Physical Sciences and Mathematics Commons^™

13C Nmr Investigation Of Nonenzymatic Glucosylation Of Protein, Carolyn I. Neglia, Helga J. Cohen, Albert R. Garber, Paul D. Ellis, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

Nonenzymatic glucosylation of protein is initiated by the reversible condensation of glucose in its open chain form with the amino groups on the protein. The initial product is an aldimine (Schiff base) which cyclizes to the glycosylamine derivative. The aldimine can undergo a slow Amadori rearrangement to yield the relatively stable ketoamine adduct which is structurally analogous to fructose. 13C NMR has been used to characterize these early products of nonenzymatic glucosylation, using RNase A as a model protein. C-1 of the beta-pyranose anomer of the glycosylamine was identified at 88.8 ppm in the spectrum of RNase glucosylated approximately 1:1 …

Plasma Polymerization Of Tetramethyldisiloxane By A Magnetron Glow Discharge, Ashok K. Sharma, H. Yasuda

Chemistry Faculty Research & Creative Works

Plasma polymerization of tetramethyldisiloxane by a magnetron glow discharge was studied. The glow discharge was created between parallel electrodes with a 10 kHz electric power source with a superimposed magnetic field using permanent bar magnets. Polymers were deposited onto moving substrates placed on the surface of a rotating disc located in between the electrodes. The deposition rates were determined with a quartz crystal thickness monitor placed on the plane of the rotating disc and just outside the edge of the disc. The current-voltage relationship observed for plasma polymerization of the monomer depends on the monomer feed rate and the conditioning …

Centers Of Polymer Research; Polymer Science In Northeastern Japan, Otto Vogl, T. Yamaguchi

Emeritus Faculty Author Gallery

No abstract provided.

Centers Of Polymer Research; Polymer Science In Northeastern Japan, Otto Vogl, T. Yamaguchi

Otto Vogl

No abstract provided.

Cationic And Anionic Micellar Catalyzed Hydrolysis Of Hydroxamic Acids, Douglas Eugene Conran

Masters Theses

The hydrolysis of octanohydroxamic and N-methyloctanohydroxamic acids in the presence of cationic and anionic micelles was investigated. Rate constants were determined for the hydrolyses in cetyltrimethylammonium bromide (ctab), the cationic surfactant, with 0.1111 N NaOH and in sodium 1-dodecanesulfonate, the anionic surfactant, with 0.09270 N HC1 at 50.01 + 0.11°C. The acid hydrolysis and the base hydrolysis of N-methyloctanobydroxamic acid followed the standard model for micellar catalysis.

Centers Of Polymer Research; Polymer Science In Hokkaido, Japan, Otto Vogl, J. Sohma

Emeritus Faculty Author Gallery

No abstract provided.

Centers Of Polymer Research; Polymer Science In Hokkaido, Japan, Otto Vogl, J. Sohma

Otto Vogl

No abstract provided.

The Qualog User’S Manual (Preliminary Version), Anne Shelly, Ernest Sibert

Electrical Engineering and Computer Science - Technical Reports

In qualitative research, data analysis is the stage of organizing, interpreting, synthesizing, conceptualizing, and reporting information collected over a period of time and by various means. The researcher organizes the information into “manageable units”, searches for recurring topics and patterns of words or phrases, decides on a focus, and refines the thesis or theme so that it accounts for supporting and negative evidence (Bogdan and Biklen, 1982). The major tasks of data analysis include organizing the data, developing categories around patterns or recurring pieces of information, discovering and testing the strength of relationships among categories, and developing a theme or …

Decomposition Rates, Synthesis, And Spectral Properties Of A Series Of Alkyl Hyponitrites, Craig A. Ogle, Steve W. Martin, Michael P. Dziobak, Marek W. Urban, G. David Mendenhall

Steve W. Martin

A number of trans-alkyl hyponitrites (RON=NOR) were synthesized and characterized. At 66.1 f 0.1 "C in isooctane and with millimolar to micromolar concentrations first-order kinetics were observed with half-lives (min) of 12.8 f 0.2 (CHJ, 32.3 f 1.1 (2-C3H7), 15.0 1 0.3 (cyclohexyl), 25.2 i 1.2 (tert-butyl), 18.3 f 0.3 (tert-pentyl), 3.0 f 0.1 (benzyl), 11.2 f 0.5 (2-phenylethyl), and 5.5 f 0.3 (1-phenylethyl). The rate constants were concentration independent and showed little change with changes in solvent polarity or viscosity. Ultraviolet, magnetic resonance, infrared, and mass spectra for the new hyponitrites are reported. Most of the hyponitrites were highly …

Solvents For Use In The Extractive Distillation Of Piperylene Concentrate, Abdulhadi Sagga

Retrospective Theses and Dissertations

This report describes an evaluation of the effectiveness of different solvents and solvent-organometallic compound mixtures for use in the extractive distillation of a piperylene mixture, consisting of five carbon olefins and diolefins obtained as a byproduct from an ethylene feedstock production plant. The most effective solvent is judged to be the one which gives the best separation of the lowest boiling and highest boiling points of the key components in the mixture. In this study twenty solvents and solvent mixtures were tested. Acetonitrile was found to be the most effective solvent and nitromethane the next most effective.

Structural Changes Induced By Addition Of A Hydrocarbon To Water/Amphiphile Mixtures, H. Sagitani, Stig Friberg

Chemistry Faculty Research & Creative Works

The phase conditions in a system of water, hexadecane, sodium dodecyl sulphate, and di-ethylene glycol dodecyl ether showed the W/O microemulsions to be obtained first after destabilization of a liquid crystalline phase by addition of the hexadecane. The original lamellar liquid crystalline phase was moved towards higher surfactant/cosurfactant ratios and a new phase with inverse amphiphile cylinders in a hexagonal packing appeared. © 1983 Steinkopff.

Part I: The Synthesis Of New Potential Insecticides. Part Ii: New Aromatic Nucleophililic Subsitution Reactions, Fluoroalkoxylation And N,N-Dimethylamination, Cesar Colon

Retrospective Theses and Dissertations

A series of routes are described for the synthesis of new potential insecticides which are symmetrical or asymmetrical similogs of 2,5-Bis (dichloropheny1)-1,3,4-oxadiazole and its precursor diacyl hydrazine. Also two new aromatic nucleophilic substitution reactions are discussed. Activated aryl halides are reacted with fluorinated alkoxide anions. In all cases, substitution of the halogen by a fluoroalkoxy group was observed, and activated aryl halides are reacted with HMPA as an N, N-dimethyl aminating agent. In all cases, substitution of the halogen by a dimethyl amino group was observed. The effect of the activating group and the leaving group is described and a …

Synthesis Of Potential Agrochemicals And Reactions Of Vinamidinium And Azavinamidinium Salts With Organometallic/Borane Reagents And Activated Nitrales, Charles N. Moorefield

Retrospective Theses and Dissertations

This report discusses research which was conducted in two areas: the synthesis of potential agrochemicals and the study of vinamidinium and azavinamidinium salt chemistry. Four classes of compounds were synthesized and characterized in the study of new potential agrochemicals. These compounds include diacylhydrazines, semicarbazides, 2,5-disubstituted-1,3,4-oxadiazoles and bis-2,5-disubstituted-1,3,4-oxadiazoles. The reaction of [3-(dimethylamino)-2-azaprop-2-en-1-ylidene] dimethylammonium chloride (Gold's reagent) with organometallic/borane reagents was examined in efforts to find convenient syntheses for N,N-dimethylamino substituted alkyl and aryl compounds. Additionally, the reaction of 1,5-diazapentadienium chloride (Nair's reagent) with nitrile activated alkanes was examined to find a convenient synthesis of 3-substituted pyridines. Subsequent intramolecular ring closure of …

The Synthesis Of Potential Insecticides: Haloalkoxy Phenyl Diacylydrazines And 1,3,4-Oxadiazoles, Kathleen S. Gibbs-Rein

Retrospective Theses and Dissertations

The syntheses of two classes pf compounds, diacylhydrazines and 2,5-disubstituted 1,3,4-oxadiazoles, intended for subsequent investigation of pesticidal activity are discussed. The experimental conditions and procedures necessary for the preparation of these potential insecticides are also revealed. Finally, spectral data are interpreted and explained, and recommendations for further research are given.

Determination Of N,N'-Diphenylguanidine In Biological Tissues And Fluids Using High Pressure Liquid Chromatography, Edward Sidney Hunter Iii

Chemistry & Biochemistry Theses & Dissertations

N,N'-Diphenylguanidine (DPG) is a potentially toxic compound used in the vulcanization of rubber products. Distribution of DPG in hybrid mice (C57BL/6J interbred with DAB₂) was determined following intraperitoneal injection. Urine, fecal material, whole blood and tissues were collected at various times after administration of DPG and the extracts analyzed for DPG by high pressure liquid chromatography. Recovery of DPG from spiked urine and whole blood exceed 90%, however, the recovery of DPG from spiked tissue samples was approximately 70%.

DPG concentration in whole blood reached a maximum within ten minutes and rapidly decreased through 180 minutes after administration …

Ab Initio Studies Of Abstraction Reactions Xhn + Hydrogen (H2) → Xhn+1 + Hydrogen (H) (X = Carbon, Nitrogen, Silicon, Or Phosphorus), Mark S. Gordon, David R. Gano, Jerry A. Boatz

Mark S. Gordon

The abstraction reactions CH3 + H2 --+ CH4 + H, SiH3 + H2 --+ SiH4 + H, NH2 + H2 --+ NH3 + H, and PH2 + H2--+ PH3 + H have been studied with a variety of methods, including MCSCF, POL-CI, UMP2, and UMP3. In agreement with the observed thermochemistry, abstraction by methyl radical is found to proceed more easily than by silyl, and the reverse of the last reaction occurs with a very small ( ~ 5.6 kcal/mol) barrier. POL-CI appears to be a consistently reliable approach for this type of reaction.

Electrical Properties Of Plasma-Polymerized Thin Organic Films, Maciej Gazicki, H. Yasuda

Chemistry Faculty Research & Creative Works

The electrical properties of plasma-polymerized films are summarized and compared to those of conventional polymers. Particular attention is devoted to the dielectric relaxation, dielectric breakdown, electric conductivity and photoconductivity, and their control via control of the plasma parameters. © 1983 Plenum Publishing Corporation.

25th Rocky Mountain Conference

Rocky Mountain Conference on Magnetic Resonance

Abstracts and meeting program from the 25th 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, August 14-17, 1983.

Nonenzymatic Glucosylation And Glucose-Dependent Cross-Linking Of Protein, Albert S. Eble, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

A model system using RNase A has been established for studying the nonenzymatic glucosylation and glucose-dependent cross-linking of protein (Maillard reaction) under physiological conditions in vitro. The rate of glucosylation of RNase was first order in glucose. Glucosylation was accompanied by a comparable decrease in primary amino groups in the protein and lysine recoverable by amino acid analysis. Analysis of glucosylation reaction mixtures by sodium dodecyl sulfate-polyacrylamide gel electrophoresis in the presence of mercaptoethanol revealed the time-dependent formation of RNase dimer and trimer. The polymerization reaction was mixed order with respect to glucose concentration, but was approximately first order with …

Analytical Pyrolysis Of Eastern Shales, Kenneth Naples

Masters Theses & Specialist Projects

The effects of pyrolysis interval, ceiling temperature, heating rate and mesh size on both the pyrolysis yield and relative product distribution for two eastern oil shales (Sunbury and Cleveland) were studied. An extension of the technique of analytical pyrolysis (pyrolysis-gas chromatography) was used. This extension employed a Chemical Data System (C.D.S.) Model 382 Extended Pyroprobe and a C.D.S. Model 310 Concentrator which enabled the pyrolysis products to be collected into a trap system. After completion of a predetermined heating interval, the trap was pulse heated to 250°C and the high and low volatile components were back-flushed into the injection port …

Transport Properties Of Ground State Nitrogen Atoms, James C. Rainwater, Louis Biolsi Jr., Kevin J. Biolsi, Paul M. Holland

Chemistry Faculty Research & Creative Works

Transport properties of dilute monatomic gases depend on the two body atom-atom interaction potential. When two ground state (⁴S) nitrogen atoms interact, they can follow any of four potential energy curves corresponding to the N₂ molecule; the X ¹Σ⁺_g, A³Σ⁺_u, ⁵Σ⁺_g, and ⁷Σ⁺_u curves. Transport collision integrals for the ¹Σ⁺_g and ³Σ⁺_u states have been calculated by representing the potentials for these states with the Hulburt-Hirschfelder potential. The⁵Σ⁺_g state has a …

A Microprocessor Controlled Pulsed Hollow Cathode Lamp For An Atomic Absorption Spectrometer, James B. Schilling

Masters Theses

A Jarrell-Ash Atomic Absorption/Flame Emission 82-360 Spectrometer was interfaced to a Heathkit ETA-3400 microprocessor. The microprocessor is used to pulse the hollow cathode lamp from a "steady" current to a "peak " current during the opening of the chopper. The current from the photomultiplier-tube is converted to a proportional voltage which is supplied to a sample-and-hold circuit. A successive approximation routine is used to convert the voltage to a representative digital value. Digital values are obtained for the "blank" and "sample" and are used to calculate percent absorption values. The system can also be used to obtain emission values.

The …

Generalized Response Of Chemiluminescence Analyzers, A. A. Mehrabzadeh, Robert J. O'Brien, Thomas M. Hard

Chemistry Faculty Publications and Presentations

The mass flow and chemical kinetic equations for a gaseous chemiluminescence (CL) analyzer are formulated and solved. The resultant equation can be used to predict the absolute response of the analyzer as a function of the sample flow rate, the sample gas pressure, the chamber pressure, the chamber volume, the mass flow rate and mole fraction of the reagent gas, and the rate constants of the relevant chemical processes. Thus, the equation allows optimization of these parameters. It is shown that for varying sample pressure the analyzer can be used to measure either concentration or mole fraction and that interfering …

The Metal In The Polarisable Interface Coupling With The Solvent Phase, Jerry Goodisman, Jean Paul Badiali, Martin Luc Rosinberg

Chemistry - All Scholarship

A quantum mechanical treatment of the conduction electrons of a metal in a polarisable interface shows that they can make an appreciable contribution to the electrical capacitance. Results for six metals are given, showing how differences in metal properties account qualitatively for experimentally observed differences in interfacial capacities, when the solvent is replaced by a dielectric film. To justify the neglect of solvent structure when metal properties are treated, the coupling between metal and solvent is discussed for orientable point solvent dipoles, and for a representation of the solvent polarisation by a pair of charged planes. The electron profile affects …

The Binding Of Ribosomal Protein Si To Si-Depleted 30s And 70s Ribosomes. A Fluorescence Anisotropy Study Of The Effects Of Mg2+, Dixie J. Goss, Lawrence J. Parkhurst, Arkesh M. Mehta, Albert J. Wahba

Lawrence Parkhurst Publications

We have determined the equilibrium constants for the binding of AEDANS-labelled Si to Sl-depleted 30S and 70S ribosomes. For “tight” ribosomes, the association of S1 increases with the sixth power of Mg²⁺ concentration, but for 30S subunits and "loose" ribosomes, there is virtually no dependence of the association on Mg²⁺ over the same concentration range, 2-1O mM in Mg²⁺. The binding of S1 to 70S ribosomes at 10 mM Mg is stabilized by 2 kcal/mol compared to the binding to 30S subunits. When intact Si binds to tight ribosomes, the fluorescence anisotropy is that for virtually …

Are The Silacyclopentadienyl Anion And The Silacyclopropenyl Cation Aromatic?, Mark S. Gordon, Philip Boudjouk, Freidun Anwari

Mark S. Gordon

Stabilization energies attributable to aromaticity in the silacyclopentadienyl anion and the silacyclopropenyl cation were found to be small in the former and absent in the latter when calculated from bond-separation reactions employing 3-21G and ST0-2G basis sets. The silacyclopentadienyl anion is approximately 25% as aromatic as the all-carbon analogue whereas silabenzene is more than 80% as aromatic as benzene. The introduction of diffuse functions into the basis sets has only a small effect on these results. The silacyclopropenyl cation is actually destabilized but strain is probably a key factor in the comparison. Also found was that the ST0-2G basis set …

Soil Degradation Of H-Coal Liquid & Various Aromatic Compounds, Kevin Wilson

Masters Theses & Specialist Projects

The common bacterial genera Pseudomonas and Acinetobacter are ubiquitous in most soils and are capable of degrading a large number of chemical compounds. While the degradative pathways of several individual aromatic compounds are known, the degradative pathways of many other aromatic compounds have not yet been elucidated. In addition, very little work has been done on the microbial degradation of coal liquids in the environment.

Previous work at Western Kentucky University has shown that decomposition of Ashland Oil Company's liquified coal can indeed be accomplished by the above bacterial genera in an enriched liquid media. The topic of this thesis …

The Products Of The Gas Phase Ozonolysis Of Tetramethylethylene, Anthony R. Deangelo

Honors Theses

The products of the ozonolysis of tetramethylethylene (TME) in the gas phase was studied. Reactions were run at concentrations between 10 and 400ppm TME and lower concentrations of ozone. The reactions were run at room temperature and atmospheric pressure. Gaseous products were studies by gas chromatography, mass spectrometry and HPLC analysis, the latter using 2, 4-dinitrophenylhydrazine derivatives of carbonyl products. Ozone concentrations and the determination of possible peroxidic products was accomplished by measuring the absorbance of a buffered KI solution (352 nm) after reaction with a known volume of gas. The possibility of acetone/ ozone and TME/ peroxides reactions were …

Fluorescence Quenching Of Peptidyl Tryptophan By External Quenchers, Richard Dennin

Honors Theses

Fluorescence quenching data have been collected on several small peptides (1-4) residues which contain tryptophan. These data have been analyzed by a variety of methods. The classical Stern-Volmer equation is utilized to obtain Stern-Volmer plots of fluorescence quenching data. Substantial upward curvature is observed in the Stern-Volmer plots of all the peptides studied. Data were also analyzed via the modified Stern-Volmer static quenching model. Although this model could explain the deviation from simple Stern-Volmer behavior found in SV plots, the parameters used by the model were often physically “unrealistic”: Therefore, another form of data analysis was used. The newly proposed …

Sterically Hindered Esters: Mechanisms Of Saponification, Frederick F. Fenter

Honors Theses

This paper discusses the mechanisms of base catalyzed hydrolysis of the secondary-butyl ester of 2, 2-dimethyl-propanoic acid (secondary-butyl pivaloate). Kinetic studies were carried out at 53° and near neutral hydroxide ion concentrations, but due to the slow velocity of reaction, no conclusions concerning the order of the kinetics of hydrolysis could be drawn. Also discussed is a scheme for an experiment involving the utilization of 018 enriched water in the saponification reaction of secondary-butyl pivolate under similar conditions of pH and temperature. The purpose of this experiment is to determine the site of oxygen cleavage during the hydrolysis. The analysis …