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 …

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. …

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 …

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 …

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 …

Remediation Of Copper(Ii) And Lead(Ii) From Aqueous Solution Using Engineered Iron Oxide And Manganese Oxide Nanomaterials, Carlos Tamez Jr.

Theses and Dissertations - UTB/UTPA

Nano-sized Fe3O4, Fe2O3, Mn3O4, and MnO2 were synthesized by titration/precipitation and characterized using powder XRD. pH assays determined that optimum binding occurred at pH 4 for Fe3O4 and Fe2O3 and pH 3 for Mn3O4 and MnO2. Maximum adsorption of Cu(II) and Pb(II) occurred within 20 min or less of contact with the nanomaterials. The synthesized nanomaterials showed a binding preference for Pb(II) over Cu(II) at concentrations above 50 ppm. Batch studies also showed no significant reduction in the binding of copper and lead to either Fe3O4, Fe2O3, Mn3O4, or MnO2 in the presence of Na+ , K+ , Mg2+ or …

Biological Compatibility And Cytotoxicity Studies Of Hepa-1c1c7, Hepg2, And Mcf-7 Cancer Cell Lines Upon Exposure To Silver, Palladium, And Gold Nanoparticles, M. Esther Salinas

Theses and Dissertations - UTB/UTPA

The field of nanomedicine has recently explored potential applications for cancer treatment ranging from drug delivery methods to cancer imaging techniques. Due to potential risks of nanomaterials affecting non-cancerous cells in the body, in vitro toxicity studies are being conducted. The nanoparticles (NPs) were synthesized from potassium tetrachloroaurate (III) hydrate, potassium tetrabromoaurate (III) dihydrate, potassium tetrachloropalladate (II), and silver nitrate. NPs were synthesized using the Turkevich method or through the sodium borohydride reduction. Particles synthesized using sodium borohydride were stabilized with cetyltrimethylammonium bromide (CTAB). The NPs under investigation were used to treat three cancer cell lines. The treated cells were …

Oxidation Of Dibenzothiophene To Dibenzothiophene Sulfone Using Tungsten (Vi) Oxide, Alejandrina Rivera

Theses and Dissertations - UTB/UTPA

The oxidation of dibenzothiophene (DBT) to dibenzothiophene-sulfone has been considered as an alternate method to remove sulfur from crude oil. This study demonstrates that the oxidative desulfurization (ODS) of DBT to DBT-sulfone occurs using WO3 as a catalyst. WO3 was synthesized and characterized using X-ray diffraction to determine the phase of WO3. Each reaction was refluxed and run for four hours using WO3 as a catalyst, dibenzothiphene, and four different solvents: decahydronapthalene, n-dodecane, decalin, and dodecane. The reactions were performed at temperatures ranging from 120 oC to 150 oC. Aliquots were taken at 30 minutes for up to four hours …

The Computation Of Fluid Velocity In A Closed Cavity With A Moving Lid, Daniel A. Montez

Theses and Dissertations - UTB/UTPA

We consider a cavity filled with fluid whose three sides are stationary and the lid at the top is moving at a constant speed. The flow in the cavity is modeled using the conservation of mass and momentum equations with proper boundary conditions. We compute the fluid velocity for the steady state case using the finite element method. We seek the weak formulation and develop a finite element model based on the Galerkin method. Furthermore we use the penalty function method to modify our weak formulation to eliminate the pressure. The Gaussian quadrature method is used to evaluate our integrals …

Reduction Of Nitroaromatic Compounds With Sodium Borohydride Using Transition Metal Sulfides, Samuel Pina Jr.

Theses and Dissertations - UTB/UTPA

The following systems: NaBH4/Fe3S4, NaBH4/Co3S4, NaBH4/NiS, NaBH4/CuS, and NaBH4/ZnS, were investigated for their nitro reducing abilities. Quantitative conversions were observed for the reduction of nitrobenzene with NaBH4/Co3S4 and NaBH4/NiS systems as opposed to only 9% conversion without any catalyst, representing a ten-fold increase in the reducing ability of NaBH4. In ethanol, various nitroaromatic compounds were also successfully reduced in moderate to high yields with 3 molar equivalents of NaBH4, demonstrating a mild alternative for the effective reduction of nitroaromatic compounds to their corresponding aryl amines. Screening of catalysts was carried out using gas chromatography. All products were characterized using 1 …

Electrospinning Polymer Blends For Biomimetic Scaffolds For Acl Tissue Engineering, Vanessa Lizeth Garcia

Theses and Dissertations - UTB/UTPA

The anterior cruciate ligament (ACL) rupture is one of the most common knee injuries. Current ACL reconstructive strategies consist of using an autograft or an allograft to replace the ligament. However, limitations have led researchers to investigate tissue engineered grafts, known as scaffolds, through electrospinning. Scaffolds made of natural and synthetic polymer blends have the potential to promote cell adhesion while having strong mechanical properties. However, enzymes found in the knee are known to degrade tissues and affect the healing of intra-articular injuries. Results suggest that the natural polymers used in this study modify the thermal properties and tensile strength …

Oxidation Of Dibenzothiophene To Dibenzothiophene Sulfone Using Tio2, Juan H. Leal

Theses and Dissertations - UTB/UTPA

The oxidation of dibenzothiophene (DBT) to dibenzothiophene-sulfone has been considered as an alternate method to remove sulfur from crude oil. This study demonstrates that the oxidative desulfurization (ODS) of DBT to DBT-sulfone occurs using rutile TiO2 as a catalyst with the aid of O2. In addition, anatase and brookite were synthesized and tested in the reaction. Particle size of the catalysts was calculated and morphology was explored using SEM. A kinetic study was performed to determine the catalytic effect and activation energy of TiO2. The oxidation reaction was carried out by refluxing TiO2 and DBT in decahydronapthalene while flowing O2 …

Disk Diffusion Breakpoint Determination Using A Bayesian Nonparametric Variation Of The Errors-In-Variables Model, Glen Richard Depalma

Open Access Dissertations

Drug dilution (MIC) and disk diffusion (DIA) are the two most common antimicrobial susceptibility tests used by hospitals and clinics to determine an unknown pathogen's susceptibility to various antibiotics. Both tests use breakpoints to classify the pathogen as either susceptible, indeterminant, or resistant to each drug under consideration. While the determination of these drug-specific MIC classification breakpoints is straightforward, determination of comparable DIA breakpoints is not. It is this issue that motivates this research.

Traditionally, the error-rate bounded (ERB) method has been used to calibrate the two tests. This procedure involves determining DIA breakpoints which minimize the observed discrepancies between …

Measurement Of A Weak Transition Moment Using Coherent Control, Dionysios Antypas

Open Access Dissertations

We have developed a two-pathway Coherent Control technique for measurements of weak optical transition moments. We demonstrate this technique through a measurement of the transition moment of the highly-forbidden magnetic dipole transition between the 6s²S_1/21/2 and 7s²S_1/21/2 states in atomic Cesium. The experimental principle is based on a two-pathway excitation, using two phase-coherent laser fields, a fundamental field at 1079 nm and its second harmonic at 539.5 nm. The IR field induces a strong two-photon transition, while the 539.5 nm field drives a pair of weak one-photon transitions: a Stark-induced transition of …

Nanoscale Semiconductor Materials And Devices Employing Hybrid 1d And 2d Structures For Tunable Electronic And Photonic Applications, Suprem Ranjan Das

Open Access Dissertations

Das, Suprem R. Ph.D., Purdue University, December 2013. Nanoscale Semiconductor Materials and Devices employing Hybrid 1D and 2D structures for Tunable Electronic and Photonic Applications. Major Professor: Dr. David B. Janes.

Continued miniaturization of microelectronic devices over past decades has brought the device feature size towards the physical limit. Likewise, enormous `waste energy' in the form of self-heating in almost all of the electronic and optoelectronic devices needs an `energy-efficient low power' and `high performance' material as well as device with alternate geometry. III-V semiconductors are proven to be one of the alternate systems of materials for various applications including …

Spectroscopic And Kinetic Study Of Copper-Exchanged Zeolites For The Selective Catalytic Reduction Of Nox With Ammonia, Shane Adam Bates

Open Access Dissertations

The recent application of metal-exchanged, small-pore zeolites for use in the selective catalytic reduction (SCR) of NO_x with ammonia NH₃ for automotive deNO_x applications has been a great stride in achieving emission standard goals. Copper-exchanged SSZ-13 (Cu-SSZ-13), the small-pore zeolite in this study, has been shown to be very hydrothermally stable and active under conditions presented in the exhaust of the lean-burn diesel engine. In this work, detailed studies were performed to identify many aspects of the active site(s) in Cu-SSZ-13 in order to learn about the standard SCR mechanism.

A series of seven Cu-SSZ-13 samples were …

Construction And Demonstration Of A Tandem Mass Spectrometer Based Instrument For Cold Ion Spectroscopy, James Gerhardt Redwine

Open Access Dissertations

A new instrument incorporating ion trap based tandem mass spectrometry and cold ion UV and UV-IR double resonance spectroscopy has been developed at Purdue University for the study of gas phase, biologically relevant ions. The instrument incorporates multiple quadrupole linear ion trap mass analyzers to prepare and isolate the precursor ions as well as to analyze the resultant photofragments. A 22-pole ion trap cooled to 5 K via a closed cycle helium cryostat is used to cool the ions for spectroscopic interrogation. Results show the vibrational and rotational temperature of a wide assortment of ions to be 12±2 K.

The …

Continued Progress Towards Efficient Syntheses Of Cephalostatin North 1 Analogs, Daniel Preston Jamieson

Open Access Dissertations

Jamieson, Daniel P. Ph.D., Purdue University, December 2013. Continued Progress Towards Efficient Syntheses of Cephalostatin North 1 Analogs. Major Professor: PhilipL. Fuchs.

The cephalostatins and ritterazines represent an intriguing class of marine natural products in both structure and biological activity, and the progress towards the synthesis of high valued analogs with a focus on process orientated methodology is described herein. Included in the pages to follow, is the further advancement of the `Red-Ox' strategy toward the highly efficient synthesis of 25-epi-4,15-dihydro-North 1, Chapter 2. A short review focusing on the earlier efforts toward the main synthetic challenges of North 1 …

Elucidation Of Chiral Recognition Mechanisms Of Solutes By Amylose Tris[(S)-Alpha-Methylbenzylcarbamate] Sorbent, Hung-Wei Tsui

Open Access Dissertations

Enantioselective separations of chiral molecules are important in various chemical fields, such as pharmaceuticals and agrochemicals industries. Polysaccharide-based sorbents have been widely used in chiral liquid chromatography. The recognition mechanisms which determine their enantioselectivities are not completely understood.

In this dissertation, the chiral recognition mechanisms of a widely used commercial sorbent, amylose tris[(S)-alpha-methylbenzylcarbamate], for benzoin (B) enantiomers were first studied. The HPLC data for benzoin with pure n-hexane as the mobile phase have been obtained. The behavior of sorbent-solute-hexane systems can be interpreted by considering only sorbent solute two-component interactions. Infrared (IR) spectra showed evidence of substantial hydrogen bonding (H-bonding) …

Design, Synthesis, And Evaluation Of Molecular Inhibitors For Biologically Relevant Enzymes, Sarah Emma St. John

Open Access Dissertations

The work in this thesis details the design, synthesis, and biological evaluation of molecular inhibitors for the inhibition of biologically relevant enzymes. The first three chapters of this thesis concern the polyphenol resveratrol and its inhibition of the quinone reductase 2 (QR2) enzyme. The work on this subject resulted in the complete design, synthesis, biological and structural evaluation of a second generation library of resveratrol analogues. From this work we identified a novel resveratrol analogue that inhibits QR2 in a previously unknown binding orientation. The fourth chapter of this thesis details the de novo design of molecules for the inhibition …

Atomistic Simulation Of Plasma Interaction With Plasma Facing Components In Fusion Reactors, Xue Yang

Open Access Dissertations

The interaction between plasma and fusion relevant materials is one of the critical issues in successfully using those materials in Tokamak reactors. This research uses molecular dynamics, kinetic Monte Carlo and binary collision approximation methods to model fusion relevant material bombarded by energetic particles to investigate retention, deposition, sputtering, erosion, blistering effects, diffusion, and so on.

The deuterium bombardment of monocrystalline tungsten was modeled by LAMMPS code using Tersoff type interatomic potential. The deuterium trapping rate, implantation depth, and stopping time in 600-2000 K tungsten bombarded by 5-100 eV deuterium atoms were simulated. Irradiated monocrystalline tungsten became amorphous prior to …

Gamma-Ray Observations Of X-Ray Binaries, Angelo Varlotta

Open Access Dissertations

The detection of GeV/TeV emission from X-ray binaries (XRBs) has established a new class of high-energy (HE, >0.1 GeV) and very-high-energy (VHE, >100 GeV) gamma-ray emitters. XRBs are formed by a compact object, either a neutron star or a black hole, and by an optical companion star. Some XRBs are known to possess collimated relativistic jets, and are called microquasars. VERITAS has conducted observations of the high-mass X-ray binary (HMXB) 1A 0535+262 and of the microquasar Cygnus X-3. Many theoretical models predict VHE emission when these sources manifest persistent relativistic jets or transient ejections. In light of these considerations, VERITAS …

Gas-Phase Covalent And Non-Covalent Ion/Ion Chemistry Of Biological Macromolecules, John Robert Stutzman

Open Access Dissertations

Gas-phase ion/ion chemistry involves the interaction of oppositely charged ions inside of the mass spectrometer. During this gas-phase chemistry, particle transfer (i.e., proton and electron) or synthesis can occur at rapid reaction rates. Particle transfer represents a mature area of ion/ion chemistry, while selective covalent modification represents a fairly new area of gas-phase chemistry. Gas-phase covalent chemistry is based on traditional solution phase organic chemistry.

The work demonstrated in this dissertation greatly involves gas-phase covalent and non-covalent Schiff base chemistry on peptide and protein ions. The reagent dianion, 4-formyl 1,3-benzene disulfonic acid, has been used to covalently modify unprotonated primary …

Estimation Of Variation For High-Throughput Molecular Biological Experiments With Small Sample Size, Danni Yu

Open Access Dissertations

Motivation: In the quantification of molecular components, a large variation can affect and even potentially mislead the biological conclusions. Meanwhile, the high-throughput experiments often involve a small number of samples due to the limitation of cost and time. In such cases, the stochastic information may dominate the outcome of an experiment because there may not be enough samples to present the true biological information. It is challenging to distinguish the changes in phenotype from the stochastic variation.

Methods: Since the biological molecules have been quantified with different technologies, different statistical methods are required. Focusing on three types of important high-throughput …

Implementation Of A Research-Based Lab Module In A High School Chemistry Curriculum: A Study Of Classroom Dynamics, Matthew Pilarz

Open Access Dissertations

Pilarz, Matthew. Ph.D., Purdue University, December 2013. Implementation of a Research-Based Lab Module in a High School Chemistry Curriculum: A Study of Classroom Dynamics. Major Professor: Gabriela C. Weaver.

For this study, a research-based lab module was implemented in two high school chemistry classes for the purpose of examining classroom dynamics throughout the process of students completing the module. A research-based lab module developed for use in undergraduate laboratories by the Center for Authentic Science Practice in Education (CASPiE) was modified and implemented in two high school settings. This module consisted of four phases: Skill Building, Experimental Design, Independent Research, …

Silica Colloidal Crystals As Emerging Materials For The High-Throughput Sizing Of Proteins By Packed Capillary Electrophoresis, Nadine K. Njoya

Open Access Dissertations

Protein heterogeneity is currently one of the leading problems in formulation of therapeutic proteins. The effectiveness of therapeutic proteins is diminished when they exhibit heterogeneity due to aggregates and degradation by-products. Furthermore, guidelines set forth by the FDA require therapeutic proteins to have high stability as well as high purity. With development time on the order of years and costs incurred in the millions, pharmaceutical companies are investing more time in finding fast and efficient ways to screen for protein heterogeneity. Current methods such as native polyacrylamide gel electrophoresis (PAGE), size-exclusion chromatography (SEC) and capillary electrophoresis (CE) are time consuming, …

Utilizing Electron Microscopy And Spectroscopy Methods To Understand Water Structure And Water Doping, Lior Miller

Open Access Dissertations

Water is the second most common element in the universe and the most studied material on earth. Most of the studies concerning water are from the fields of chemistry and biology. Hence, the structure of water molecules and short range order and interactions are well characterized and understood. However, the collective arrangement of water molecules and the long range order are still missing. Understanding of this long range order in water is needed, as it is the key to many water activities.

To fill this gap, this study utilizes a new direct method for characterization of water in the vapor …

Spectroscopic Characterization Of The Water-Oxidation Intermediates In The Ru-Based Catalysts For Artificial Photosynthesis, Dooshaye Moonshiram

Open Access Dissertations

Utilization of sunlight requires solar capture, light-to-energy conversion and storage. One effective way to store energy is to convert it into chemical energy by fuel-forming reactions, such as water splitting into hydrogen and oxygen. Ruthenium complexes are among few molecular-defined catalysts capable of water splitting. Insight into the mechanism of their action will help to design future robust and economically feasible catalysts for light-to-energy conversion. Mechanistic insights about the design of such catalysts can be acquired through spectroscopic analysis of short-lived intermediates of catalytic water oxidation. Development of time-resolved approaches through stopped flow UV-Vis Spectroscopy to follow the catalysis of …

Methods For Increasing Domains Of Convergence In Iterative Linear System Solvers, David Michael Imberti

Open Access Dissertations

In this thesis, we introduce and improve various methods for increasing the domains of convergence for iterative linear system solvers. We rely on the following three approaches: making the iteration adaptive, or nesting an inner iteration inside of a previously determined outer iteration; using deflation and projections to manipulate the spectra inherent to the iteration; and/or focusing on reordering schemes. We will analyze a specific combination of these three strategies. In particular, we propose to examine the influence of nesting a Flexible Generalized Minimum Residual algorithm together with an inner Recursive Projection Method using a banded preconditioner resulting from the …