of Parkinson’s disease. The highlighted chemical reactions include an asymmetric transfer hydrogenation (ATH), Ireland-Claisen rearrangement (ICR), directed hydrogenation and allylic diazene rearrangement.

Photoluminescence Measurement On Low-Temperature Metal Modulation Epitaxy Grown Gan, Yang Wu

Graduate Theses and Dissertations

A low-temperature photoluminescence (PL) study was conducted on low-temperature metal modulation epitaxy (MME) grown GaN. By comparing the PL signal from high temperature grown GaN buffer layers, and MME grown cap layers on top of the buffer layers, it was found that MME grown GaN cap has a significantly greater defect-related emission. The band edge PL from MME grown GaN found to be 3.51eV at low temperature. The binding energy of the exciton in GaN is determined to be 21meV through temperature dependence analysis. A PL peak at 3.29eV was found in the luminescence of the MME grown cap layer, …

On Compactness And Closed-Rangeness Of Composition Operators, Arnab Dutta

Graduate Theses and Dissertations

Let $\phi$ be an analytic self-map of the unit disk $\mathbb{D}:=\{z:\lvert z\rvert

Conformally Invariant Operators In Higher Spin Spaces, Chao Ding

Graduate Theses and Dissertations

In this dissertation, we complete the work of constructing arbitrary order conformally invariant operators in higher spin spaces, where functions take values in irreducible representations of Spin groups. We provide explicit formulas for them.

We first construct the Dirac operator and Rarita-Schwinger operator as Stein Weiss type operators. This motivates us to consider representation theory in higher spin spaces. We provide corrections to the proof of conformal invariance of the Rarita-Schwinger operator in [15]. With the techniques used in the second order case [7, 18], we construct conformally invariant differential operators of arbitrary order with the target space being degree-1 …

Study Of Plasmonic Properties Of The Gold Nanorods In The Visible To Near Infrared Light Regime, Pijush Kanti Ghosh

Graduate Theses and Dissertations

Nanostructures of noble metals show unique plasmonic behavior in the visible to near-infrared light range. Gold nanostructures exhibit a particularly strong plasmonic response for these wavelengths of light. In this study we have investigated optical enhancement and absorption of gold nanorods with different thickness using finite element method simulations. This study reports on the resonance wavelength of the sharp-corner and round-corner rectangles of constant length 100 nm and width 60 nm. The result shows that resonance wavelength depends on the polarization of the incident light; there also exists a strong dependence of the optical enhancement and absorption on the thickness …

Mechanism Of Rapid Electron Transfer Reactions Involving Cytochrome Bc1, Cytochrome C And Cytochrome Oxidase, Jeremy Erik Durchman

Graduate Theses and Dissertations

Electron transfer between mitochondrial proteins complexes represents the primary means by which living things acquire the requisite energy for survival. The coupling of electron transfer to proton translocation creates an electrochemical gradient that drives the synthesis of highly energetic compounds such as ATP. The purpose of these studies is to measure rates of electron transfer and elucidate the important governing factors in the redox events involving cytochrome bc1, cytochrome c and cytochrome oxidase. Using rapid initiation of redox events triggered by laser flash excitation of ruthenium compounds, and strategically monitoring unique spectral properties of these proteins in the visible region …

Two Studies: Stereoselective C-C Bond Formations Of N-Boc-Piperidines Using Selected Organolithiums And Visible-Light-Mediated Synthesis Of Fused Indolines Using Tethered Styrenes, Scott Alan Morris

Graduate Theses and Dissertations

Chemists worldwide have accepted the challenge of developing methods to access a variety of compounds as single enantiomers, including the use of enzymes, chiral auxiliaries, and resolutions. In particular, dynamic resolutions offer a unique way to access chiral compounds using a few controllable steps, including the variation of both time and temperature. Many groups have implemented this methodology to generate various polysubstituted pyrrolidines and piperidines, which are substructures ranking high on the list of nitrogen–containing pharmaceuticals.

The Gawley group revealed a catalytic dynamic resolution (CDR) of N–Boc–piperidine using a chiral ligand. Impressively, the chemistry was tolerant of a variety of …