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 …

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 …

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.

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.

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 …

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 …

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 …

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 …

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 …

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 …

Dmf Extractability As A Predictor Of Plasticity In Bituminous Coals, Jana Whitt

Masters Theses & Specialist Projects

Plasticity is a phenomenon of certain coals that is not completely understood. Some bituminous coals go through a softening and swelling state upon heating before they re-solidify. It is this softening and swelling state that is labeled as the "plastic state" of the coal. Concurrent with the plastic state of the coal, thermal decomposition of the coal takes place. Several low molecular weight gases are also evolved. These occur at a temperature of approximately 450° C.

The plasticity of a coal is a good indication of the coking ability of a coal. Plastic coals tend to give higher yields in …

Kinetic & Spectral Studies Of Copper(Ii)-4,4',4",4'"-Tetrasulfophthalocyanine In Aqueous Solution, Stephen Scholl

Masters Theses & Specialist Projects

The monomer-dimer equilibrium of CuTSPC^4- was examined by spectral methods in aqueous solution over a total dye concentration of 2 x 10^-8M to 8 x 10^-7M at 24°C. The value obtained for the dimerization constant, KD,was 1.1 x 10⁷M^-1 which is smaller than literature values. However, the discrepancy is not appreciable considering the differences in the methods used and the experimental conditions of the different solutions. Spectral measurements of the dimerization constant were made at only one temperature since the spectral changes were quite small when the temperature was varied. This observation …

Analytical Pyrolysis Of Eastern Oil Shales, Lizbeth Sturgeon

Masters Theses & Specialist Projects

The Sunbury shale and the Cleveland member of the Ohio shale were studied utilizing the technique of analytical pyrolysis (pyrolysis gas chromatography). The effects of ceiling temperature, heating rate, and pyrolysis interval on the pyrolysis yield and relative product distribution for these eastern oil shales were observed. Carefully monitored pyrolysis of the shale allows separation of high and low volatile components and measurement of the relative peak areas in the pyrogram provides the yield of the high and low volatile fractions. Linear temperature ramps of 5000, 2000, and 100°C per second were employed. Ceiling temperatures of 450°C to 950°C and …

Density Functional Calculations For Liquid Metal Surfaces, Jerry Goodisman, M-L Rosinberg

Chemistry - All Scholarship

Various forms for the ion density profiles of Cs and Na have been tested in the density functional formalism. The large oscillations expected for Coulombic systems are largely suppressed by the pseudopotential. While oscillatory profiles give some improvement in surface tension, the values obtained are still about twice the experimental ones. It is concluded that the treatment of the pseudopotential or the gradient expansion of the functional is responsible for the unsatisfactory results obtained.

On Surface Properties Of The One-Component Plasma, M-L Rosinberg, J-P Badiali, Jerry Goodisman

Chemistry - All Scholarship

We consider a plasma of point ions in the presence of a non-uniform neutralising background. This background. the source of an external field, may have some of its parameters (density, form of surface profile, etc) modified, as long as the total charge is maintained. By considering such modifications in the context of the density-functional formalism for the ions, we prove sum rules giving the first and second moments of the ion density p(z) in terms of other properties (bulk pressure and temperature derivative of surface tension). The Poisson-Boltzmann functional is considered in detail. We show that the first and second …

General Correction For Electrode Sphericity In Voltammetry Of Nernstian Systems, Jerry Goodisman

Chemistry - All Scholarship

The current is considered at a stationary reversible spherical electrode whose potential E(t) as a function of time is given, such that E(t) determines the ratio of oxidized to reduced species at the electrode surface. Writing the current as that for planar geometry, I0, plus corrections for sphericity, we derive formulae for the corrections. The first two are expressed as integrals over I0, with no explicit dependence on the potential, for any form of E(t), and whether the reduced species diffuses into the electrode or into the solution. If the ratio of diffusion constants for oxidized and reduced species is …

Contribution Of The Metal To The Differential Capacity Of An Ideally Polarisable Electrode, Jerry Goodisman, Jean Paul Badiali, Martin Luc Rosinberg

Chemistry - All Scholarship

We consider the response of the metal in the ideally polarisable electrode to charging of the electrode, using a model for the metal surface in contact with the solvent of the electrolyte phase previously presented by us in this journal. We show that the effect of the solvent on the electrons of the metal cannot be considered to be simply that of a repulsive barrier. When the electrode charge varies, qM(dip), the metal contribution to the double layer, is modified, implying a contribution which varies along the electrocapillary curve. By considering an electrostatic interaction between metal and solvent, we find …

Preliminary Rovibrational Analysis Of The Nν6+Ν1−Nν6 Vibration In Hcn⋅⋅⋅Hf, E. Kyrö, K. Mcmillan, M. Eliades, D. Danzeiser, P. Shoja-Chaghervand, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

A preliminary rotation‐vibration analysis of the n=0 and n=1 subbands associated with the nν₆+ν₁−nν₆ hydrogen‐bonded vibration in HCN⋅⋅⋅HF has been completed. The following excited staterotational constantsB′ and band origin frequencies ν₀ have been determined for the complex. The results are consistent with a rotation‐vibration interaction constant α₁=−68.3±1 MHz which correlates with an excited stater(N⋅⋅⋅F) internuclear distance of 2.762 Å, a decrease of 0.034 Å relative to the ground state.Excited state lifetimes associated with assigned transitions are demonstrated to be …

Fluorine, Richard H. Langley, Larry Welch

Faculty Publications

Considering the long time in which fluorine compounds have been used it seems rather surprising that it was not isolated as an element until 1886. This long delay was not due to lack of effort, but to the reactivity of fluorine and the hazards of working with it and many of its compounds.

Xanes In (Tmtsef)2re04: Polarization Dependence Of The Se K-Edge, Juana Vivó Acrivos, S.S. P. Parkin

Faculty Publications, Chemistry

We have measured XANES (X-ray Absorption Near Edge Spectra) near the Re Li (i=l,II,III) edges in (TMTTF)2Re04 and (TMTSeF) 2Re04 and the Se K edge in the latter compound. An important dependence of the XANES at the Se K edge on the polarisation of the incident beam with respect to the crystal axes was observed, whose interpretation can give information on the symmetry of the unoccupied conduction band states. The positions of the Re L edges were compared with those in several inorganic compounds containing Re in various oxidation states, and were found to be, within experimental error, the same …

Metal Ion Oxidative Decarboxylations. 13.¹ Kinetics And Mechanisms Of The Oxidation Of N-Benzyliminodiacetic Acid With Cerium(Iv) In Acidic Perchlorate And Acidic Sulfate Media2, Samir B. Hanna, Marilyn E. Moehlenkamp

Chemistry Faculty Research & Creative Works

The Ce(IV)-mediated decarboxylation of N-benzyliminodiacetic acid (BIDA) produces benzaldehyde, formaldehyde, dimethylamine, benzylmethylamine, and N-benzylglycine in acidic perchlorate and acidic sulfate media. Spectrophotometric evidence of an intermediate Ce(IV)-BIDA complex is given. The data may be interpreted in terms of a mechanism which involves sequential reactions, the first of which is a reversible reaction: BIDA + Ce(IV) (k1) ⇄ (k-1) complex (k2) → products. The rapid complex formation is followed by a slower oxidative decomposition to give a free radical capable of inducing free-radical polymerization. The free radical reacts rapidly with another Ce(IV) to give an iminium ion which undergoes either hydrolysis …

Cerebral Embolism In The Michael Reese Stroke Registry, L. R. Caplan, D. (Daniel) B. Hier, I. D'Cruz

Chemistry Faculty Research & Creative Works

Infarction Secondary to Cerebral Embolism Was Diagnosed in 127 (23.5%) of 540 Patients in the Michael Reese Stroke Registry. Coronary Artery Disease, Atrial Fibrillation, Valvular Heart Disease, Mitral Annulus Calcification, and Cardiomyopathy Were the Commonest Etiologies. Echocardiography Documented a Potential Embolic Source in 7 Patients Without Previously Known Heart Disease and Clarified the Cardiac Pathology in Many of the Patients with Known Heart Disease. the Left Anterior Circulation Was Affected in 48%, Right Anterior in 37%, and Posterior Circulation in 15% of patients. CT Was Abnormal in 71% of the Patients and Was Approximately Equally Helpful in All Locations. Nineteen …

Evaluation Of A New Silicone-Methane Polymer Contact Lens, Jeffrey E. Koziol, Gholam A. Peyman, Hirotsuga Yasuda

Chemistry Faculty Research & Creative Works

A new gas permeable contact lens is produced using a solid silicone core and a plasma polymer surface. This surface is hydrophilic and impermeable to macromolecules. The surface characteristics of this lens were compared with the surface characteristics of available silicone contact lenses. We found that in contrast to our lens, the silicone contact lenses lost their hydrophilic surface with time. In addition, they are permeable to lipid dyes, eg, Sudan red. © 1983 Arch Ophthalmol All rights reserved.

Intermolecular Interactions For Phosphatidyl Choline And Phosphatidyl Ethanolamine, Tony Flaim, Stig Friberg, Patricia L.M. Plummer

Chemistry Faculty Research & Creative Works

Intermolecular interaction between pairs of methylphosphocholine (MPC) and methylphosphoethanolamine were calculated using an extended CNDO/2 program. Experimentally determined conformations were used for the ethanolamine and choline groups. In the methylphosphocholine the major interaction was intramolecular, involving the phosphate ester-choline groups, while in the ethanolamine the maximum attraction was intermolecular between the ethanolamine and the phophate ester of a neighboring molecule(s). © 1983.

Use Of Hydroelectric Dams To Control Evaporation And Salinity In The Colorado River System, Larry J. Paulson

Publications (WR)

The main stem reservoirs on the Colorado River comprise one of the largest and most heavily used freshwater bodies in the nation. These reservoirs (Lake Powell, Lake Mead, Lake Mohave and Lake Havasu) can store up to 53,590,400 acre-feet of water at their maximum capacities. Nonetheless, local water shortages still exist in some areas of the Colorado River Basin. There is also concern that salt concentrations are approaching levels that could severely affect municipal and agricultural uses. Water shortages will become even more acute as demands for water increase with continued urban and agricultural development in the basin.

Water conservation …

The Effects Of Impoundments On Salinity In The Colorado River, Larry J. Paulson, John R. Baker

Publications (WR)

The increase in salinity of our western rivers has been identified as one of the most serious water quality problems in the nation. This is of special concern in the Colorado River where salinity has increased from pristine levels estimated at 380 mg/1 to present-day levels of 825 mg/1 at Imperial Dam. Flow depletions, associated with decreased runoff and increased evaporation and diversions, coupled with high salt loading from natural and man-created sources are considered the primary causes for rising salinity in the river. The urban and agricultural development projected to occur in the basin through this century could deplete …

Thermal Decomposition Kinetics Of Iodine‐Doped Polyacetylene In Vacuum, J. ‐E Osterholm, H. Yasuda, L. L. Levenson

Physics Faculty Research & Creative Works

The thermal stability of iodine‐doped polyacetylene films, (CHIy)x, has been studied by means of electrical conductivity measurements, measurements on weight loss, and mass spectrometric analysis of desorbing species. When heated between room temperature and 125°C in vacuum, these films proved to be of poor thermal stability, being unstable at temperatures above 20°C. During the thermal treatments, molecular iodine desorbs from the films, resulting in an appreciable dopant weight loss with accompanying decrease in the electrical conductivity. The decomposition process does not follow simple kinetics. Copyright © 1983 John Wiley & Sons, Inc.

Role Of D Functions In Ab Initio Calculation Of The Equilibrium Structure Of H2s–Hf, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Full geometry optimizations are performed to determine the equilibrium geometry of the hydrogen‐bonded complex H₂S–HF. The angle between the plane of the H₂S moiety and the H‐bond axis calculated with the 4–31 G basis set is 106° as compared to the experimental value of 91±5°. This quantity is reduced significantly when d orbitals are added to the basis set, yielding an angle within experimental error of 91°. (AIP)