Physical Sciences and Mathematics Commons^™

32nd Rocky Mountain Conference

Rocky Mountain Conference on Magnetic Resonance

Program and registration information for the 32nd annual meeting of the Rocky Mountain Conference, co-sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy and the Rocky Mountain Chromatography Discussion Group. Held in Denver, Colorado, July 29 - August 3, 1990.

Theoretical Studies Of The Metallacyclopropenes C-[Mx2c2h2] (M = C, Sl, Ge, Sn; X = H, F), Jerry A. Boatz, Mark S. Gordon, Lawrence R. Sita

Mark S. Gordon

The geometries of the metallacyclopropenes c-[MX 2C2H2] (M = C, Si, Ge, Sn; X= H, F) are predicted by using the 3-21G(d) basis set and SCF wave functions. The nature of the ring bonding is investigated via analysis of the total electron density and is found to have little or no 11'-complex character. As a further probe of the electronic structure, bent bond lengths and intrinsic vibrational frequencies are computed. The classical barrier heights and the thermodynamics of the reaction MX 2 + HC==CH-- c-[MX 2C2H2] are predicted by using MP2/3-21G(d) energies.

Thermal Decomposition Processes For Sllanol, Mark S. Gordon, Lisa A. Pederson

Mark S. Gordon

Six alternative decomposition modes of silanol are examined with ab initio electronic structure theory. Geometries determined at the MP2/6-31 G( d,p) level of computation and single-point energetics obtained with MP4/MC-311 G{d,p) wave functions predict that the I, 1- and I ,2-eliminations of molecular hydrogen are both thermodynamically and kinetically competitive, with all other processes requiring at least 10 kcaljmol more energy to occur. At the highest level of theory, silanone is predicted to be 2.7 kcaljmollower in energy than hydroxysilylene.

Mössbauer-Effect, Magnetic, And Neutron-Diffraction Study Of Nafep₂O₇, R. C. Mercader, L. Terminiello, Gary J. Long, D. G. Reichel, K. Dickhaus, R. Zysler, R. Sanchez, M. Tovar

Chemistry Faculty Research & Creative Works

Neutron-diffraction, magnetic-susceptibility, specific-heat, and Mössbauer-effect studies of NaFeP₂O₇ reveal that it is a normal Heisenberg isotropic three-dimensional antiferromagnetic material with a Néel temperature of 29.0 K. NaFeP₂O₇ has the monoclinic P2₁/c magnetic space group, which is the same as the nuclear crystallographic space group. The easy axis of magnetization lies in the monoclinic ac plane at an angle of 21.0° from the c axis. The specific-heat measurements reveal a λ-type anomaly at 28.7(2) K. A molecular-field model analysis indicates that the intrasublattice magnetic exchange coupling J_aa=J_bb=-0.37 cm-1, whereas …

Ua66/7/3 Coal & Fuel Characterization Laboratory: The First Ten Years, Wku Chemistry

WKU Archives Records

Report of work completed in the first ten years of the Coal & Fuel Characterization Laboratory.

A Potentiometric Gaseous Hydrogen Sensor, Anne Guillory

Chemistry & Biochemistry Theses & Dissertations

The development of a potentiometric gaseous hydrogen sensor using a 75% palladium - 25% silver alloy as a selectively hydrogen permeable electrode is described. The sensor showed some promise when used with a molten base electrolyte. Other electrolytes are investigated at ambient and higher temperatures. Various cell designs including a platinum/silver-silver chloride sensor with a gel electrolyte are discussed.

Photoinduced Electron-Transfer In Self-Associated Complexes Of Several Uroporphyrins And Cytochrome-C, J. S. Zhou, E. S. V. Granada, Neocles B. Leontis, M. A. J. Rodgers

Chemistry Faculty Publications

Photoinduced electron transfer between cytochrome c and free base and metallouroporphyrin (Up, MUp) has been studied. Difference absorption spectrophotometry showed that the electrostatic interactions between Up and cytc(II1) result in their forming a self-associated 1:l complex in the ground state with a binding constant that depends upon the ionic strength. In the complex, the photoexcited uroporphyrin singlet state was quenched through a static interaction with the protein. Even under the most favorable quenching conditions, Le., when all porphyrin was complexed, residual fluorescence was noted. More significantly the excited singlet state of the complex was shown to undergo small, but significant, …

The Use Of Fluorescence Quenching Measurements To Study The Cyclodextrin Inclusion Complexes Of 2-Aceotonaphthone, Elie K. Fraiji Jr

Honors Theses

2-Acetonaphthone (2-AN) is an unusual molecule in that it will only fluoresce in the presence ot strong hydrogen bond donors such as water. Less than a 10 mol % addition of a weaker hydrogen bonding molecule such as ethanol results in significant quenching of the 2-AN fluorescence in water. We have used this behavior to monitor the binding of 2-AN to the ethanol-like interior of the α-, β-, and y-Cyclodextrin (CD) C2'1ities. The addition of CO's to aqueous solutions of 2-AN causes a dramatic quenching of the 2-AN fluorescence. Because the quenching is static, we attribute the observed behavior to …

Analysis Of Dolemitic Limestone Ore Using Direct Current Plasma Spectroscopy, Edward M. Kulback

Honors Theses

Four samples of dolemitic limestone ore, provided by the Thorne-Smith Company were analyzed for trace elements. Composition of limestone is important because this ore is often found with ground water (a primary source of drinking water); and in acidic conditions, certain elements can leach out of the ore and into the water supply, possibly in toxic levels, depending on the element. The elements that were found are: aluminum, iron, manganese, tin, and chromium. This last element is of particular concern because it appears in the ore in relatively high concentrations, and chromium can be a very toxic substance if its …

Linear Free Energy Correlations Of The Effect Of Substituents On The Cinnamaldehyde-Bisulfite Reaction, Susanne M. Hoff

Honors Theses

This thesis was primarily concerned with the correlation of the kinetics and equilibrium of the cinnamaldehyde-bisulfite reaction with the effect of ortho, meta, and para substituents. The cinnamaldehyde-bisulfite reaction is seen below: where X=p-NMe2, p-MeO, p-Me, H, p-Cl, p-Br, p-NO2, m-Br, o-NO2, and o-MeO. The cinnamaldehydes were synthesized via a crossed aldol condensation reaction between acetaldehyde and the corresponding substituted benzaldehyde. The equilibrium constant and second order rate constant for the cinnamaldehyde-bisulfite reaction were determined through UV-visible spectroscopy. The equilibrium and kinetics data was then correlated by Hammet’s equation (log K/KH=pσ°) for the meta and para derivatives. In order to …

Conformational Energy Calculations Of The Pentapeptide Phe-Dphe-Asn-Gln-Tyr Of Tyrocidine, Douglas H. Reamer

Honors Theses

By virtue of employing a modified version of a popular program for the calculation of polypeptide conformational energies, the lowest energy conformation of the tyrocidine molecule is being sought. This antibiotic molecule, a cyclic decapeptide, invited study due to its role in the process of bacterial sporulation in the Bacillus Brevis ATCC 818!2 strain. In the process of performing this investigation, lists of monopeptide lowest energy conformations, as determined by x-ray crystallographic studies, were combined to yield all possible combinations of half of the polypeptide chain. Beginning with a dipeptide, the conformations of lowest energy were calculated within a 'local-minimum' …

The Synthesis Of Allylic Organotin Compounds For The Enantioselective Formation Of Homoallylic Alcohols, Jean-Claude David Abed

Honors Theses

Allylic tins when reacted with aldehydes are known to be diastereoselective for the resulting homoallylic alcohols. It is believed that a diastereomeric transition state can be created if the allylic tin contains a chiral ligand. Enantiomerically enriched α-pinene was chosen for the chiral ligand and brominated by an electroptilic addition of HBr to form enantiomerically enriched endo-2-bromobornane. This was then reacted with various alkyltin anions prepared from the chlorides, R3SnCl (R=Ph, Bu, & Me). Of the alkyltin chlorides chosen Me3SnCl produced the desired product in the best yield; the others were either very slow in reacting or unreactive. The final …

X-Ray Powder Diffraction, Scanning Electron Microscopy And Energy Dispersive Spectroscopy Studies Of Soil Containing Chromium Immobilized By Microwave Treatment, Nagui Ibrahim

Theses

The orientation of soil contaminants such as chromium is altered during microwave heating. The SEM and EDS were utilized in the study. The nature of the orientation is related to the heating time. This results in immobilizing the contaminant in leaching tests. The non-leachibility was related to the reactivity of the chromium salt with the soil hematite phase (Fe2O3) during the microwaving. This was proved By the X-ray diffraction analysis. The spectrums obtained from 30 and 60 minutes microwaved samples were identical in the crystal phases and were significantly different from the contaminated unheated sample.

Quantitative Determination Of Adsorption Using A Semi-Integral Method, Mark Anderson

Mark R. Anderson

No abstract is currently available.

Two-Dimensional Gel Electrophoretic Analysis Of Cellular Proteins From Escherichia Coli In The Presence Of Mutated And Homologous Genes For 4.5s Rna, Michael O'Loughlin

Senior Scholar Papers

4.5S RNA is a small. stable, required molecule in Escherichia coli whose precise function is not known. Previous evidence suggests an involvement with the ribosome during translation. In this study, four base insertion and four base deletion mutations were constructed in a plasmid borne copy of the 4.55 RN A gene. These copies and two homologous genes from Pseudomonas aeruginosa and Thermus thermophilus were transformed into an E. coli strain which then had its only wild-type 4.5S RNA gene inactivated. In order to assess the effect of the alternative gene copies. the patterns of proteins synthesized in the presence of …

Predicted Enthalpies Of Formation For Methyl-Substituted Disilanes, Jerry A. Boatz, Mark S. Gordon

Mark S. Gordon

Entha1pies of formation of the entire series of methyl-substituted disilanes, Si2(CH3)kH6_k (k = 1-6), are predicted by using homodesmic reactions at the MP2/6-31G(d)/ /RHF /3-21G* level of theory. The calculated values are systematically higher than the values suggested by Walsh but are in excellent agreement with the kinetic data of O'Neal, Ring, and co-workers.

Calculated Oscillator Strengths Between Vibrational Levels Of The Rotational And Trans-Bending Modes In The Ground And Lowest Excited States Of Disilene, Shiro Koseki, Mark S. Gordon

Mark S. Gordon

Starting from the D2h structures of disilene and ethylene, the potential energy surfaces of the ground and excited singlet ( π → π) states along the rotational coordinate (au) and the trans-bending coordinate (b28) and the transition moments between these two states are calculated by using the multiconfigurational self-consistent-field (MCSCF) method with the 3-21G(d) basis set. Based on these results, the vibrational wave functions of these two states are expanded in Fourier series, and the Franck-Condon factors and the oscillator strengths are calculated between the vibrational levels of these two states. Though the transition moments are not constants along these …

Measuring Δh Using Dsc, Tga & Dta, Roland Hoffman

Masters Theses & Specialist Projects

The purpose of this study was to obtain greater accuracy in the measurement of the heat of reaction by combining data from various thermal analysis techniques. Conventional equations that calculate heat of reaction are limited because they do not take in to account mass change. Therefore, an enhanced equation was developed to integrate mass (weight) change to provide greater accuracy. The path chosen to implement this new equation employed simultaneous Thermogravimetric / Differential Thermal Analysis (TG/DTA) that could provide both ΔT and weight data simultaneously. Computer programs were written in C and Pascal languages to provide communication capabilities between computers …

Production And Deexcitation Of Hot Nuclei In Collisions Of 27 Mev/Nucleon 40ar + 238u, D. Jacquet, Graham F. Peaslee, John M. Alexander, B. Borderie, E. Duek, J. Galin, D. Gardes, C. Grégorie, D. Guerreau, H. Fuchs, M. Lefort, M. F. Rivet, X. Tarrago

Faculty Publications

Hot nuclei, produced in the reaction 1080 MeV 40Ar+238U, have been studied by means of the light charged particles emitted in coincidence with fission fragments. A dominant fraction of the light charged particles emitted in the backward hemisphere (60%, 75%, 80% and 85% for 1,2,3H and 4He, respectively) comes from evaporation from a composite nucleus prior to scission. Careful analysis of the cross sections and energy spectra of these evaporated particles yields several properties of the hot nuclear emitters: (i) they are thermalized with an average temperature of 4.0–4.6 MeV, (ii) they are quite deformed (mean axis ratio ) and …

A Prostaglandin Synthase Inhibition Assay With Detection By Elisa, Patricia Scott

Theses & Honors Papers

A simple, reliable method is described for the routine measurement of non-steroidal anti-inflammatory drugs (NSAIDs) as inhibitors of prostaglandin synthase. Appropriate concentrations of inhibitor are incubated with ram seminal vesical prostaglandin synthase, sodium arachidonate and reduced glutathione. Prostaglandin E₂ (PGE₂) production is then quantitated by and enzyme linked immunosorbant assay (ELISA), in which anti-PGE₂ antibody is utilized in a binding competition between test sample and adsorbed conjugate of PGE₂-BSA. The antibody which remains bound to the solid phase is quantitatively determined colorimetrically by incubation with horse radish peroxidase labeled goat anti-rabbit IgG followed by …

Polar-Liquid, Derivatized Cyclodextrin Stationary Phases For The Capillary Gas Chromatography Separation Of Enantiomers, Daniel W. Armstrong, Weiyong Li, Chau Dung Chang, Josef Pitha

Chemistry Faculty Research & Creative Works

A new class of hydrophilic, relatively polar liquid, cyclodextrin (CD) derivatives have been used as highly selective chiral stationary phases (CSPs) for capillary gas chromatography (GC). Several possible requirements for liquidity In CD derivatives are discussed. O-(S)-2-Hydroxypropyl derivatives of α-, β-, and γ-cyclodextrlns were synthesized, exclusively characterized, permethylated, and evaluated for enantloselectlvity. Seventy pairs of enantiomers were resolved. They represent a wide variety of structural types and classes of compounds including chlral alkyl amines, amino alcohols, epoxides, pyrans, furans, sugars, dlols, esters, ketones, bicyclic compounds, alcohols, and so on. Many of these compounds were not aromatic and cannot be resolved …

Thermodynamic Data From Drug-Dna Footprinting Experiments, James C. Dabrowiak, Jerry Goodisman, Koren Kissinger

Chemistry - All Scholarship

Sequence-dependent thermodynamic quantities for the antiviral agent netropsin and a related bis(N-methylimidazole) dipeptide, lexitropsin, have been determined by DNase I footprinting techniques. The primary data are autoradiographic spot intensities derived from 10 footprinting experiments carried out in the temperature range 0-45 OC. After exclusion effects due to overlapped drug sites on DNA and redistribution phenomena associated with the enzyme were accounted for, sequence-dependent binding constants for the two ligands were calculated. Our approach does not require an independent determination of the free drug concentration, which is calculated, with individual site binding constants, by using only footprinting data. The temperature dependence …

Chloroplast And Mitochondrial: Dna Polymerases From Cultured Soybean Cells, Sabine Heinhorst, Gordon C. Cannon, Arthur Weissbach

Faculty Publications

DNA polymerases were purified from chloroplasts and mitochondria of cultured Glycine max cells. The chloroplast enzyme exists in two forms which are indistinguishable from each other biochemically. All three organellar enzymes have an estimated molecular weight of 85,000 to 90,000 and prefer poly(rA)dT12-18 over activated DNA as a template in vitro. Maximum activity of the chloroplast and mitochondrial DNA polymerases requires KCI and a reducing agent, and the enzymes are completely resistant to inhibitors of DNA polymerase a. Taken together, these properties classify the soybean organellar enzymes as DNA polymerases y. A unique feature that distinguishes the plant enzymes from …

Photochemistry Of Nitrous Acid And Nitrite Ion, Christopher L. Exstrom '90

Honors Projects

Aqueous solutions of HONO (ranging from 0.010M to 0.057M) and NO2 (ranging from 0.025M to 0.035M) were each photolyzed with nm ultraviolet (UV) light. In the presence of benzene scavenger, DH radical intermediate was indicated by formation of p-nitrosophenol (PNP). Ultraviolet/visible (UV/vis) absorption spectra of photolyzed aqueous HONO/benzene solutions showed the presence of PNP by its characteristic absorption at 298 nm. UV/vis absorption spectra of photolyzed aqueous NO -benzene solutions showed no evidence of PNP formation. Other compounds such as scavengers were toluene, benzoic acid, and terephthalic acid. UV/vis spectra of photolyzed aqueous HOND/scavenger solutions showed an Int n e …

Kinetics Of The Metal-Exchange Reaction Between Ortho-Phospho-Dl -Serinenickelate(Ii) And Copper(Ii), Jeffrey M. Peterman

Masters Theses

No abstract provided.

The Reaction Of Organoboranes With N-Chloro-N-Sodiocarbamates: A Convenient Synthesis Of N-Alkylcarbamates, Nanette M. Wachter-Jurcsak

Chemistry & Biochemistry Theses & Dissertations

N-alkylcarbamic acid esters are used extensively as fungicides, herbicides and pesticides. Industrial methods of preparation employ highly toxic reagents in their synthesis. Convenient and safe alternative methods are necessary.

Organoboranes are electrophilic compounds which can be employed as a source of alkyl substituents. They have been shown to successfully transfer alkyl groups to the nitrogen of chloramines. N-Alkylation of carbamic acid esters by reacting the corresponding N-chloro-N-sodiocarbamate with a variety of trialkylboranes is described. The yields of the various N-substituted products are discussed.

Two synthetic methods were devised. Originally, an equivalent of the isolated N-chlorocarbamate salt was added to the …

A Pulse Gas Chromatographic Method For Determining The Dispersion And Surface Area Of Co Oxidation Catalysts, Susan Kay Ohorodnik

Chemistry & Biochemistry Theses & Dissertations

Catalysts composed of platinum and/or palladium on tin(IV) oxide supports with or without silica gel have been developed for the recombination of carbon monoxide and oxygen to form carbon dioxide for use in carbon dioxide lasers. A pulse gas chromatographic method has been developed to measure the chemisorption properties of the catalysts. From the chemisorption measurements, the active surface area and dispersion of the catalysts have been determined.

The Role Of The Voltage Gradient In The Agarose Gel Electrophoresis Of Dna, David Wheeler

Theses and Dissertations in Biomedical Sciences

In Part I of this dissertation, empirical equations for predicting DNA mobility during agarose gel electrophoresis (AGE) from voltage gradient are developed from the data of McDonnel (36) for electrophoresis in a 1.6% agarose gel. These equations represented the data well for DNA between 2 and 10 kilobase pairs (KBp) in length. A computer program, called GELSIM, which incorporates these equations is described in Part II. GELSIM was designed to allow researchers to analyze electrophoresis data by predicting the effect on DNA migration of altering the voltage of electrophoresis. In this way, electrophoretic banding patterns produced using different voltages could …

New .Mu.2-S2--Coupled, Singly Bridged Double Cubane With The [(Fe4s4cl3)2s]4- Core. The Stepwise Synthesis And Structural Characterization Of (N-Bu4n)2(Ph4p)2[(Fe4s4cl3)2s], Paul Challen, Sang Koo, W. Dunham, D. Coucouvanis

Paul R. Challen

No abstract provided.

Evaluation Of The Function Exp (X2) Erfc (X) To Higher Precisions For Higher-Order Derivative Polarography Of Ce-Type Electrode Process, Myung-Hoon Kim, Veriti P. Smith, Tae-Kee Hong

Chemistry & Biochemistry Faculty Publications

The function exp(x2)erfc(x), which is often encountered in studies of electrode kinetics, is evaluated to an extended precision with 32 significant decimal digits in order to find theoretical relationships used in derivative polarography/voltammetry for a chemically-coupled electrode process. Computations with a lower precision are not successful. Evaluation of the function is accomplished by using three types of expansions for the function. Best ranges of arguments are selected for each equation for particular precisions for efficiencies. The method is successfully applied to calculate higher-order derivatives of the current-potential curves in all potential ranges for a reversible electron transfer reaction coupled with …