Physical Sciences and Mathematics Commons^™

Applications Of The Semiclassical Spectral Method To Nuclear, Atomic, Molecular, And Polymeric Dynamics, M. L. Koszykowski, George A. Pfeffer, Donald W. Noid

Chemistry Faculty Publications

Nonlinear dynamics plays a dominant role in a variety of important problems in chemical physics. Examples are unimolecular reactions,’ infrared multiphoton decomposition of molecules,’ the pumping process of the gamma ray laser,’ dissociation of vibrationally excited state-selected van der Waals’s complexes,’ and many other chemical and atomic processes. The present article discusses recent theoretical studies on the quasi-periodic and chaotic dynamical aspects of vibrational-rotational states of atomic, nuclear, and molecular systems using the semiclassical spectral method (SSM).’ We note that the coordinates, momenta, and so on, are found using classical mechanics in the studies included in this review. Consequently, certain …

Identification Of Fibroblasts As A Major Site Of Albumin Catabolism In Peripheral Tissues, Jeffrey L. Strobel, Susan G. Cady, Thomas K. Borg, Louis Terracio, John W. Baynes, Suzanne R. Thorpe

Faculty Publications

Rat serum albumin has been labeledw ith dilactitollZ5I- tyramine,( 12‘I-DLT) a radioactive tracer which remains entrappedw ithin lysosomes following cellular uptake and degradation of the carrier protein. Similar kinetics of clearance from the rat circulation were observed for albumin labeled conventionally with lZsI or 12‘I-DLT-albumin, both proteinhsa ving circulating half-lives of -2.2 days. In contrast, the recovery of whole body radioactivity had half-lives of -2.2 and 5.1 days, respectively, for the two protein preparations, indicating substantial retention of degradation products derived from catabolism of ”‘I-DLT-albumin. Measurement of total and acid-soluble radioactivity in tissues 2 or 4 days after injection of …

Identification Of N Epsilon-Carboxymethyllysine As A Degradation Product Of Fructoselysine In Glycated Protein, Mahtab U. Ahmed, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

The chemistry of Maillard or browning reactionosf glycated proteins was studied using the model compound, Nu-formyl-W-fructoselysine(f FL), an analog of glycated lysine residues in protein. Incubation of fFL (15 mM) at physiological pH and temperature in 0.2 M phosphate buffer resulted in formation of lVcarboxymethyllysine (CML) in about 40% yield after 15 days. CML was formed by oxidative cleavage of fFL between C-2 and C-3 of the carbohydrate chain and erythronic acid (EA) was identified a s , the split product formed in the reaction. Neither CML nor EA was formed from fFL under a nitrogen atmosphere. The rate of …

Calculated Electronic Profiles For Liquid-Metal Surfaces, Jerry Goodisman

Chemistry - All Scholarship

The electronic density profile for a liquid-metal surface can be calculated by solving the self-consistent Lang-Kohn equations for the electronic wave functions. One requires a surface density profile for the ion cores, which enters the electrostatic and pseudopotential parts of the electronic Hamiltonian. We use oscillatory profiles, suggested by those found by molecular-dynamics simulations on a pseudoatom model. Calculating surface potentials and work functions, we obtain excellent agreement with experiment (within 0.2 eV). It is shown that use of either step-function ion profiles or a simple variational method leads to serious errors (12 eV) for these quantities.

Glycation Of Amino Groups In Protein, Nancy G. Watkins, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

Ribonuclease A has been used as a model protein for studying the specificity of glycation of amino groups in protein under physiological conditions (phosphate buffer, pH 7.4, 37 “C). Incubation of RNase with glucose led to an enhanced rate of inactivation of the enzyme relative to the rate of modification of lysine residues, suggesting preferential modification of active site lysine residues. Sites of glycation of RNase were identified by amino acid analysis of tryptic peptides isolated by reverse-phase high pressure liquid chromatography and phenylboronate affinity chromatography. Schiff base adducts were trapped with Na- BH&N and the a-amino group of Lys-1 …

Characterization Of Glycated Proteins By 13C Nmr Spectroscopy, Carolyn I. Neglia, Helga J. Cohen, Albert R. Garber, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

13C NMR spectroscopy has been used to characterize Amadori (ketoamine) adducts formed by reaction of [2-13C]glucose with free amino groups of protein. The spectra of glycated proteins were acquired in phosphate buffer at pH 7.4 and were interpreted by reference to the spectra of model compounds, N alpha-formyl-N epsilon-fructose-lysine and glycated poly-L-lysine (GlcPLL). The anomeric carbon region of the spectrum (approximately 90-105 ppm) of glycated cytochrome c was superimposable on that of N alpha-formyl-N epsilon-fructose-lysine, and contained three peaks characteristic of the alpha- and beta-furanose and beta-pyranose anomers of Amadori adducts to peripheral lysine residues on protein (pK alpha approximately …

Copper And Barium As Dietary Discriminants: The Effects Of Diagenesis, J B. Lambert, S V. Simpson, Carole B. Szpunar, J E. Buikstra

Chemistry: Faculty Publications and Other Works

In skeletons excavated from Woodland sites, copper and barium levels are found to have been contaminated by influx from the soil environment. Electron microprobe scans for both elements show build-up along the outer surface of femur cross sections. Elemental levels for Cu and Ba are lower in the femur or fibula than in the more porous rib. The distribution of Cu in the immediately surrounding soil is highly anisotropic. These observations indicate that Cu and Ba should not be used for dietary inferences about ancient populations without independent evidence that diagenesis is not important.

A Three Part Research Report: The Synthesis Of Potential Insecticides, N-(4-Heteroaryloxybenzoyl)-N'-(2,4-Dichlorobenzoyl) Hydrazines: A Reinvestigation Of Hexamethylphosphoramide With Ketoximes; Regioselective Fluoralkoxylation And Polyfluoroalkoxylation Of Activated Dihalobenzenes And Dihaloheterocycles, Gary A. Decrescenzo

Retrospective Theses and Dissertations

This report discusses research in three areas of organic synthesis: The synthesis of potential insecticides; the reinvestigation of the reaction of hexamethylphosphoramide with ketoximes; and the regioselective fluoroalkoxylation and polyfluoroalkoxylation of activated dihalobenzenes and dihaloheterocycles. In Part I, a series of N-(4-heteroaryloxybenzoyl)-N'-(2, 3-dichlorobenzoyl) hydrazines are synthesized, and attempts at cyclic dehydration to the corresponding 2, 5-disubstituted-1, 3, 4-oxadiazoles are discussed. In Part II, the synthesis of N, N-dimethyl-N'-aryl amidines by the reaction of aryl alkyl and diaryl ketoximes with HMPA is discussed. In Part III, a series of activated dihalobenzenes and dihaloheterocycles are reacted with sodium trifluoroethoxide to study the …

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 …

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 …

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 …

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 …

Calculated Electrocapillary Curve For A Molten Salt, Jerry Goodisman, S Amokrane

Chemistry - All Scholarship

If bulk properties of simple molten salts may be reasonably well understood in terms of the primitive model, the situation with respect to surface properties is less satisfactory. It has been shown that a simple model for the distributions at the free surface of a molten salt can give surface tension and surface energy in reasonable accord with experiment, provided that a factor guaranteeing local electroneutrality is introduced. In this model, properties are given in terms of bulk-salt distribution functions, for which the primitive model is used. The present work extends this model to the electrocapillary curve, i.e., variation of …

The Effect Of Tungsten(0)Pentacarbonyl On Coordinated Ligands, Janice Imada Byington

University of the Pacific Theses and Dissertations

A series of monosubstituted tungsten(0)pentacarbonyl complexes, W(CO)₅L (L = water, hydrogen sulfide, pyrazine, pyrimidine, 4,4'-bipyridine, 4-cyanopyridine, isonicotinamide, and methanol) were synthesized and characterized. The purpose of this project was to determine the effect of the W(CO)₅ moiety on the coordinated ligand, L.

The visible spectra of the synthesized W(CO)₅L complexes typically exhibited a maximum around 400 nm ((epsilon) (TURN) 4000). The infrared spectra of these complexes exhibited the characteristic three band pattern (2A₁ + E) in the carbonyl region ((TURN)2070 cm^-1, (TURN)1930 cm^-1, (TURN)1900 cm^-1. The pKa's of …

Effect Of Solvent On Properties Of The Liquid Metal Surface, J. P. Badiali, M. I. Rosinberg, Jerry Goodisman

Chemistry - All Scholarship

We calculate the difference in the surface potentials between the free surface of a liquid metal and the same metal in an ideally polarizable interface at the point of zero charge. This difference, δXm, is due to the deformation of the electronic cloud of the metal by the solvent molecules. The simple model used for the free (metal-metal vapor) surface yields qualitatively correct work functions for a number of metals (Hg, Cd, In, Zn, Pb, Ga, A1). Two simple ways to model the metal-solvent interaction are proposed and calculations of δXm made for each. One, the dielectric film model, considers …

A Matrix Isolation Study Of The Reactions Of Oxygen(Singlet-D) With The Chlorofluoromethanes Fluorotrichloromethane, Dichlorodifluoromethane And Chlorotrifluoromethane, Richard Thomason Burke

University of the Pacific Theses and Dissertations

We have studied the reactions of O(¹D) with CC1₃F, CC1₂F₂ and CC1F₃ in CO₂, SF₆ and N₂O matrices, and in neat mixtures. Photolysis of cryogenic mixtures of ozone and the chlorofluoromethanes in various matrix hosts resulted in production of O(¹D) which migrated through the matrix to react with the Freon molecules. Products were detected by infrared spectroscopy of the matrix deposits, with assignments confirmed by comparison of ¹⁶O and ¹⁸O absorption bands with literature values. Evidence for oxygen atom insertion into a C-C1 …

Method For Direct Preparation For 1,2,4-Triazole From Hydrazine And Formamide, Harris E. Petree, Joseph R. Pociask, John T. Gupton

Chemistry Faculty Publications

Process for the preparation of 1,2,4-triazole comprises contacting hydrazine or its aqueous solutions with at least about 2.5 moles of formamide at a temperature of 140° to 210° C. and then recovering the resultant 1,2,4- triazole in yields of 92-98% with 94-98% purity. The formamide is maintained in an excess over about the 2.5 molar amount consumed in the reaction with the hydrazine. Recovery steps for isolating the 1,2,4-triazole are disclosed.

Nonenzymatic Glucosylation Of Rat Albumin: Studies In Vitro And In Vivo, James F. Day, Robert W. Thornburg, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

Incubation of rat serum with D-glucose in vitro resulted in nonenzymatic glucosylation of serum proteins. Analysis of freshly isolated rat albumin by ion exchange chromatography indicated that the glucosylated albumin accounts for 6.7.+-. 0.9% of total albumin in normal rat serum. Glucosylation of rat albumin in vitro was 1st order with respect to glucose and albumin concentrations and occurs primarily (> 90%) at intrachain lysine residues. Kinetic analysis and inhibition of glucosylation by aspirin suggest that 1 reactive lysine residue is the primary site of glucosylation. Less than 5% of the radioactivity from glucosyl-albumin was released as glucose or mannose …

Isomerization And Dehydrocyclization Of 1,3-Pentadiene, Thomas E. Marcinkowski

Retrospective Theses and Dissertations

Piperylene concentrate is a complex mixture of 5-carbon unsaturated hydrocarbons obtained as a by-product when naphtha or gas oils are cracked. The major component in this mixture is 1,3-pentadiene. During the course of this study, a number of trials, utilizing liquid phase reaction conditions, were made to investigate the geometric isomerization of 1,3-pentadiene and its separation from the piperylene concentrate. Isomerization was accomplished employing catalytic amounts of iodine at temperatures ranging from 0°C to reflux. Using this method, the maximum amount of trans-1,3-pentadiene obtained was 70% as compared to 51% in the piperylene concentrate. Recovery of the product was 90%, …

Surface Tensions Of Molten Salt Mixtures, Jerry Goodisman

Chemistry - All Scholarship

It is always found that the surface tension of a mixture of molten salts lies below the mean of the surface tensions of the pure components, weighted by mole fractions. Part of this effect is certainly due to the well-known fact that the composition near the surface is enriched in the component of lower surface tension. We show that an effect of the long-range forces, present for fluids involving Coulombic interactions, is of greater importance. The effect is due to the electroneutrality constraint on the distribution functions. As we show by separate calculations, both effects must be considered to obtain …

Nonenzymatically Glucosylated Albumin: In Vitro Preparation And Isolation From Normal Human Serum, James F. Day, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

Incubation of human serum with D-[6-3H]glucose resulted in the gradual accumulation of radioactivity in acid-precipitable material. Upon chromatography on Sephadex G-200, radioactivity was found associated with each of the major molecular weight classes of serum protein. Purified human serum albumin was also glucosylated in vitro upon exposure to D-[6-3H]glucose in phosphate-buffered saline. The glucosylated and unmodified albumins were separated by ion exchange chromatography. The physiological significance of these observations in vitro was confirmed by the isolation and quantitation of glucosylated albumin from normal human serum. Glucosylated albumin represents approximately 6 to 15% of total serum albumin in normal adults. The …

Determination Of Surface Thickness Assuming A Linear-Density Profile, Jerry Goodisman

Chemistry - All Scholarship

Assuming a one-parameter model for the two-particle distribution function of a surface, one can choose a value of the "width parameter" to yield a correct surface tension. In order to then identify the width of the surface layer with the value of the width parameter, as is often done, one can check the validity of the model by verifying that other properties (e.g., surface energy) are correctly calculated, or, as proposed herein, by demonstrating that different formulas for the surface tension give identical results. A new formula is derived, and the relation between the different formulas discussed. Calculations are performed …

A Process For The Production Of 2-Alkyl Or 2-Cycloalkyl-4-Methyl-6-Hydroxypyrimidines, Joseph T. Blackwell Iii, John T. Gupton, Teruko U. Miyazaki, James B. Nabors, Joseph R. Pociask

Chemistry Faculty Publications

Production of 2-alkyl- or cycloalkyl-4-methyl-6- hydroxypyrimidines by first neutralizing an alkyl imidate ester hydrochloride with a base in the presence of a water-immiscible solvent for the alkyl imidate ester to be freed thereby; condensing the alkyl imidate ester with diketene to form an oxazinone intermediate, which is then reacted in organic solution with gaseous ammonia and recovering the desired substituted 6-hydroxypyrimidine.

[3H]‑Raffinose, A Novel Radioactive Label For Determining Organ Sites Of Catabolism Of Proteins In The Circulation, Jonathon Van Zile, Lee A. Henderson, John W. Baynes, Suzanne R. Thorpe

Faculty Publications

The primary tissue sites of catabolism of plasma proteins with long circulating half-lives are unknown. It has been difficult to identify these sites because plasma proteins are delivered to tissues at relatively slow rates but are rapidly degraded intracellularly within lysosomes. Therefore, a tracer attached to protein is lost from the site of uptake before an amount sufficient for quantitation can accumulate. We hypothesized that sucrose (Glupal-2 /3Fruf) would be a useful label to circumvent this difficulty because of the stability of sucrose in lysosomes; and thus, sucrose should remain in tissue long after the protein to which it was …

A Model For The Surface Of A Molten Salt, Jerry Goodisman, R. W. Pastor

Chemistry - All Scholarship

A model is proposed for the two-particle distribution functions for the surface region of a system composed of two oppositely charged species with identical hard sphere repulsions. The distribution functions are formed from those for the bulk fluid by incorporating a cutoff corresponding to the surface and a multiplying factor defined so as to guarantee electroneutrality while maintaining the proper symmetry. Various methods for doing this are discussed. Good agreement is obtained for surface tension and surface energy. Density oscillations are predicted.

Coordination Chemistry Of Bidentate Difluorophosphines, Darrell Lynn Gallup

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The reactions of 1, 2–bis(difluorophosphino)cyclohexane, PF₂C₆H₁₀PF₂, with hexacarbonyls of Cr(O), Mo(O), and W(O) have been extensively investigated. The hexacarbonyls react, either under photolytic or thermolytic conditions, to produce carbon monoxide and oily mixtures of products of the general formulations, [M(CO)₄(PF₂C₆H₁₀PF₂C)]_x, where x varies apparently from 1 – 4. The higher values of x, corresponding to species involving bridging ligands, are more common to the photolysis rather than the thermolysis reactions. Photolysis reactions of Mo(Co)₆ with increasing amounts of the …

Thermodynamics And Statistical Mechanics Of The Ideally Polarisable Electrode Gibbs Isotherm And Surface Tension, Jean-Pierre Badiali, Jerry Goodisman

Chemistry - All Scholarship

A definition of the ideally polarisable electrode which allows a general statistical mechanical treatment is given, comparisons with the usual thermodynamic approach being made. It is shown that, with this definition, the system behaves as a pure capacitance to an imposed alternating potential of sufficiently low frequency. The equilibrium states of the system are described by the grand canonical distribution. Thermodynamic functions, given in terms of the grand canonical partition function, can be computed in molecular terms: In particular, general expressions for the surface tension and the pressure are obtained, and compared to those proposed by various authors. The separation …