Physical Sciences and Mathematics Commons^™

Effects Of Basis Set And Electron Correlation On The Calculated Properties Of The Ammonia Dimer, Z. Latajka, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Ab initio calculations are carried out for (NH₃)₂ with a 6‐31G∗∗(1p,2d) basis set containing diffuse polarization functions. Electron correlation is included via second‐order Møller–Plesset perturbation theory (MP2). At the SCF level, the equilibrium R(NN) distance is 3.54 Å and the interaction energy is −2.35 kcal/mol. Inclusion of correlation enhances the attraction substantially, increasing the energy to −4.05 kcal/mol and reducing the intermolecular separation by 0.20 Å. Comparison with previous results at the SCF level demonstrates a variety of errors including exaggerated dipole moments, underestimation of polarization …

A Re-Examination Of The Reactions Of Cyanide With Cytochrome C Oxidase, M. G. Jones, D. Bickar, M. T. Wilson, M. Brunori, A. Colosimo, P. Sarti

Chemistry: Faculty Publications

Experiments were performed to examine the cyanide-binding properties of resting and pulsed cytochrome c oxidase in both their stable and transient turnover states. Inhibition of the oxidation of ferrocytochrome c was monitored as a function of cyanide concentration. Cyanide binding to partially reduced forms produced by mixing cytochrome c oxidase with sodium dithionite was also examined. A model is presented that accounts fully for cyanide inhibition of the enzyme, the essential feature of which is the rapid, tight, binding of cyanide to transient, partially reduced, forms of the enzyme populated during turnover. Computer fitting of the experimentally obtained data to …

The Synthesis Of Various Substituted 3-Amino-7-Hydroxy-2,2-Dimethyltetralins And Their Opioid-Related Activities, David Alan Lippman

University of the Pacific Theses and Dissertations

A series of aminotetralones and aminotetralins were synthesized from the common intermediate F, 3-amino-2,2-dimethyl-7-methoxy- 1-tetralone. The final compounds derived from F were simple substituted and/or reduced analogues. The products would allow a progressive structure activity relationship to be drawn based on pharmacological testing.

The common intermediate F was synthesized utilizing a six step procedure starting with p-methoxyphenylacetic acid. The overall yield from the precursor to the F:HC1 was 25%. Compound F was either O-demethylated to form 3-amino-2,2-dimethyl-7-hydroxy-l-tetralone (I) or was dimethylated on the amine and subsequently O-demethylated to yield the 3-dimethylamino-7-hydroxy-2,2-dimethyl-l-tetralone (J). The last major modification was the reduction of …

Sulphur Needs Of Crops And Pastures, J S. Yeates

Journal of the Department of Agriculture, Western Australia, Series 4

Sulphur deficiency has long been recognised as a potential problem of legume pastures in the higher rainfall areas (over 750 mm a year) of south-west Western Australia. Before the introduction of granulated superphosphate (about 1970), sulfer deficiencies commonly developed in spring on susceptible soils despite autumn applications of superphosphate (containing about 10.5 per cent sulphur).

In loww and medium rainfall areas sulphur deficiency is rarely reported, at least partly because of annual superphosphate applications. However large areas of the sandy-surfaced soils of Western Australia would become sulphur deficient for pastures and crops if sulphur inputsd in fertilisers were substantially reduced. …

Soil Acidity In The Eastern Wheatbelt, W M. Porter, I. R. Wilson

Journal of the Department of Agriculture, Western Australia, Series 4

In Western Australia parts of the sandplain of the eastern wheatbelt are very acid and produce poor crops, It was not until the late 1970s that the effect of soil acidity on the productivity of the sandplain soils was examined in any detail.

Since then researchers have learnt a great deal about the nature of soil acidity in the eastern wheatbelt sandplain soils and can suggest management options for farmers.

This article discisses the problem of the very acid soils. It does not deal with the moderately acid, medium textured soils of the eastern wheatbelt. Although the acidity of these …

Soil Acidity On High Rainfall Pastures, J S. Yeates, D. A. Mcghie, I. R. Wilson

Journal of the Department of Agriculture, Western Australia, Series 4

Most soils of the high rainfall area of south-western Western Australia are naturally acis.

The most acid group of soils, the peaty sands. have been routinely limed before subterranean clover pastures were established since research in the 1950s showed that poor Rhizobium nodulation could be overcome with the application of about 2 tonnes per hectare of coastal limesand.

Soil Acidity And Liming In The Lower Great Southern, R N. Glencross, M. G. Clarke

Journal of the Department of Agriculture, Western Australia, Series 4

In the 375 to 750 millimetre rainfall area of the Lower Great Southern, reports of loss of subterranean clover from established pastures, reduced carrying capacity for sheep and increasing soil acidity lead to the establishment in 1981 of a research programme into the effects of soil acidity on pasture productivity in that region.

Solvolysis Of 2-Buten-2-Yl Triflates, Michael M. Mellis

Dissertations, Theses, and Masters Projects

No abstract provided.

Synthesis Of 2-Alkylidene-1,3-Cyclohexanediones, Mary Virginia Manson

Dissertations, Theses, and Masters Projects

No abstract provided.

Synthesis And Characterization Of Some Oxoperoxopolycarboxylato Vanadates (V) And Their Biochemical Significance, Myunghi Lee

Dissertations, Theses, and Masters Projects

No abstract provided.

Electrochemical Studies On Peroxo Heteroligand Vanadates (V) In Aqueous Solution, David J. Mayonado

Dissertations, Theses, and Masters Projects

No abstract provided.

Semi-Flexible Polyimide And Polyamide Systems, John Ryan Evans

Dissertations, Theses, and Masters Projects

No abstract provided.

High Valent Chromium (V) And Chromium (Vi) Complexes, Harry Bennett Davis

Dissertations and Theses

A new preparative route to the only neutral chromium (V) oxide fluoride, chromium oxide trifluoride, has been accomplished by the reaction of xenon difluoride with chromyl fluoride at high temperature. The chromium oxide trifluoride is produced as crystals which are suitable for single crystal studies. In reactions of chromium oxide trifluoride with alkali and alkaline metal fluorides in anhydrous hydrogen fluoride, new chromium(V) oxide fluoride salts were obtained; these salts were not of high purity due to unknown problems. An attempt to prepare chromium oxide tetrafluoride by the reaction of xenon difluoride with chromyl fluoride in anhydrous hydrogen fluoride failed …

The Intermolecular Force Field Of Acetylene-Hcl: The Normal Coordinate And Centrifugal Distortion Analysis Of Two Weakly Bound Rigid Rods, Rebecca S. Lee

Masters Theses

In order to determine the intermolecular force field of C₂H₂⋅⋅HCl, a normal coordinate analysis appropriate for two weakly bound rigid rods is developed. An exact centrifugal distortion analysis is then carried out on the microwave spectrum of this "T''-shaped hydrogen-bonded π complex. The distortion constants and published matrix-isolated vibrational frequencies are employed in the normal coordinate analysis to obtain the intermolecular force field and refinements in the structural parameters. The following van der Waals force field is found to reproduce the existing spectroscopic constants of C₂H₂⋅⋅H³⁵Cl … . This study …

The Purification And Partial Characterization Of The Surface Polysaccharides From Three Fast-Growing Rhizobium Japonicum Strains, Madhav P. Yadav

Masters Theses

The fast-growing strains of R. japonicum were originally isolated from China. They are acid-producing Rhizobia and are capable of nodulating soybeans. These isolates share a common host-specificity (Peking soybean) with the slow-growing R. japonicum strains even though their biochemical properties are more closely related to other fast-growing Rhizobium species. The surface polysaccharides from three fast-growing R. japonicum strains--USDA201, USDA205, and HC205--were isolated and partially characterized. Strain HC205 is a nod⁻ mutant of USDA205 which lacks the symbiotic plasmid. These surface polysaccharides consist of extracellular, capsular and lipopolysaccharides (EPSs, CPSs and LPSs). The EPSs from all three strains are very similar …

A Study Of Oxygen Functional Groups In Illinois Coal Fractions, Kenneth R. Osborne

Masters Theses

Ferric chloride/acetic anhydride reacted with butyl phenyl ether in acetonitrile at 80° to give a 75.6% yield of p-butoxyacetophenone. Reactions with benzyl aryl ethers gave 30% cleavage. The reaction of benzyl phenyl ether gave 10.3% p-benzyloxyacetophenone as well as cleavage product. Reaction of a pyridine soluble, toluene insoluble fraction (preasphaltene) of an Illinois No. 6 coal with ferric chloride/acetic anhydride in acetonitrile gave a product 94% insoluble in pyridine. The insolubility was ascribed to condensation reactions.

Phenols were measured in coals, preasphaltenes and preasphaltene derivatives by acetylation with acetic anhydride in pyridine. Suggestions for improvement in the method were presented. …

Totally Empirical Wavefunctions From X-Ray Diffraction Data, Martin Jeffry Goldberg

Dissertations, Theses, and Capstone Projects

The interpretation of coherent x-ray diffraction experiments by a quantum model is described. Adjusting the coefficients of an LCAO expansion to best fit measured Bragg intensities results in a totally empirical quantum wavefunction. The quantum model is compared to a multipole expansion. The constraints imposed by quantum mechanics are examined, and several methods of satisfying these constraints while best fitting a wavefunction to measured Bragg intensities are detailed. Application is made to beryllium metal, with a resultant fit R(,1) = .00249. Similar applications to graphite and diamond are outlined. The formalism is extended to explicitly include solid-state effects, and this …

Mass Spectrometric Studies Of Oxygen Isotope Exchange Reactions With Oxide Surfaces, Gayle J. Allen

Chemistry & Biochemistry Theses & Dissertations

Isotopic exchange reactions with the surface of amorphous silica and crystalline quartz were studied mass spectrometrically. A mixture of approximately 2%18_o2 in neon was used as the test gas, and was passed over the surface of the oxides. Measurements were taken as a function of temperature and residence time, for kinetic studies.

These studies clearly show a second order rate law for the surfaces examined. The rate constant on amorphous silica was 2.2xl0²L/mol/sec. The energy of activation was 35.3 kcal/mol and the frequency factor was l.35xl0⁹L/mol/sec. On the crystalline quartz the rate constant was 2.0xl0 …

Chemistry Of Singlet Oxygen. 47. 9,10-Dicyanoanthracene-Sensitized Photooxygenation Of Alkyl-Substituted Olefins, Thomas Goyne, Yasuhiko Araki, Diane Dobrowolski, Douglas Hanson, Zhi Jiang, Kenneth Lee, Christopher Foote

Thomas Goyne

No abstract provided.

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

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

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 …

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.

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.

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 …