Physical Sciences and Mathematics Commons^™

A Diffuse Reflectance Infrared Fourier Transform Spectroscopic Investigation Of The Oxidation Of Co On Platinum/Tin(Iv) Oxide-Based Catalysts, Julie Christi Stiltner Patrick

Chemistry & Biochemistry Theses & Dissertations

Platinum/tin(IV) oxide-based catalysts have been developed for the oxidation of carbon monoxide at 55 °C and 1 atmosphere pressure. A diffuse reflectance infrared fourier transform spectroscopic (DRIFTS) investigation of this oxidation has been performed. Four catalyst samples have been subjected to a 5% carbon monoxide pretreatment at 125 °C, helium exposure at 55 °C, bottled air (20% oxygen) exposure at 55 °c, and exposure to a 2:1 stoichiometric mixture of carbon monoxide and oxygen at 55 °C. During the course of these exposures, evidence for the development of two different surface carbon monoxide configurations has been found: one that is …

An Ultra-Sensitive Electrochemical Enzyme Immunoassay For Thyroid Stimulating Hormone In Human Serum, Zhengrong Yu, Yan Xu, Michael P.C. Ip

Chemistry Faculty Publications

A sensitive heterogeneous electrochemical enzyme immunoassay has been developed for thyroid stimulating hormone (TSH) by modifying a commercially available two-site immunoenzymometric assay. p-Aminophenyl phosphate (PAPP) was used as the substrate of alkaline phosphatase, and hydrolysed to p-aminophenol (PAP). The amount of PAP produced from the assay was proportional to the amount of TSH in the sample. Detection of PAP was done by oxidative amperometry in a flow injection system. The working electrode was a glassy carbon electrode whose potential was held at +325 mV (vs Ag/AgCl). The amperometric detection of PAP required only 1 μl of sample (the range of …

Synthesis Of A Hybrid Baldwin Peptide: A Study In The Factors That Influence Helix Formation, Jay Steven Berger

Honors Theses

In this study, a hybrid i+4/i+3 peptide will be synthesized. It is assumed that this configuration will enhance the formation of the alpha­helix. Previous research has determined that a complete helical tum requires 3.6 amino acid residues. The hybrid peptide will include four residues followed by a second helical tum which will only encompass three residues. It is hoped that by slightly over turning and then under turning the helix, the stability of the overall helix formation will be enhanced.

The Binding Of 2-Acetylnaphthalene To Beta-Cyclodextrin Polymers Studied By Fluorescence Quenching, Jason T. Graves

Honors Theses

Cyclodextrin (CD) molecules can form inclusion complexes with many different types of organics due to the hydrophobic environment of the CD internal cavity. The flurophore-2-acetylnapthalene (2-AN) has a high flourescence intensity in polar solvents such as water. Therefore, its fluorescence is quenched when it forms a complex with a CD molecule and is contained in the non-polar cavity. By measuring the change in flourescence intensity in the presence of CD, we can calculate the binding constant for CD:2-AN complex formation.

The Charge Of The Zinc Ion In Atcase And Its Effect On Tertiary Structure, Michelle L. Dietrich

Honors Theses

Metals present in enzymes serve a variety of functions. Often they are involved in enzyme catalysis or regulation of enzymatic activity. Another interesting role metals play In enzymes is a structural one. A few enzymes depend on metals for their structural stability, such as the protein ATCase. The B chain of the protein contains a zinc ion that does not have a catalytic role and is predicted to stabilize the protein structure. The goal of this research is to model the area around the zinc In the B chain and to determine what effect the zinc has on the stability …

Nmr Studies Of Short Salt Bridged Peptides, James A. Ernst

Honors Theses

The study of small helical peptides is an area of great interest in biochemistry. Baldwin has shown that salt bridging between residues with oppositely charged side chains can act to stabilize short helices. The order of increased helix stabilization shown by Baldwin was i+4AB>i+4BA>i+3AB>i+3BA where A is a positively charges amino acid side chain and B is a negatively charged amino acid side chain. Most previous studies have dealt with a single type of salt bridge stabilization, either i,i+3, or i,i+4 in a single peptide. This study will address the question of helix stabilization in a system …

Application Of A Modified Analytical Derivatization Method To The Determination Of Microbial Metabolites In Aquifer Systems, Jie Lu

Masters Theses

The geochemical evolution of Low Molecular Weight Fatty Acids (LMWFA's) in various ground water samples and aquifer solid samples from both contaminated and uncontaminated sites has been studied. An improved analytical method has been established for both qualitative and quantitative determination of LMWFA's. The low molecular weight (LMW) organic acids are metabolic intermediates of the oxidative biodegradation of hydrocarbon contaminants. The hydrocarbons are believed to be the electron donors in these redox reactions. Formic and acetic acids were found to be the major LMWFA's in these ground water samples and aquifer solid samples. Their concentrations increase as the redox condition …

The Thermodynamics Of Formation Of A 3-Strand, Dna 3-Way Junction Complex, John E. Ladbury, Julian M. Sturtevant, Neocles B. Leontis

Chemistry Faculty Publications

Isothermal titration calorimetry (ITC) is used to study the thermodynamics of assembly of the three DNA oligonucleotides S1 (5'GCCTGCCACCGC), S2 (5'-GCGGTGCGTCCG), and S3AA (5'-CGGACGAAGCAGGC) to form a three-way junction (TWJ) complex consisting of three double-helical arms radiating from a junction region having two unpaired adenosines in one strand (S3AA). The thermodynamics of assembly were measured for three different orders of addition of the component oligonucleotides at four temperatures between 10 and 25 degrees C. At each temperature studied, the overall values of Delta H, Delta S degrees, and Delta G degrees for assembly of the complex from the component single …

Controlled Oxidation Studies Of Coal/Refuse Fuel Blends, Aiping Wu

Masters Theses & Specialist Projects

A study of the controlled combustion of blends of biomass materials and coals was conducted. Crushed limestone was added to the blends as an absorbent for sulfur oxides. The samples were combusted in quartz-fiber crucibles in a forced air furnace. Combustion at different times and temperatures were studied. The amount of carbon, hydrogen, and sulfur in the residues, as well as the amount of ash formed, were used as measures of combustion efficiency. The optimum temperature for combustion of most blends was found to be in the 700 - 800°C range. A study of methods for determining the amounts of …

Effect Of Applied Potential Upon The In Situ Structure Of Self-Assembled Monolayers On Gold Electrodes, Mark Anderson, Marilyn Gatin

Mark R. Anderson

Polarization modulation Fourier transform infrared reflection absorption spectroscopy (PM-FTIRRAS) has been utilized to study the in situ structure of octadecanethiol when adsorbed to gold electrode surfaces and with the application of potential to the substrate. It is found that applied potential has little effect upon the spectrum of the monolayer in the presence of D2O solutions containing 0.10 M NaClO4. The presence of an acetonitrile solution contacting the monolayer leads to small changes in the infrared spectrum relative to that seen in D2O solutions, suggestive of some small disordering of the monolayer caused by the presence of the acetonitrile. With …

Application Of The Quartz Crystal Microbalance To Characterize The Interaction Of Solutes With Modified Interfaces, John Roush, David Thacker, Mark Anderson

Mark R. Anderson

Piezoelectric quartz crystals, modified by the spontaneous adsorption of either 4-aminothiophenol or octadecanethiol, were utilized to investigate the selective interactions that exist between solutes and the surface modification layer. It is found that the exposed amine functionality of the 4-aminothiophenol monolayer increases the sensitivity of the quartz crystal microbalance to phenols relative to the response found at either a crystal modified with an octadecanethiol monolayer or an unmodified quartz crystal. Protonation of the amino group decreases the sensitivity of the 4-aminothiophenol modified crystal toward the phenol solutes, to a level approximately the same as seen for the octadecanethiol monolayer and …

The Application Of Stereolithography To The Creation Of Molecular Models Of Amiloride And Its Analogues, Thomas John Busanic

Theses

Stereolithography, a process by which a computer-guided Ultraviolet (UV) laser is applied onto a liquid monomer resin to form a solid polymer, was used to create solid models of amiloride and two of its analogues. The Cartesian coordinates used as input for the orientation of each atom in a molecule were calculated using ab initio molecular orbital theory. Since the structures of the molecules are calculated in this fashion, they represent a more accurate representation of the molecules than that provided by standard molecular modeling kits.

The original purpose of this work was to assist a blind chemist in appreciating …

Smectic-A —Smectic-C* —Smectic-C Multicritical Point In Ferroelectric Liquid Crystals, Shankar B. Rananavare, V. G. K. M. Pisipati, E. W. Wong

Chemistry Faculty Publications and Presentations

We report a smectic-A–smectic-C–smectic-C* (ACC*) multicritical point in mixtures of chiral DOBAMBC [p-(n-decyloxybenzylidene)-p-amino-(2-methyl-butyl)] cinnamate and achiral 10O.8 (4-decyloxybenzylidene-4-octylaniline). Studies of the phase diagram, tilt angle (θ), polarization (P), and helix pitch (p) indicate an ACC* Lifshitz point that can be described in terms of the extended Landau theory. Specifically, the T*_AC and the maximum polarization (P_m) exhibit quadratic composition dependence while the helical pitch length (p=2π/q) varies linearly. Both q and P_m vanish discontinuously at the C-C* …

Application Of Polarization Modulation Infrared Relection Absorption Spectroscopy To Study The In Situ Structure Of Monolayers Prepared By Spontaneous Adsorption, Mark Anderson, Mark Evaniak, Minhui Zhang

Mark R. Anderson

No abstract is currently available.

The Photochemistry Of The Nitrite Ion, Deborah Anna Cull '94

Honors Projects

The photolysis of aqueous nitrite ion, N02-, yields the free radicals nitric oxide, NO*, and hydroxyl radical, *OH. It has been found by Treinin and Hayon and supported in this laboratory that no net reaction occurs when nitrite is photolyzed in pure water. Zafiriou has extensively studied the solar photolysis of nitrite-containing seawater, and has detected increased partial pressures of NO* during the day, as well as decreased nitrite concentrations, which both suggest that net photolysis of nitrite has occurred. In pure water, the *OH and NO* radicals produced from the photolysis of NO2- presumably recombine and ultimately reproduce NO2-. …

A Synthetic Study Of An Organophosphorous Compound As An Acetylcholinesterase Inhibitor, Sulay Jhaveri '94

Honors Projects

Acetylcholinesterase is the enzyme that catalyzes the hydrolysis of acetylcholine. Based on the transition state of the catalysis, and what is known about the structure of the enzyme, a synthetic study has been conducted on an organophosphorous inhibitor which is capable of probing into the stereospecificity of the enzyme. The asymmetric synthesis was initiated with I-proline, and several methods were employed in phosphorylation in order to get the desired product.

Electrocrystallization Of Strongly Adherent Brushite Coatings On Prosthetic Alloys, Jody G. Redepenning

Chemistry Department: Faculty Publications

An electrolytic method for providing bone-emulating, phosphate coatings on prosthetic appliances. Such coatings serve to enhance bone fixation after implantation of the appliances. The method of the invention is an electrolysis process wherein the appliance to be coated is immersed in a phosphate-containing electrolyte to serve as the cathode of the electrolysis process. When current is applied to the electrolysis cell, the electrolyte solution, which includes calcium ions and dihydrogen phosphate ions, is caused to rapidly increase in (localized) pH proximate the cathode element. The localized pH increase creates a supersaturated local condition causing less soluble calcium phosphate salts to …

Characterization Of The 4.5s Rna Molecule In Escherichia Coli, Bruce John Panilaitis

Senior Scholar Papers

The 4.5S RNA molecule of Escherichia coli is essential to cell viability. It has been shown that depletion of this molecule inhibits protein synthesis, induces the heat shock response, and generally slows cell growth. The molecule has also been implicated in protein secretion, as in cells depleted of 4.5S RNA, an unsecreted precursor to ?-lactamase accumulates (pre-?-lactamase). A role in protein secretion is further supported by structural similarities with the 7S RNA molecule of eukaryotic SRP, specific binding to SRP54, and its homolog in E. coli, P48, and the ability of 7S RNA from certain archaebacteria to suppress 4.5S RNA …

Electron Stimulated Desorption Of Alkali Halides, Islamshah Amlani

Mahurin Honors College Capstone Experience/Thesis Projects

No abstract provided.

The Crystalline Structure Of Mm3, A Derivative Of Dapsone, Tommie L. Heltcel

McCabe Thesis Collection

Dapsone is a drug which has recently been discovered as a potential treatment for the disease of leprosy. Many of the derivatives of dapsone have been sent to the United States by Dr. M. Muhundam and Professor M.S.R. Naidu of the Department of Chemistry, S.V. University, Tirupati, India, for structure analysis. One such derivative is (E)-3-[2-[(4-Chlorophenyl) sulphonyl] ethenyl]-4H-l-benzopyran-4-one, which will hereafter be referred to as MM3. MM3 was synthesized and the initial data for the structural analysis taken in the departments of Physics and Chemistry at S.V. University, Tirupati, India. The drug has been found to have a high antibacterial …

Energy Dependence Of Multifragmentation In 84kr+197au Reactions, Graham F. Peaslee, M. B. Tsang, C. Schwarz, M. J. Huang, W. S. Huang, W. C. Hsi, C. Williams, W. Bauer, D. R. Bowman, M. Chartier, J. Dinius, C. K. Gelbke, T. Glasmacher, D. O. Handzy, M. A. Lisa, W. G. Lynch, C. M. Mader, L. Phair, M-C. Lemaire, S. R. Souza, G. Van Buren, R. J. Charity, L. G. Sobotka, G. J. Kunde, U. Lynen, J. Pochodzalla, H. Sann, W. Trautmann, D. Fox, R. T. De Souza, G. Peilert, W. A. Friedman, N. Carlin

Faculty Publications

The relationship between observed intermediate mass fragment and total charged particle multiplicities has been measured for Kr84 + Au197 collisions at energies between E/A=35 and 400 MeV. Fragment multiplicities are greatest for central or near-central collisions. For these collisions, fragment production increases up to E/A≊100 MeV, and then decreases at higher energies.

Effect Of Iron Binding On The Ability Of Crocidolite To Cause Dna Single-Strand Breaks, Jeanne Ann Hardy

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Fibrous carcinogens, such as crocidolite asbestos, are known to catalyze many of the same reactions as iron, namely O₂ consumption, generation of reduced oxygen species, and damage to DNA, such as strand breaks, and modifications of bases. Upon inhalation, fibers are also known to become coated with an iron-rich material. The mechanism by which this iron is bound to fibers in the lung is not known, and the effect of this additional iron on the reactivity of the fibers is also not well understood. The studies described here were undertaken to elucidate the abilities of crocidolite asbestos, in its …

The Pharmacodynamics And Toxicodynamics Of Inotropic Drugs In Calves With Natural And Artificial Hearts, Scott D. Everett

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Inotropic support for the failing myocardium as the therapy for congestive heart failure (CHF) is intended to achieve an increase in cardiac output via positive responses in myocardial contractility and vasodilation. A novel approach to differentiate these two responses is the use of an animal with an implanted total artificial heart (TAH). Three inotropic drugs, dobutamine, enoximone, and pimobendan, were tested in eight animals with their natural heart intact and five animals implanted with a TAH. Baseline values of the TAH and natural heart (NH) were compared to determine their hemodynamic similarities. Each of the three drugs was given randomly …

Comparative Mössbauer Effect Study Of Several R₂Fe₁₇ And R₂Fe₁₇Nₓ Compounds, Gary J. Long, Sanjay R. Mishra, Oran Allan Pringle, Fernande Grandjean, K. H. Buschow

Chemistry Faculty Research & Creative Works

The Mössbauer spectra of Sm₂Fe₁₇ and Ho ₂Fe₁₇ and their nitrides have been measured between 295 and 85 K and analyzed with a model which is consistent with our earlier work on R₂Fe₁₇ and R₂Fe₁₇N_x compounds, where R is Pr, Nd, and Th. This model is completely consistent throughout these rare-earth compounds and is in agreement with the crystallographic changes occurring upon nitrogenation and with the prediction of band structure calculations. The dramatic increase in Curie temperature in the nitrides results from the expansion of the crystallographic …

Macrocyclic Antibiotics As A New Class Of Chiral Selectors For Liquid Chromatography, Daniel W. Armstrong, Yublng Tang, Shushi Chen, Yiwen Zhou, Christina Bagwlll, Jing Ran Chen

Chemistry Faculty Research & Creative Works

There are a large number of antibiotic macrocycles which include several different structural types. Three representative macrocyclic compounds were covalently linked to silica gel and evaluated by HPLC for their ability to resolve racemic mixtures as well as for their stability and loadability. Over 70 compounds were resolved. In some cases separations were achieved that have not been reported on any other chiral stationary phase (CSP). These stationary phases appear to be multimodal in that they can be used in both the normal-phase and reversed-phase modes. Different compounds are resolved in each mode. There does not appear to be any …

Use Of A Macrocyclic Antibiotic, Rifamycin B, And Indirect Detection For The Resolution Of Racemic Amino Alcohols By Ce, Daniel W. Armstrong, Kumber Rundlett, George L. Reid

Chemistry Faculty Research & Creative Works

Ansamycins are a very specific class of macrocyclic antibiotics of which the rifamycins are among the better-known members. Rifamycins bind to and inhibit DNA polymerase. Rifamycin B (the most easily obtained ansamycin) is negatively charged and is shown to associate with and enantioselectively resolve several chiral amino alcohols including terbutaline, isoproterenol, bamethan, metaproterenoi, synephrine, metanephrine, salbutamol, epinephrine, norphenylephrine, ephedrine, ψ-ephedrine, octopamine, norepinephrine, normetanephrine, metoprolol, alprenolol, atenolol, and oxprenolol. A description of the structure and properties of rifamycins, in general, and rifamycin B, in particular, is given. The complexation and chiral recognition of the aforementioned racemic compounds by rifamycin B is …

Structure And Phase Transition Of The 6,5-Annulene Isomer Of C_{61}H_{2}, Andrea N. Lommen, Paul A. Heiney, Gavin B. M. Vaughan, Peter W. Stephens, Dengfa Liu, Dayin Li, Allan L. Smith, Andrew R. Mcghie, Robert M. Strongin, Laurent Brard, Amos B. Smith Iii

Chemistry Faculty Publications and Presentations

We have used differential scanning calorimetry and x-ray diffraction to study the crystalline phases of the 6,5-annulene isomer of C₆₁H₂. At 308 K the methylenated fullerenes are orientationally disordered in a face-centered cubic lattice with lattice parameter 14.19±0.02 Å. Below Tc=290 K the symmetry is lowered to Pa3¯, a simple-cubic structure. At 20 K the lattice parameter is 14.06±0.02 Å, with substantial statistical disorder remaining. The transition temperature in C₆₁H₂ is slightly higher than in C₆₀O and higher still than in C₆₀, but the three compounds exhibit orientationally …

Electrochemical Detection Of Aliphatic Sulfur Compounds In Liquid Coal Extracts, Samuel Myers

Masters Theses & Specialist Projects

The presence of sulfur compounds in coal is a serious environmental problem that affects the coal industry. This problem is due to the fact that organic sulfur is not separated or removed during any physical cleaning process. Organic sulfur is removed only during a more costly chemical desulfurization process. The kinds of organosulfur compounds in coal are generally known, but the quantity of each type of compound and the distribution of these compounds throughout the coal matrix has not been studied extensively. The objective of this research was to investigate the more reactive and chemically labile organosulfur compounds in liquid …

The Effects Of Chlorine On Boiler Corrosion, Marian Upchurch

Masters Theses & Specialist Projects

The amount of corrosion of six metal samples was measured by a change in weight over time. The simulated flue gas stream consisted of 0.2% SO2,14% C02 / and 4% O2, with the HC1 percentage varied from 0.2% to 0.0% and the balance of gas being N2. A Lindbergh Three Temperature Tube Furnace was used to house the metal samples at 100°C, 200°C, and 600°C while being subjected to the simulated flue gas stream. The six metal samples were chosen on the frequency of industrial use. Two carbon steels, C1018 and C1010, contain no chromium and were chosen because of …

Quantitative Analysis Of Steroids By 13C Nmr Spectroscopy, Pei Wang

Masters Theses

Steroids are usually analyzed quantitatively by using HPLC with ultraviolet detection and are confirmed by FTIR, GC-MS. Quantitative ¹³C NMR method provide an alternative means to analyze steroids. Chromatographic separation and subsequent identification by match with a spectroscopic data base spectrum is not required for quantitative analysis of mixture components. Instead, equivalent information is obtained by creating subspectra from resonances with equivalent peak areas within a quantitative NMR spectrum. Techniques for eliminating Nuclear Overhauser Enhancement (NOE) effect is described.