Chemistry Commons^™

Cell-Mediated Immunity Of The Dog Lung And Effects Of Inhaled 239puo2 Or Pulmonary Tumors, Jennifer Baker Galvin

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Cell-mediated immunity (CMI) in the lung has not been well characterized due to the lack of applicable tests. A major objective was to define pulmonary CMI serially in immunized and control lung lobes using the leukocyte procoagulant (LPCA) assay in young adult dogs. This was compared to a standard, but less reproducible CMI assay, macrophage migration inhibition facet (MIF). The CMI response, as measured by the LPCA assay, peaked in the blood 7 days after lung immunization. The pulmonary CMI response measured with cells obtained by bronchial lavage from the immunized and control lung lobes peaked at 9 to 12 …

Cow Brain Glutaminase: Purification And Influence Of Phosphate And Borate Ions On Its Activity And Molecular Weight, Mahnaz Badamchian

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

An efficient and simple purification procedure for cow brain glutaminase (L- glutamine amidohydrolase, EC 3.5.1.2) is described. The main steps consisted of acetone extraction and French press treatment in the presence of phosphate ions, precipitation of nucleic acids and lipids by 0.08 % protamine·S04 and high speed centrifugation (300,000xg), ammonium sulfate fractionation, and gel filtration on Sepharose 4B first as the low molecular weight and then as the aggregated form. The yield was 22% and the final preparation had a specific activity of 142 μmoles/min/mg. The purification was more than 8000-fold over crude brain homogenate. The enzyme showed one strong …

Studies In Peptide Synthesis Towards The Lanthionine Analog Of Des-N-Tetramethyl Triostin A, Ganesh Devdas Kini

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Studies have been carried out towards the synthesis of bicyclic octadidepsipeptide lanthionine 4, an analog of des-N-tetramethyl triostin A. Starting with a symmetrical lanthionine unit 5 (R₁, R₃ = Me; R₂, R₄ = t-butyloxycarbonyl), synthesized from the corresponding cystine by contraction with hexaethylphosphorus triamide, linear octadidepsipeptides 29 and 32 were synthesized.

Attempted cyclizations of 29 and 32 to the bicyclic octapeptide were unsuccessful.

The failure of the symmetrical approach to 4 prompted the synthesis of an unsymmetrical lanthionine unit with appropriate compatible protecting groups. Attempts to synthesize unsymmetrical lanthionines by nucleophilic displacement on …

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)

Møller-Plesset Treatment Of Electron Correlation In (Hohoh)-, M. M. Szczesniak, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The effects of electron correlation on the calculated properties of the (HOHOH)⁻ anion are studied using Møller–Plesset (MP) perturbation theory. With this technique, inclusion of corrections up to third order are shown to provide results quite similar to those obtained with an extensive CI approach when equivalent basis sets are used. Barriers to proton transfer between the two oxygen atoms at a fixed R(OO) distance are computed with a number of basis sets ranging from split‐valence 4–31G to triple‐valence with polarization functions on all atoms, 6–311G∗∗. Each successive enlargement of the basis set leads to a greater barrier. …

Comparison Of Proton Transfers In Cationic Heterodimers And Homodimers Of Nh3 And Oh2, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Ab initio molecular orbital methods are used to study proton transfers in the cationic heterodimer (H₃NHOH₂)⁺ as well as the symmetric homodimers (H₂OHOH₂)⁺ and (H₃NHNH₃)⁺. All calculations are carried out at the Hartree–Fock level with a 4‐31G basis set to ensure consistency. For proton transfers along a linear hydrogen bond in the heterodimer, asymmetric single‐well potentials with a minimum corresponding to (NH₄)⁺(OH₂) are obtained for R(NO) distances of less than 2.85 …

The Transport And Intracellular Distribution Of Iron In The Basidiomycete, Ustilago Sphaerogena, Charles W. Passavant

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The transport and intracellular distribution of iron in Ustilago sphaerogena via the native siderochrome ferrichrome A has been examined. Evidence is presented which suggests the involvement of deferriferrichrome in iron transport when the metal is supplied to the cell as ferrichrome A. This process requires both oxygen and ATP synthesis and may require a transmembrane electrochemical gradient. Once inside the cell, iron derived from ferrichrome A is rapidly distributed, with a major fraction found in the mitochondria, presumably as heme.

The kinetics of ferrichrome and ferrichrome A uptake have also been investigated. The Km of transport of ferrichrome was …

Mechanism Of Two Homogeneous Reactions; Co Self Exchange And N2 Self Exchange, Alan L. Rockwood

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The two atom switching reactions referred to in the title were originally studied at temperatures greater than 2000°K in shock tubes by other investigators. For each reaction they proposed a direct four-center exchange mechanism in which one of the reactant molecules must be vibrationally excited, (the vibrational excitation mechanism or VEM). One of the predictions of the VEM is that molecules which are vibrationally hot but translationally cold should react through the four center transition state that leads to exchange.

Using a mercury photosensitization technique, it is shown in the present work that excitation of CO to high vibrational levels …

Comparison Of Toxicological Models For Evaluation Of Air Pollutants: Response Of The Pulmonary Alveolar Macrophage To Hexavalent Chromium, Jennifer Baker Galvin

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

This study was designed to accomplish two primary objectives: (1) to compare two test methods commonly used to evaluate toxicity of inhaled air pollutants, and (2) to observe the response as measured by each of the methods, of pulmonary alveolar macrophages exposed to 2μg hexavalent chromium.

The first method evaluated featured use of intratracheal injections to simulate live inhalation exposures, and the second required exposure of macrophages cultured on petri plates. Pulmonary alveolar macrophages harvested from Long Evans rats were used. The two cell function parameters measured in the evaluations were chemiluminescence and oxygen consumption (which was determined for cells …

Theory And Intuition, E. A. Mccullough Jr.

Faculty Honor Lectures

Among the practitioners of science are people who are called theorists , and this lecture is concerned with the question, Just what is it that a theorist does?

If an experimentalist does experiments, then a theorist presumably does theories. What is a theory? My dictionary defines it as ". . . a system of assumptions, accepted principles, or rules of pro· cedure devised to analyze, predict or otherwise explain the nature or behavior of a specified set of phenomena."

Those who now understand perfectly what a theorist does may stop reading here because everything that follows will be superfluous. For …

Proton Transfers In Hydrogen‐Bonded Systems. Vi. Electronic Redistributions In (N2h7)+ And (O2h5)+, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Electronic rearrangements accompanying transfer of the central proton between the two XH_n units of (H₃NHNH₃)⁺ and (H₂OHOH₂)⁺ are studied using ab initio molecular orbital methods. Electron density difference maps are calculated by subtracting the density of the equilibrium structure (X–H‐‐‐X) from that of the midpoint geometry (X‐‐H‐‐X) using the split‐valence 4‐31G basis set. Some of the features revealed by the maps are common to both systems while others indicate significant differences between nitrogen and oxygen. Decomposition of the total electron density into …

Iron And Life, Thomas Emery

Faculty Honor Lectures

Iron, iron, everywhere but. . . . The plight of the ancient mariner surrounded by undrinkable water could hardly have been more frustrating than life on earth with respect to iron. Iron is the fourth most abundant element of the earth's surface, exceeded only by oxygen, silicon, and aluminum. Virtually all forms of life from the simplest bacteria to humans require iron to catalyze numerous and complex metabolic reactions. Because of the diversity and complexity of the role of iron in the life process, it has even been suggested that the origin of life on earth centered around the catalytic …

Effects Of Pesticides On Immune Competency: Influence Of Methyl Parathion And Carbofuran On Immunologic Responses To Salmonella Typhimurium Infection, Anna M. Fan

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Immunologic competence is correlated with resistance to infectious disease which may be affected by exposure to certain compounds. Methyl parathion (MP) and carbofuran (CF) have been reported to affect the development of active immunity in the rabbit and the present research was conducted to quantify the dosage relationships of these two pesticides to both host resistance and acquired resistance in the mouse.

Preliminary study was made on the virulence of Salmonella typhimurium in mice. Mortality rates among infected animals fed Purina Laboratory Chow diet providing 0.08, 0.7 3.0 mg MP/kg/day or 0.1, 0.6, 1.0 mg CF/kg/day along with untreated controls …

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 …

Studies Toward The Synthesis Of A- And B- Mercapto Alanine Derivatives, And Of A,B- And B, B- Dimercapto Alanine Derivatives, Aldean James Kolar

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

A convenient, economical, large scale synthesis of N-acetyldehydro-alanine (a-acetamidoacrylic acid) and its methyl ester was developed via a sequence of N-chlorination-dehydrochlorination. The method was extended to the synthesis of the corresponding N-benzoyl, N-phenylacetyl and N-benzyloxycarbonyl derivatives.

The conversion of a-methoxy-N-acetyl alanine derivatives to the corresponding a-mercapto alanine derivatives, using zinc chloride and an appropriate mercaptan, was investigated. Methyl a-methoxy-N-acetyl-D, L-alaninate was successfully converted to the a-acetylthio derivative, in 24% yield; however, a 90% yield could be obtained by treatment of the dehydroalanine derivative with hydrogen chloride gas in neat thiolacetic acid.

A facile conversion of the a-acetylthio derivative to the …

The Reaction Of Dimethyl-And Di-N-Butylcopper Lithium With 3-Bromo-2-(2-Phenylacetamido) Acrylic Acid, Kim David Richards

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The reaction of dimethylcopper lithium and di-n-butylcopper lithium with 3-bromo-2-(2-phenylacetamido) acrylic acid, mp 174 - 175°, produced as major products 3-methyl-2-(2-phenylacetamido) acrylic acid and 3-n-butyl-2-(2-phenylacetamido) acrylic acid, respectively. The dimethylcopper lithium reaction was stereospecific for the E geometrical isomer, mp 198 - 199°, and produced 3-methyl-2-(2-phenylacetamido) acrylic acid and 2-(2-phenylacetamido) acrylic acid in a 3:1 molar ratio, respectively. The di-n-butylcopper lithium reaction produced as the main products 3-n-butyl-2-(2-phenylacetamido) acrylic acid and 2-(2- phenylacetamido) acrylic acid in a 7:1 molar ratio, respectively, with the 3-n-butylacrylic acid comprising 83% of the product. The reaction …

Oxidation Of Thin Silver Films By Ozone And Atomic Oxygen, Lawrence R. Thorne

Undergraduate Honors Capstone Projects

Recently, thin silver film detectors have been used to determine atomic oxygen profiles in the 70-100 km region of the upper atmosphere. The detectors' sensitivity to atomic oxygen is the result of the formation of silver oxide(s) which cause their electrical resistance to increase. A common procedure to calibrate and to make these detectors more sensitive is to cycle them through a series of three or more oxidations and reductions. This paper indicates that this cycling makes silver films more sensitive to ozone, causing them to be usable only at heights greater than 38 km. Also reported herein are experimentally …

I. Studies Toward The Synthesis Of Echinodithianic Acid And Ii. The Temperature Dependent Nmr Spectrum Of Methyl N-Acetylsarcosinate, Alan Leroy Love

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Approaches to the preparation of echinodithianic acid (5) from 2,5-dicarbomethoxy-1,4-dithiane (1) were not successful, due to the inability to carboxylate or carboalkoxylate 1 at carbons 2 and 5. Studies toward the synthesis of 5 utilizing methyl 2-acetamidoacrylate (8) have been investigated. The electrophilic addition of sulfur dichloride to 8 yielded bis-(2-acetamido-2-carbo-methoxyvin-1-yl) sulfide, while the addition of thiocyanogen chloride to 8 produced methyl 2-acetamido-3-thiocyanato-acrylate.

As electrophilic additions of unsymmetrical dipolar reagents to methyl 2-acetamidoacrylate (8) are not reported in the literature, the addition of hydrogen bromide to 8 was studied to determine the orientation effect of the acetamido group.

Methyl 2-acetamido-2-bromopropionate …

Calcium Carbonate Dissolution And Precipitation In Water: Factors Affecting The Carbonate Saturometer Method, Lyle M. Dabb

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The carbonate saturometer method developed by Weyl (1961) was studied in respect to the effect of several variables on the solubility of carbonates. The solubility of three solid carbonate materials was measured in four different salt solutions, at four ionic strengths, and at two different temperatures. The solids studied included: calcite, dolomite, and a calcareous soil.

It was found that the three solid carbonate materials varied in solubility from a low in the soil carbonates to a high in dolomite.

Increasing the ionic strength of the solution increased the solubility of most of the solid carbonate materials.

By decreasing the …

The Photochemical Reduction Of Octacyanomolybdate(V) Ion In Aqueous Solutions, Gordon W. Gray

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The photochemical reactions occurring in aqueous solutions of octacyanomolybdate(V) ion, Mo(CN)₈^3-, during irradiation with light of 365 and 436 nm wavelengths were studied. The quantum yields and reaction products were determined for neutral, unbuffered solutions as well as solutions buffered at pH 4.0, 7.0, and 9.0.

The results of these studies showed that the Mo(CN)₈^3- ion is rapidly reduced by light to a Mo(IV) complex. In neutral or acidic media, the initial photoreduction product was found to be the red heptacyanoaquomolybdate(IV) ion, Mo(CN)₇(H₂O)^3-. Photolysis in basic solution gave the …

Magnesium Ion Inhibition Of Calcium Carbonate Precipitation And Its Relation To Water Quality, John J. Hassett

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The effect of Mg⁺⁺ ion on the solubility of calcium carbonate was determined using P. K. Weyls "carbonate saturometer."

The amount of calcium carbonate precipitated or dissolved was measured for five series of waters when equilibrated with solid carbonate.

It was found that the effect of Mg⁺⁺ ion on solubility depend upon the nature of the solid phase: surface area, coprecipitated Mg⁺⁺, minerology, etc.

Pure low area calcite showed an increase in solubility which could be explained by ion-pair formation, while its other carbonates departed from this behavior.

Experiments On The Inactivation Of Zinc By The Mineral Fractions Of The Soil, John J. Hassett

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Zinc deficiency, in many cases, is closely related to organic matter decomposition. DeRemer and Smith (1964) studied the effects of decomposing sugar beet tops on the reactions of Zn⁶⁵ in a Portneuf soil. They found that with time the Zn⁶⁵ associated with lime minerals, exchangeable, and water soluble fractions of the soil decreased, while that found with the organic and mineral fractions increased. This increase in the mineral fraction is of particular interest, since the majority of the Zn⁶⁵ was found to be with this fraction after a period of time. They also showed that the increase …

A Modern Philosopher's Stone, Grant Gill Smith

Faculty Honor Lectures

Alchemists, the forerunners of chemists, for more than a millennium sought the "Philosopher's Stone"-the transmuting agent that could change imperfect base metals such as lead and tin to the noble metals, gold and silver, and also serve as the Elixir of Life to heal the infirmities of man and prolong his existence on earth.

Where alchemy failed, chemistry, in little more than a century, has succeeded in finding the "Philosopher's Stone," for it is now not only possible to transmute one metal into another and heal many of man's infirmities, but scarcely a facet of man's life has not been …

Nature Of Non-Biological Decomposition Of Nitrite In Acid Media, Mukkatira Kariappa Mahendrappa

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Curiosity is the cause of investigations, and the thirst for knowledge originates from it. Many times at the end of investigations, the number of questions raised are greater than those for which answers are sought. Therefore, all the information gathered through scientific investigations may not be of value for immediate application in practical life. Nevertheless, no research can be considered less important than the other because the integration of several scientific findings considered less less important at the time of investigation may reveal something of very high significance. Similarly, the study of various transformation reactions that the added fertilizers undergo …

Thermochemistry Of Cyclophanes, Chyi-Feng Shieh

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The syntheses and properties of various cyclophanes have been extensively investigated by Cram and others. The paracyclophanes are compounds in which benzene rings are linked to each other by two saturated chains at the para positions, as in structure I. When they are joined to the meta positions, they are called metacyclophanes.

The Kinetics And Mechanism Of The Reaction Of Molybdenum(V) With Iodine, Oxygen And Nitrate, Ervin Park Guymon

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Molybdenum compounds present a series of baffling chemical puzzles. By no means are all of these yet even clearly defined and many may never be. This complexity results from the ability of molybdenum to form six different oxidation states, which can possess three different coordination numbers. Furthermore, molybdenum compounds readily disproportionate to yield mixed valence compounds; and finally, molybdate ions readily aggregate in solution to form a variety of polyions by polymerization-condensation reactions which are controlled by pH and the concentration of the system. Molybdenum's complexity can best be summed up in the words of the late Edgar Smith who …

Molybdenum-L-Histidine Complexes, Jiing-Yun Lee

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

L- Histidine is a very important amino acid and is widely distributed in living systems. In the growth and multiplication of animal cells, it was found that L-histidine is one of the amino acids that must be present. From the kinetic studies of certain enzymes such as chymotrypsin and ribonuclease, it has been proposed that the imidazolyl group of the histidine residue may serve as the basic electron donor, and that the histidine residue in some cases may be the active site of the enzyme. The interactions of L-histidine with heavy metal ions, including Ni (II) (1), Zn (II) (1, …

Nitrite Reactions In Soil, John Otto Reuss

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Losses of soil nitrogen that cannot be attributed to leaching or crop removal have been observed in many field experiments. Several mechanisms have been proposed to account for these losses.

Differentiation Between The Ph Effect And The Bicarbonate Ion Effect In Causing Lime-Induced Chlorosis, Hyrum Del Var Petersen

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Lime-induced chlorosis has been recognized for many years as a problem where plants are grown on calcareous soils. There are many factors associated with and influencing this form of iron chlorosis and because of this it has been very difficult to determine the relationship between the factors and chlorosis.

The Effect Of Chelates On Phosphorus Availability And Mobility, Salah Ahmed Tahoun

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Soil-phosphorus relations and plant-phosphorus relations have attracted the interest of many investigators since Liebig introduced his famous theory about the importance of the mineral matters to the plant in 1840. It was soon realized that phosphorus nutrition was a problem not easily solved for two reasons. 1. The added phosphorus fertilizers, soon after soil application are converted by some reactions in the soil to complex compounds far less soluble, consequently less available to the plant. Conclusions about this process led to controversial debates until it was discovered that a general statement covering all soils was impossible since the reactions involved …