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Asymptotic Evaluation Of Wkb Matrix Elements. Ii. Use Of Langer's Uniform Asymptotic Wavefunctions, Wesley D. Smith, Russell T. Pack

Faculty Publications

An improvement in a previous procedure for the analytic asymptotic evaluation of integrals arising in the quantum-mechanical theory of inelastic molecular collisions is presented. The integrals are evaluated using Langer's uniform asymptotic wavefunctions and the higher-order saddle-point or steepest-descents method. It is found that the Langer functions give no better results than WKB functions, but the higher-order steepest-descents corrections produce a marked improvement. The result is a simple method for evaluating a large class of integrals with an error of 0.1%-2.1%.

The Synthesis Of Some New Azabenzo[A]Pyrene And Monomethyl Azabenzo[A]Pyrene Derivatives, Richard E. Phillips

Chemistry and Chemical Biology ETDs

The synthesis of six new azabenzo[a]pyrenes was undertaken in order that the carcinogenic and carcinostatic properties of these com­pounds might be tested. The compounds thus synthesized were 4-aza­ benzo[a]pyrene (1), 5-methyl-4-azabenzo[a]pyrene (2), 12-azabenzo[a]­pyrene (3), 11-methyl-12-azabenzo [a]pyrene (4),5 -azabenzo [a]pyrene (5), and 4-methy1-5-azabenzo[a]pyrene (6).

Compounds 1 and 2 were prepared from the intermediate 4-keto-1,2,3,4-tctrahydrochrysene. The azine from this ketone was dehydro­genated and the resulting aromatic amine was both formylated and acetylated. The amides were cyclized with polyphosphoric acid in a Bischler-Napieralski cyclodchydration giving fair yields of 1 and 2. The synthesis of compounds 3 and 4 was carried out in a …

Paths Of Energy Degradation In Transition Metal Complexes, James N. Demas

Chemistry and Chemical Biology ETDs

To elucidate the paths and rates of energy degradation in transition-metal complexes following photoexcitation, a comprehensive experimental study was carried out on a total of fourteen complexes of Ru(II), Os(II), Ir(III), and Rh(III). Photoluminescence lifetimes, spectra, wavelength dependences of the quantum yields, and absolute quantum yields were determined. The complexes all contained organic ligands—pyridine, 2, 2’bypyridine, 2, 2’ 2”-terpyridine, and 1, 10-phenanthroline. The ruthenium, osmium, and iridium complexes all exhibited charge transfer (CT) phosphorescences with quantum yields of 1-60% and lifetimes of 0.6-11 µsec in an alcoholic glass at 77°K. The rhodium complexes gave d-d* phosphorescences with yields in the …

Analysis Of Solutions For Surface Active Agents, Henry H. Bauer

KWRRI Research Reports

The objective of this study was to obtain a better understanding of the behavior of surfactants in aqueous solutions at electrodes. With this understanding it should be possible to design electrochemical methods for the detection, identification, and quantitative determination of such substances. This study was concerned primarily with the influence of extraneous salts on the behavior of surface active agents when these are examined by the electrochemical technique known as tensammetry.

The tensammetric method consists essentially of the measurement of the electrical impedance of an electrochemical cell. This impedance is characteristically increased in the presence of surfactants at those potentials …

Magnetic Solid-Phase Extraction Of Trace Cobalt(Ii) On Iron Oxide-Hexagonal Boron Nitride In Water And Food Samples, Mustafa Soylak, Ali Mohammednour Ali Mohammed, Furkan Uzcan

Turkish Journal of Chemistry

Determination of trace cobalt(II) (Co(II)) in real samples remains challenging because of its very low concentration and strong matrix interferences. In this study, a simple and green magnetic solid-phase extraction (mSPE) method was developed for the selective separation and preconcentration of Co(II) ions using a newly designed iron oxide/hexagonal boron nitride (IOhBN) nanocomposite. The material was synthesized through a one-step, surfactant-free coprecipitation process, combining the high surface area, stability, and layered structure of hBN with the magnetic and reactive features of Fe₃O₄ nanoparticles. This hybrid structure provided abundant active sites and rapid magnetic separability, enabling efficient extraction within 5 min …

The Possible Correlation Of Carcinogenic Activity With Electronic Structure Of Benz(A)Anthracene, Patricia Joan Blair

Masters Theses

"The electronic structure of benz(a)anthracene based on the sigma and pi electrons was predicted by the modified intermediate neglect of differential overlap (MINDO) molecular orbital method and compared with the pi electronic structure determined by the Pople method. The crystalline molecular structure was used for both methods. The Pople calculation was also done on the aromatic molecular structure and a combination structure which assumed the bond lengths of the crystal structure and the bond angles of the aromatic structure. Chemical properties predicted by the MINDO and POPLE electronic structures were compared; the MINDO results provided the best agreement with experimental …

Papain-Papaya Protein Interactions : Resistance Of Papaya Protein To Proteolytic Digestion By Papain, John Leonard Rudy

University of the Pacific Theses and Dissertations

The proteolytic actjvity of papain was investigated with respect to its action on both natural substrates (native papaya protein and bovine serum albumin) and artificial synthetic substrate (benzoyl~l-arginine ethyl ester). Following removal of 30 percent and 40 percent of the amino acid residues from the amine terminus, the activity of the degraded papain was determined with respect to the above substrates, and compared to the activity of the intact papain molecule.

Native papaya protein showed resistance to digestion by both intact papain and 30 percent 'degraded papain. This resistance to digestion persisted for time periods ranging from three to six …

A Study Of The Esterification Of 2,2,4,4-Tetramethyl-1,3-Cyclobutanediol, Lewis Metzler Naylor

Dissertations and Theses @ UNI

The purpose of this research was to prepare, identify, and characterize 2,2,4,4-tetramethyl-1,.3-cyclobutanediol bischloroacetate using 2,2,4,4-tetramethyl-1,3-cyclobutanediol and monochloroacetic acid as starting materials. The synthesis of this diester has not been reported previously.

Catalyzed and uncatalyzed reactions were attempted, with the uncatalyzed having, in general, the better yield. The diester, trans-2,2,4,4-tetrametbyl-1,3-cyclobutanediol bischloroacetate (mp, 103.5-104; n²², 1.516-1.520), was isolated from a mixture of the isomers. The trans configuration of the diester was confirmed by comparing known nuclear magnetic resonance spectra to that of the diester. Infrared spectroscopy was used to confirm functional groups. Standard analytical techniques were used to determine chloride …

Ua66/7/2 Newsletter, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

Quasilattice Interpretation Of The Thermodynamic Properties Of Mixing Of Binary Alkali-Metal Systems, J. Bevan Ott, J. Rex Goates

Faculty Publications

Quasilattice theory was applied to heats of mixing in the six systems formed from the binary combinations of Na, K, Rb, and Cs. The alkali-metal systems are particularly well suited for a critical test of the quasi-crystalline assumption since the theoretical model for these systems is relatively simple and the thermodynamic data are fairly complex. Very good fits of the heat-of-mixing data were achieved by assuming that the larger atom in the binary system covered multiple sites on the quasilattice. The values of the empirically determined constants appear to fit the physical significance accorded to them by the quasilattice model. …

Thermodynamics Of Proton Ionization In Dilute Aqueous Solution At 25°, Ernest J. Baca Jr.

Chemistry and Chemical Biology ETDs

This dissertation consists of four studies and is divided into five parts. Part I contains a description of the calculations and equipment used for these four studies.

Part II is a study of tris(hydroxymethyl)nminomethane (THAM) for use as a standard in solution calorimetry. The heat of solution of THAM in 0.100 M HCL was determined at 25°.

Part III is a study of the thermodynamics of proton ionization

from some unsaturated, five membered, nitrogen ring compounds in dilute aqueous solution at 25°. Values of deltaK, pK and deltaS are reported for 1,2,3-triazole, benzotriazole, 4,5-dibromo-1,2,3-triazole, 1-phenyl- 5-methyl-1, 2, 3-triazole-4-carboxylic acid, …

Spectroscopic Studies Of Complexes Of Rhodium (Iii) And Iridium (Iii), Dean H. W. Carstens

Chemistry and Chemical Biology ETDs

A comprehensive experimental and theoretical study of complex compounds of two d6 transition metal ions, rhodium(III) and iridium(III), was made to characterize the electronic transitions responsible for the various bands seen in the absorption and emission spectra and to determine the dependence of the energies of the excited states of a complex ion on the nature of the ligands and the central metal ion. All the complex compounds contained organic ligands—pyridine, 2,2’-bipyridine, or l,l0-phenanthroline—in the principal coordination sphere. Most also had halide ions bonded directly to the central ion. An ancillary study was made of 2,2’,2’’-terpyridine complexes of two d10 …

The Effects Of Herbicides On Three Soil Inhabiting Blue Green Algal Species, Lee C. Darlington

All Master's Theses

The object of this study was to examine the effects of varying concentrations of 2, 4-D, Dalapon, and Tordon on the growth of several nitrogen-fixing blue-green algal species obtained from soil samples and grown under culture conditions in the laboratory.

Thermodynamics Of Proton Dissociation And Metal Ion Complexation In Aqueous Solution. I, Cation Binding With Cyclic Polyethers: Significance In Ion Transport Processes. Ii, Proton Dissociation From Adenosine, Several Monosaccharides And Related Compounds. Iii, Proton Dissociation From Several Pyrimidines And Their Nucleosides At 10, 25 And 40°, Joseph Howard Ryttling

Theses and Dissertations

The log K, ΔH° and ΔS° values for the interaction of several metal ions with the two isomers of the cyclic polyether, 2,5,8,15,-18,21 hexaoxatricyclo[20.4.0.0^9,14]hexacosane are reported. The stability order found for alkali metal ion interaction with either isomer is identical to the order of ion permeability through reconstituted biological membranes for structurally related antibiotics. The size of the metal ion is critical in determining the extent of interaction. A calorimetric titration study of proton ionization from several monosaccharides and derivatives, pyrimidine bases and their nucleosides, adenosine and its derivatives, and cycloheptaamylose is described. The heats of reaction obtained in this …

Mechanism Of Water Transport Through Reverse Osmotic Membranes, Cheryl Kay Murphy

Theses and Dissertations

Cellulose acetate membranes show a higher permeability to water than to salt and are being used for desalination of salt water by reverse osmosis. Use of highly acetylated cellulose membranes give a higher salt rejection but also decrease flow rate of the water. The addition of very-short-chain substances or alkyl groups larger than one carbon atom to the cellulose membrane also decreases water flux. A proposed mechanism of transport through the membrane is that the water molecule is passed along the chain by hydrogen bonding with the acetyl groups, The NMR shows a change in the chemical shift of water …

Trace Metal Analysis Of Barren River And Nolin River Reservoirs By Atomic Absorption Spectroscopy, Mary Jo Kennedy

Masters Theses & Specialist Projects

This research was part of a project underway at Barren River and Nolin River Reservoirs in south-central Kentucky. The research was partially supported by a grant through the Sport Fishing Institute, Washington, D.C.

The study reported herein was concerned with the analysis of trace metal concentrations in the two reservoirs. It is believed that the fish population may in part depend upon the trace metals present in the water. It is anticipated that the data presented in this paper will eventually be correlated with the biology studies of the reservoirs being carried out by the Department of Biology of Western …

Peracid Oxidation Of 3-Phenylindene, Christopher Peter Johnson

Master's Theses

Indene oxide (indan, 1,2-epoxy; indene 2,3-oxid is first recorded in the literature in 1919. This compound was formed in practically quantitative yield by the treatment of indene bromo­ hydrin in ether with powdered potassium hydroxide. At this time Van Loon also reported the preparation of indene oxide by mechanical shaking of an anhydrous, ethere!al solution of the bromohydrin with finely powdered potassium hydroxide. The desired product was obtained in a 92-97% yield by this method. Indene oxide has been prepared in a similar manner from trans-2-chloro-l-indanol by treatment "with soda," distillation of the acetone in vacuo after 15 hours, and …

Syntheses Via Modifications Of The Knorr-Paal Procedure :|Ba. Derivatives Of 2,6-Dioxa-10-Azatricyclo[5.2.1.0[Superscript 4,10]]Decane ; B. Highly Sterically Crowded 1,2,5-Trialkylpyrroles And Pyrrolidines, Weldron Severin Burnham

Theses and Dissertations

Earlier work in these laboratories on the heterotricyclic system 2,6-dioxa-10-azatricyclo[5.2.1.04,10]-decane, formed from 1,4-diketones and 2-amino-1,3-propanediols by a product-water-azeotroping procedure, was extended with the synthesis of analogous compounds, e.g., the 1,4,7-triethyl-, 1,7-dimethyl-4-isopropyl-1,7-diethyl-4-isopropyl-, 1,7-dimethyl-3- and 4-phenyl- compounds. The 1,7-dimethyl heterotricycle, the kinetically-controlled product, was accompanied by the thermodynamically-controlled product, 2-(2,5-dimethyl-1-pyrryl)-1,3-propanediol. The 1,7-diethyl heterotricycle was also accompanied by the isomeric pyrrole as were the 1,7-dimethyl-3- and 4-phenyl compounds. A scheme postulating a common intermediate is presented. The interesting analogous compounds, 1,7-dimethyl-2-oxa-6-thia-10-azatricyclo[5.2.1.04,10]decane, 1,4,7-trimethyl-2,6-dioxa-11-azatricyclo[5.3.1.04,11]undecane and 11-hydroxymethyl- and 11-methyl-9,13-dioxa-14- azatetracyclo[6.5.1.02,7 011,14]tetradeca-2,4,6-triene were also prepared. The syntheses in good yields of a considerable number of moderately to …

A Comparison Of The Effects Of Fluoride And Chloride Ions Upon The Activity Of Yeast Alcohol Dehydrogenase, Ellen J. Hannan

Dissertations and Theses

Very little is known about the effect of hydrofluoric acid and of the fluoride ion on enzyme systems. The purpose of this work was to determine the effect of hydrofluoric acid and of the fluoride ion on the enzyme, yeast alcohol dehydrogenase and to distinguish between the effect of the fluoride ion and of hydrofluoric acid. The rate of the enzyme reaction was followed spectrophotometrically at 340 mμ on the Cary 14 Model spectrophotometer according to the method of Racker. The data taken from the instrument recordings were plotted on two types of graphs, the Lineweaver-Burk plot and the Hanes …

Liquid Scintillators. The Decomposition Of 2, 5-Diphenyloxazole In Ultraviolet Light. A Thin Layer Chromatography Study, John W. Hustler

Chemistry and Chemical Biology ETDs

A study has been initiated in order to understand more completely the manner in which a model organic scintil­lator decomposes in ultraviolet light. The compound, 2,5-diphenyloxazole (PPO), was dissolved in toluene in quartz vials and irradiated with ultraviolet light for various intervals of time. Both. vacuum-dried and untreated samples of PPO \·1ere subjected to UV excitation in sodium-dried and water-saturated solutions of toluene. The effect of passing oxygen and nitrogen through the solutions was also studied with the confirmation that dissolved oxygen and water accelerated the decomposition leading to the formation above the meniscus of the vial of a white …

The Chemical Behaviour Of Iodine At Low Concentrations In Strongly Acidic Solutions, Howard Allen Boyd Jr.

Chemistry and Chemical Biology ETDs

Radioactive tracers have been used extensively to investigate the behavior of substances at concentration too low to be detected by ordinary chemical or instrumental methods (1). Some elements exist only as short lived isotopes, and their chemistry is known only

in terms of their behavior at low concentrations, Other elements that have stable or long lived isotopes may be studied at low con­centrations by the use of suitable tracers, usually carrier-free radioisotopes when they are available,

The Thermodynamics Of Transition Metal Chelation In Dilute Aqueous Solution.|Ni.|Pthe Thermodynamics Of Interaction Of Serinate Ion With Divalent Co, Ni, Cu, Zn, And Cd Ions In Aqueous Solution.|Nii.|Pthe Calorimetric Standardization Of Dilute Ferrous Ion Solutions For Use In Determining 2,2'-Bipyridine, Joseph Willard Richards

Theses and Dissertations

Calorimetrically determined ΔH° values are given for the stepwise formation of chelate species between serinate ion and the divalent metal ions of Co, Ni, Cu, Zn, and Cd. These values of ΔH° are compared with those reported in the literature and were combined with values of ΔG° (log K) found in the literature to calculate values of ΔS°. These values of ΔG° and ΔS° are listed also. A new method of standardizing dilute ferrous ion solutions is reported. This procedure makes use of the thermometric titration technique to detect the equivalence point for the reaction of K_2Cr_2O_7 with ferrous ion. …

A Study Of V(Iii) - V(Iv) And Ti(Iii) - Ti (Iv) Isotopic Exchange Reactions In Acid Solutions, Charles J. Orth

Chemistry and Chemical Biology ETDs

The subject of this dissertation is primarily the mechanisms and kinetics ot V(III) - V(IV) and Ti(III) - Ti(IV) electron exchange reactions in homogeneous solutions. The electron exchange process is a form of oxidation-reduction or electron transfer reaction where there is no net chemical change, i.e., the concentrations of the chemical species remain unchanged. In such cases there is a continuous exchange of electrons between a reduced and an oxidized form of the same element, such as between Fe(II) - Fe(III), V(III) - V(IV) or Tl(I) - Tl(III). The first two pairs involve one-electron changes while the thallium pair involves …

Chemical Firebreaks, Geoffrey A. Pearce

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

MANY public bodies are making regular use of herbicides to create firebreaks. In Western Australia more than $200,000 is being spent on chemicals each year to protect property from fire.

In many situations where the buildings and property are of great value, the cost of the chemical becomes insignificant.

The Control Of Weeds In Cereals, Geoffrey A. Pearce

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

PRACTICALLY all broadleaved weeds found in cereals can now be killed with herbicides and with most, the farmer has a choice of chemicals.

Two more new products are now available and these have several advantages over other herbicides.

Chemical Ploughing, Geoffrey A. Pearce

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

PROGRESS in the field of chemical weed control has been spectacular in recent years. One field that is attracting interest is the idea of replacing cultivation with chemical sprays.

The Incorporation Of Oxygen-18 Into Oxindole Acid By Cells Of Hygrophorous Conicus, William Green Allen

Masters Theses

"To understand the mechanism of a biological oxidation in which oxygen is incorporated into a substrate, it is necessary to determine the origin of the incorporated oxygen. The objective of this investigation was to determine the origin of the oxygen atom incorporated into indoleacetic acid (IAA) by the IAA oxidase of Hygrophorous conicus through the use of oxygen-18. To determine the source of the oxygen atom incorporated into IAA it is necessary to incubate H. conicus cells with tryptamine or IAA in the presence of ¹⁸O₂ and H₂¹⁶O in one case and ¹⁶O₂ and H₂¹⁸O in another. An examination of …

Studies On 4-Hydroxycoumarin Anticoagulants Part I: The Reversible Removal Of Carbon 2 Of 3-Substituted-4-Hydroxycoumarins Part Ii: The Synthesis And Urinary Excretion Rates Of The Enantiomers Of Warfarin-4-14c And Marcumar-2-14c, Lloyd Allen Goding

Chemistry and Chemical Biology ETDs

The hydrolytic removal and subsequent reinsertion of carbon 2 of a series of 3-substituted-4-hydroxycoumarins has been accomplished. The removal of carbon 2 presents an effective synthetic route to o-hydroxyketones with complex side chains. o-Hydroxyketones when condensed with alkyl carbonates gave good yields of 4-hydroxycoumarins. When this was carried out with ethyl carbonate-carbonyl-¹⁴C a radio label was inserted in position 2. It was shown that this decarboxylation-carboxylation cycle did not involve racemization of an optically active α-carbon on a side chain in position 3. This method was used to prepare the enantiomers of Marcumar-2-¹⁴C(3-α-ethyl-benzyl-4-hydroxycoumarin). The enantiomers of …

Expectation Values Of Simple Correlated Helium-Atom Wavefunctions, Thomas P. Tsien, Russell T. Pack

Faculty Publications

In this Note we present the results of a calculation of the expectation values of a number of one- and two electron properties of the ground-state helium atom using two very simple correlated wavefunctions.

Biological Studies Of Selected Reaches And Tributaries Of The Colorado River, Nelson Thomas, Federal Water Pollution Control Administration

Publications (WR)

This report fulfills the request of the Colorado River Basin Project, Denver, Colorado, to determine the effects of municipal and industrial wastes on the aquatic life in selected waters of the Colorado River Basin. These studies were conducted with the assistance of personnel from the Colorado River Basin Project.