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The Synthesis Of Pyrimidines And Condensed Pyridazines As Potential Antimetabolites, Judith A. Wagner

Chemistry and Chemical Biology ETDs

Interest in the compounds described by this thesis was first aroused in the early 1930's when a research team began to investigate the mass poisonings of the population in Indonesia. The cause of the poisonings seemed to be the foodstuffs which the people made for themselves from the abundant coconut. Two products in particular, Bongkrek and Semaji, made from coconut presscakes and grated coconut, were apparently the source of the toxic substance. When made under improper conditions, the toxic principle developed in an otherwise harmless food product. A compound was finally isolated and established as the toxic principle by …

Development Of Standard Procedures For Determination Of [Delta]G° (K), [Delta]H° And [Delta]S° Values Via Potentiometric And Calorimetric Titration Techniques, Jack Hugh Ruckman

Theses and Dissertations

Standard computer techniques were developed for computation of ΔG° values from potentiometric titration data and ΔH° values from calorimetric titration data. The procedures developed can be used for any systems having the general equations HA = W^+ + A^- ; H_2A = 2H^+ + A^2- ; and H_3A = 3H^+ + A^3-, where the proton ionizations may be consecutive or simultaneous. The thermodynamic values ΔG°(K), ΔH° and ΔS° were determined for the ionization of protons from the protonated compounds methionine (-NH_3^+ group only), phosphoethanalomine and phosphoserine. The compounds studied were selected because they contain one, two and three ionizable protons …

The Determination Of Thiamin And Its Derivatives In Brain Tissue Of Control, Thiamin-Deficient, Oxythiamin- And Pyrithiamin-Treated Rats, David S. Murdock

Theses and Dissertations

The determination of total thiamin, free thiamin, thiamin di phosphate (TDP) plus thiamin triphosphate (TTP), and total α- hydroxyethylthiamin (HET) levels in rat brain in control, deficient, oxythiamin- (OTH) and pyrithiamin- (PTH) treated rats was accomplished. It was found that the TDP + TTP/thiamin ratio observed in the thiamin-deficient, OTH- and PTH-treated rats was constant and did not differ from the ratio observed in the control rat brains. The brain levels of TDP + TTP decreased to 39% and 12% of the control thiamin levels in deficient and PTH-treated rats respectively. The brain HET and TDP + TTP levels of …

The Purification And Characterization Of Cytochrome B₅ From Porcine Kidney, M. Dean Klingler

Theses and Dissertations

A soluble form of cytochrome b_5, with a 413/280 nm ratio of nearly unity, has been isolated and purified from porcine kidney using fractional precipitation, ion exchange resins, and gel filtration procedures. The cytochrome b_5 shows heat stability up to 50° and is stable in the pH range 6.0 to 8.5. The oxidized protein exhibits an absorption maximum at 413 nm, while the reduced form shows three peaks: 423, 526, 556 nm. Molecular weight determinations have given variable results, suggesting the possibility of a polymer composed of four and eight units of a 13,500 molecular weight protomer. This study has …

|Ni.|Pa Calorimetric Study Of The Heat Of Ionization Of Water At 10 And 40°C, And,|Nii.|Pa Calorimetric Determination Of The Heat Of Reaction Of Tris (Hydroxymethyl) Aminomethane (Tham) With Hydrochloric Acid In Aqueous Solution At 10, 25, And 40°C, Griffith Lyn Kimball

Theses and Dissertations

The heat of neutralization, ΔH_-N, of perchloric acid with sodium hydroxide has been determined at 10 and 40° in a low ionic strength, μ, region using a nonisothermal, constant-temperature-environment solution calorimeter. Correction of the data to infinite dilution by extrapolation of a plot of ΔH_-N vs μ^0.5 gives values at zero ionic strength for the heat of ionization of water of 14.216 and 12.695 kcal/mole, respectively, at 10 and 40° . The data are correlated with those of earlier workers to give an equation allowing the calculation of the heat of ionization of water at zero ionic strength over the …

⁷Li(D,P)⁸Li Excitation Function :|Be[Subscript D] = 0.623 Mev To 1.968 Mev, Albert E. Schilling

Theses and Dissertations

In this study the excitation function for the ^7Li(d,p)^8Li reaction is determined at incident deuteron energies ranging from 0.623MeV to 1.968MeV by counting the delayed alpha-particles as a result of the ^8Li beta decay. This excitation function reveals resonances at 0.777±0.012MeV and 1.031±0.015MeV with cross sections of 202±9mb and 188±8mb respectively. The uncertainty in the cross section values was due to three independent sources of error within this experiment, the solid angle, the ^8Li half-life, and the target (LiF) thickness. The uncertainty in the energy values was determined from an energy calibration of the accelerator used in this study. Resonances …

Reactions Of N₂F₄ And Sf₆ With H₂ Induced By Co₂ Laser Pulses And By Electrical Discharge, John Leslie Lyman

Theses and Dissertations

A high power pulsed CO_2 laser was used to induce reactions in gas mixtures containing either N_2F_4 or SF_6. The rate of laser induced dissociation of N_2F_4 to NF_2 was as much as 1000 times faster than the thermal rate, and the rate law was of lower order than the thermal, bimolecular rate law. Explosion threshold and induction time data were obtained for butene stabilized mixtures of N_2F_4 and H_2. HF laser gain was observed during the first few microseconds of CO_2 laser pulse, but it was strongly quenched by the explosion. The laser driven reaction of SF_6 with H_2 …

Thermodynamic Equilibrium Formation Constants And Molal Concentrations Of The Complexed Mercury-Containing Species Of Mercuric Chloride In Added Hydrochloric Acid And Methanol-Water Solvent Mixtures, Karl Jennings Walker

Theses and Dissertations

Saturated solutions of mercuric chloride in different methanol-water and hydrochloric acid solvent mixtures were equilibrated at 25.00 ± 0.01°C. Total mercury and free chloride concentrations were determined by analytical procedures and the data were analyzed with the aid of the computer. Tabulated below are the results of this study: [--see thesis for table--]

The Photolysis Of Propane At 123.6 Nm, James H. Vorachek, Robert D. Koob

Office of the Provost Scholarship

Propane has been photolyzed at 123.6 nm, in the presence and absence of O₂, at pressures from 2–380 Torr. All products except ethane exhibit a pressure dependence which is attributed to secondary dissociation of the primary fragments, H₂, CH₄, C₂H₄, and C₃H₆. It is assumed that the range of energies carried by these fragments is broad enough that some will not dissociate even at low pressures while others of the same species cannot be stabilized even at high pressures. An internally consistent analysis rationalizes the entire …

An External Goniometer For Orientation Of A Cryostat, N.C. Lockhart, L.F. Nichols, Craig J. Eckhardt

Craig J. Eckhardt Publications

An economical two-circle orienting external goniometer has been designed and fabricated for an Andonian liquid helium Dewar. The Dewar can be tilted ±30° from the vertical in two perpendicular directions. The geometrical center of the Dewar's optical cavity moves a maximum of 1 mm when the cryostat is tilted the full 30°. The basic design involves the rotation of two concentric cylinders riding on bearing surfaces. Two chain belts and gear boxes are used as drive mechanisms.

Radiative And Predissociative Lifetimes Of The A ²Σ+ State Of Oh, Richard Orlin Sutherland, Richard A. Anderson

Chemistry Faculty Research & Creative Works

Lifetime measurements have been made on the A 2Σ+ state of OH by the delayed coincidence technique in conjunction with an interrupted rf discharge through water vapor. Lifetimes are reported for rotational states up to K=29 and K=20 in the ν=0 and ν=1 vibrational levels, respectively, and on the unresolved levels of ν=2. A predissociation, previously predicted from relative intensity measurements, resulting from a curve crossing by the repulsive 4Σ− state, was observed for the rotational states above K=23 of ν=0, for those above K=14 of ν=1, and for all those of ν=2. These lifetime data are discussed qualitatively in …

A Pycnometer Of Improved Design, Richard Moore

Journal of the Minnesota Academy of Science

The density of a solution must be known to laboratory medicine , biochemistry, and physical chemistry. Knowledge of the density may permit calculation of solution concentration, solute molecular weight, solute partial, or specific volume , for example. Therefore, the determination of the density of a solution is a measurement which must be made with precision, accuracy, and sensitivity. This report describes a pycnometer which permits making such measurements.

A Study Of Bisimines Of Tetramethyl-1,3-Cyclobutanedione, Edward Albert Schmidt

Electronic Theses and Dissertations

It was the purpose, therefore, of this work, to investigate the preparation, properties, and reactions of bisimines of 2,2,4,4- tetramethyl-1,3-cyclobutanedione, to determine the chemical effects of carbon π-bonded to nitrogen. Certain of these effects are compared to carbon π-bonded to oxygen in a structurally similar environment.

The Consideration Of Some Aspects Of Two Methods Used To Study Ion Association, Richard Karl Gard

Masters Theses

An investigation was made into the possibility of determining thermodynamic ion association equilibrium constants for salts important in the study of seawater using spectrophotometry and ion selective electrodes. Calcium sulfate was used as the test salt. The success of the spectrophotometric method was found to depend upon the choice of a suitable indicator and refinement of the proper instrumental techniques. The indicators investigated were 1-(2'-hydroxy-1'-benzeneazo)-2-hydroxynaphthalene, 1-(2'-hydroxy-5'-chloro-1'-benzeneazo)-2-hydroxynaphthalene, and ammonium purpurate (murexide). Ammonium purpurate was found to be the most suitable indicator. Spectra of these three indicators and their calcium complexes at pH 10 are included in the paper. The ion selective …

Final Report On Interrelationships Between Chemical, Physical And Biological Conditions Of The Waters Of Las Vegas Bay Of Lake Mead, James E. Deacon, Richard W. Tew

Publications (WR)

This program was a status study of the interaction between Las Vegas Wash, an enriched stream, and Las Vegas Bay, a wedge shaped arm of one of the world's deeper reservoirs. The program centered primarily on identification and counting of planktonic algae from several points in Las Vegas Bay. Additional work on nutrient enrichment of water samples was conducted to aid in interpretation of algal distribution related to nutrient input. Examination of a variety of physical, chemical, and biological parameters, both at many surface points in the bay, as well as in vertical profile, was also accomplished and further aided …

Polarographic Trace Analysis Of Copper, Lead And Cadmium, Donald Paul Jepson

University of the Pacific Theses and Dissertations

The area of study for this project was the development of an accurate, reliable, and inexpensive method of trace analysis for copper, cadmium, and lead in foods. AT this time, the Association of Official Analytical Chemists Manual, eleventh edition, (4) has only official and recognized methods of analysis for copper (25.023), cadmium (25.018), and lead (25.041). In general, these procedures are long and tedious. The digestions involved often require many hours and are quite dangerous due to leakage of metallic and organometallic fumes from the digestion apparatus. The official methods of analysis for these elements require a very large outlay …

The Kinetics And Mechanism Of The Reaction Of Chromium(Ii) With Pentaaquodiiodomethyl Chromium(Iii) And Pentaaquomonoiodomethyl Chromium(Iii) Ions., Ronald Sinclair Nohr

University of the Pacific Theses and Dissertations

Transition metal ions, in low oxidation states, have gained increasing use as versatile reducing agents for a number of organic compounds. The ability of metal ion to act as reducing agents in organic reactions is frequently thought to be due to the formation of intermediates which contain an organic species bound to a metal, although the identy of these organo-metallic intermediates has been determined in relatively few cases.

The purpose of this research was to investigate the kinetics and mechanism of one such reaction: the reduction of iodoform to methane by chromium(II). Two air stable organochromium(III) intermediates were separated and …

Applications Of New Methods Of Structure Determination, Richard Earl Wagner

Electronic Theses and Dissertations

The structures of: 1) 2-piperidino-5-chlorornethyl-5-rnethyl-2- oxo-1, 3,2-dioxaphosphorinan; 2) 2-phenoxy-5-chloromethyl-5-methyl-2- oxo-1, 3,2-dioxaphosphorinan; 3) 2-p-bromophenoxy-5-chloromethyl-5- chloromethyl-5-methyl-2-oxo-1, 3, 2-dioxaphosphorinan have been resolved by x-ray single crystal studies. A Picker 4 circle diffractometer employing molybdenum x-rays and a zirconium filter was used to obtain accurate data. The space group of the first two compounds is P2₁/c while that of the third is Pca2₁. The lattice constants of the compounds are: 1) a = 10.035(8)Å, b = 6.503(4), c = 20.19(1), β = 96.8(3)°; 2) a = 6.237(3)Å, b = 11.437(5), c = 19.419(9), β = 109.95(3); and 3) a = …

The Primary Structure Of Nifungin, Marvin Lee Withrow

Electronic Theses and Dissertations

The primary structure of the antifungal peptide nifungin was studied. Amino acid analysis of nifungin before and after performic acid oxidation revealed 51 amino acids and the presence of an unidentified ninhydrin positive material. The unidentified material constituted approximately ten per cent of nifungin by weight. It contains nitrogen but, as reported by others (2), did not contain phosphate or reducing sugars. It was not hydrolyzed into smaller compounds by strong mineral acids. Carboxyl terminal analysis was conducted utilizing carboxy-peptidase A and B on both the oxidized and unoxidized nifungin. Tyrosine appeared to be released most rapidly followed by lysine, …

Ferroxidase-Ii: A Blood Serum Lipo-Protein, Christine Shih Ming Sung

Master's Theses

Ferroxidase-II was definitely identified as a lipoprotein. Cholesterol and phospholipids remained tightly associated with the ferroxidase-II protein following extensive purification. Quantitative analysis showed that it is a high-density lipoprotein. Thin-layer chromatographic analyses indicated that phosphatidylcholine accounts for the majority of the bound phospholipid with lysophosphatidyl choline and sphingomyel in accounting for the remaining phospholipid.

Treatment of purified ferroxidase-II with phospholipase C or A resulted in a loss of ferroxidase activity which paralleled the hydrolysis of phospholipid. Phospholipid D treatment also resulted in the loss of ferroxidase activity, yet the loss was not as great as with other phospholipases. A lipid-depleted …

Xanthine Oxidase Catalyzed Oxidation Of Acetaldehyde Substrate And Carboxylate Inhibition, Patrick A. Goodman

All Master's Theses

In recent years, interest in an enzyme which catalyzes the oxidation of a variety of aldehydes and purines has been growing steadily. In fact, this enzyme commonly known as xanthine oxidase, has been implicated by some (1) in the regulation of nucleic acid synthesis and cellular growth - an important consideration in the study of caner. Unfortunately, detailed investigations directly pertaining to biological aspects of this enzyme have as yet been somewhat limited. Nevertheless, the amount of information concerning the nature of the enzyme and its catalytic effects upon different classes of substrates, through far from complete, is indeed significant.

Preparation And Characterization Of The Addition Compounds Formed By Trifluoromethylsulfur Trifluoride With The Lewis Acids Pf5, Bf3, Asf5, And Sbf5, Maria Kramar

All Master's Theses

Addition compounds of the monosubstituted derivative of sulfur tetrafluoride, trifluormethlysulfur trifluoride with the Lewis acids PF₅, BF_3, AsF₅, and SbF₅ were prepared, isolated and characterized. On the basis of their infrared spectra, it is suggested that these new compounds can be classified as types of fluoronium adducts and that their ionic formulation can be expressed as CF₃SF₂⁺MF^-_n+1 where MF_n represents the acceptor used. Upon oxidative hydrolysis of trifluoromethylsulfur trifluoride, trifluormethlsulfonic acid was prepared. Further investigations included the preparation and isolation of perfluoroethysulfur trifluoride and its addition …

Cadmium In Kittitas County Soils, Don G. Muller

All Master's Theses

This paper deals with a survey of soil cadmium concentrations in Kittitas County, Washington, using atomic absorption spectrophotometry as the analytical method. The purpose of the survey was to establish, in an area relatively free from cadmium contamination, background levels for a wide variety of soil conditions. The results showed cadmium concentrations ranging from amounts below the detection limit in remote areas to 2.58ppm in cultivated, inhabited areas, with an overall average concentration of 0.12 ppm cadmium

Preparation And Spectral Characterization Of Select Cyclic Ethynyl Carbinols, William C. Wilkinson

All Master's Theses

The preparation and characterization of select cyclic ethynyl carbinols is presented as a preliminary step for a more detailed investigation of the Rupe rearrangement. The objective of the research work was to attempt to predict abnormal chemical behavior from spectral characteristics of each of the cyclic ethynyl carbinols. Preparation of the starting carbinols was accomplished by a modified Grignard synthesis. Nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy were used for characterization of each new carbinol prepared. The spectral data available from the characterization work were then used to establish a correlation between ring size and appropriate absorption maxima. …

Desorption Of Phosphorus From Si (111) Surfaces, Cesar Michel Magnin

Masters Theses

"Auger electron spectroscopy and mass analysis are used as complementary methods in evaluating desorption kinetics. For phosphorus on silicon, the order of desorption and activation energies of desorption are determined from continuously monitored phosphorus Auger electron signals during heating. These measurements indicate that diatomic phosphorus dissociates when adsorbed onto clean silicon. Mass spectrometer flash desorption spectra show that at least four distinct surface bonds are associated with the desorption of phosphorus. The dominant desorbed species is diatomic phosphorus at high coverage (> 0. 1 monolayer) and atomic phosphorus at low coverage (< 0.07 monolayer)"--Abstract, page ii.

A Comparison Of The Effects Of Aspirin, Sodium Salicylate, And Acetate On Cells In Vitro, Roger Scott Barron

University of the Pacific Theses and Dissertations

Salicylic acid and its concern have long been used for the management of pain, fever, and inflammation. Of this group, acetyl-salicylic acid, or aspirin (ASA) has proved to be the most potent in each case. Although hydrolysis, the first step in biotransformation of aspirin takes place very rapidly, many workers feel that the greater effectiveness is due to a unique action of the intact molecule; however, others disagree. In this study, the effects of aspirin and in vitro were compared in order to obtain a greater amount of information relating to the problem.

Synthesis Of Uranium Fluorosulfates And The Group Vi B Difluorophosphates, Larry Mccain Emme

Dissertations and Theses

Some reactions leading to several anhydrous Uranium fluorosulfates through the use of fluorosulfonic acid or peroxydisulfuryl di-fluoride have been studied. It was found that HS0F can oxidize uranium 3metal to the +4 state or the +2 state depending on the reaction conditions. The synthesis of the tan solid; U(S0₃F)₄ and the pale green solid thought to be U(S0₃F)₂ were prepared in this manner. It was found that S₂0₆F₂ can also oxidize uranium to yield the green solid U(S0₃F)₃. S₂0₆F₂ was …

A Crystalline Fragment Of The Double Helix: The Structure Of The Dinucleoside Phosphate Guanylyl-3',5'-Cytidine, Roberta Ogilvie Day, Nadrian C. Seeman, John M. Rosenberg, Alexander Rich

Department of Chemistry: Faculty Publications

The sodium silt of guanylyl-3',5'-cytidine crystallizes in a monoclinic unit cell with one molecule in the asymmetric unit. Each molecule is related to another molecule by a 2-fold rotation axis which results in the formation of an antiparallel; right-handed .double helix with complementary hydrogen bonding between the guanine and cytosine residues. The crystal is heavily hydrated with 36 water molecules in the unit cell. The geometry of this crystalline double helix is. very similar to those which have been derived from studies of fiber x-ray diffraction patterns of double-stranded RNA; even though the latter do not yield data at atomic …

Computer Investigation Of The Variation Of Conductivity With Concentration, Larry Macpeers Shadwick

Masters Theses

Computer programs were developed tor the conductance equations of R. M. Fuoss and L. Onsager as well as for the conductance equations of T. J. Murphy and E. G. D. Cohen. These programs were used to calculate values from selected conductance measurements. The resulting values were compared with values produced by other computer programs using the equations of Fuoss and Onsager as well as the equations of E. Pitts. The comparisons demonstrated the equations of Murphy and Cohen to be the equal of or superior to the other equations for the majority of cases. The equations of Pitta were superior …

The Conductance Of Some Polyvalent Electrolytes, Jack Lee Worthington

Masters Theses

A new compound, 1,3,5-triphenylbenzene-4' ,4",4"'-trisulfonic acid, was synthesized by treating triphenylbenzene in 1,2-dichloroethane with chlorosulfonic acid. The reaction appears to be quantitative. Conductance measurements were then made on the sodium, potassium, and lanthanum salts of this new acid and of 1,3,5-benzenetrisulfonic acid.

The choice of these acids was based on two factors: 1) the desire to prepare a 3-3 symmetrical unassociated electrolyte which would allow the determination of a more reliable equivalent ionic conductance value for La³⁺ and 2) an interest in using the Murphy-Cohen equation to determine solute parameters such as association constants if association is present.

Conductance …