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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 …

High Performance Liquid Chromatographic Analysis Of Biogenic Amines, Thais Edwina Ahrendt Keegan

Chemistry & Biochemistry Theses & Dissertations

The objectives of this research were to develop a sensitive method for separation and quantitation of biogenic amines and to apply that procedure by monitoring neurochemical changes resulting from stimuli to the test system.

Primary aromatic amines were derivatized with o-phthalaldehyde-mercaptoethanol prior to chromatography, Separation of the fluorescent adduct was achieved using a μBondapak/ phenyl reversed-phase column and a two-step gradient of methanol:0.08 M acetic acid, pH J.O. Fluorescence was monitored using a J40 nm excitation energy and an emission filter which transmits radiation greater than 400 nm (50% T at 418 nanometers).

Following optimization of the chromatographic conditions, studies …

Chemistry Of Organic N-Chloramines, Formation Of Arenesulfonamides By Derivatization Of Organic N-Chloramine With Sodium Arenesulfinate, Katherine F. Bowdring

Chemistry & Biochemistry Theses & Dissertations

Organic N-chloramines are recognized by-products of chlorinated water systems. Because of their chemistry, none have been isolated or identified.

This paper discusses a method for the derivatization of the organic N-chloramines based on a nucleophillic substitution mechanism. N-Chloro derivatives of amines of various structures were studied including primary and secondary aliphatic amines, as well as amino acids. The effect of the presence of other functional groups including aromatic and unsaturated systems was investigated.

Derivatization was done by three different methods, one involving derivatization of the pure N-chloramine, and two involving derivatizations of the N-chloramine generated in situ. Seventeen arenesulfonamides have …

Determination Of Diffusion Coefficients Of Ions In Gels, Kelly A. Sanderson

Theses & Honors Papers

No abstract provided.

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 …

The Structure Of Lamellar Lyotropic Liquid Crystals From Lecithin And Alkanediols, Magda A. El-Nokaly, Larry D. Ford, Stig Friberg, David W. Larsen

Chemistry Faculty Research & Creative Works

Lamellar liquid crystals from lecithin and alkane diols were studied to determine the composition range of stability and geometrical dimensions using low-angle X-ray scattering. An estimation of the dislocation pattern was made from the optical pattern in polarized light. The ethylene glycol gave the widest range of stability for the lamellar structure, the range being reduced toward heptane diol, the longest member to give liquid crystals. The interlayer spacing was reduced with increasing chain length of the diol and the dislocation pattern remained identical. © 1981.

Sodium Accumulation In Serpentine And Non-Serpentine Populations Of The Milkweed Asclepias Fascicularis, Paul N. Thomas

University of the Pacific Theses and Dissertations

Because Asclepias fascicularis is found on both serpentine and non-serpentine soils in California and because it was reported to accumulate sodium, this study was initiated to establish the degree of accumulation of this ion in these two soil types. Two other species, Asclepias speciosa Torr. and Asclepias cordifolia (Benth.) Jeps. were included to determine if this characteristic of accumulation occurs in other members of this genus.

Neutron Activation Analysis Of Nuclides From Stellar And Man-Induced Nuclear Reactions, Lawrence Lee Oliver

Doctoral Dissertations

"Neutron activation and γ-counting were used to determine the relative abundances of six stable tellurium isotopes in the acid-etched residues of the Allende meteorite. The results were correlated with the isotopic compositions of xenon and the elemental abundances of helium and neon in similarly prepared residues. Nucleosynthesis appears to be the only viable explanation for the anomalous isotopic and elemental compositions observed in these residues. Our results suggest that the solar system condensed from an isotopically and chemically zoned nebula that was produced by the explosion of a supernova, concentric with the present sun.

A combination of neutron activation and …

Mode Of Action Of The Heme-Controlled Translational Inhibitor: Relationship Of Eukaryotic Initiation Factor 2-Stimulating Protein To Translation Restoring Factor., John Siekierka, Ken-Ichiro Mitsui, Severo Ochoa

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

We have purified the translation restoring factor (RF) and the eukaryotic initiation factor 2 (eIF-2) stimulating protein (ESP) to near homogeneity from the postribosomal supernatant and the ribosomal salt wash, respectively, of rabbit reticulocyte lysate. They were isolated in the form of eIF-2 complexes, apparently in a 1:1 ratio. Their virtually identical NaDodSO4/polyacrylamide gel electrophoretic patterns show, in addition to the eIF-2 alpha (38,000), beta (52,000), and gamma (54,000) bands, peptide bands at approximately 80, 65, 57, 40, and 32 kilodaltons. The apparent Mr of either complex is about 450,000, whereas that of free translation restoring factor (RF) is approximately …

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 …

Influence Of Las Vegas Wash Density Current On Nutrient Availability And Phytoplankton Growth In Lake Mead, John R. Baker, Larry J. Paulson

Publications (WR)

Density currents are commonly formed in reservoirs because of temperature or salinity induced density differences between inflowing and receiving waters. Anderson and Pritchard (1951) were among the first to demonstrate this in their investigations of density currents in Lake Mead. They found that the Colorado River formed an underflow in Lake Mead during the winter, an overflow in the spring and an interflow in the summer and fall. Wunderlich and Elder (1973) have since described the hydromechanics of these types of flow patterns, and density currents have been reported for several other large reservoirs (Carmack et al. 1979, Johnson and …

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 …

Studies Of The Reorientational Relaxation Of Pyridine In Water By Depolarized Rayleigh Light Scattering, C. H. Wang, Scott L. Whittenburg, P. A. Lund, D. H. Christensen

Chemistry and Biochemistry Faculty Publications

The depolarized Rayleigh spectra of aqueous solutions of pyridine have been studied using a high‐finesse Fabry–Perot interferometer as a function of temperature and concentration. The Rayleigh relaxation times are found to have a complex concentration and viscosity dependence. The classical Stokes–Einstein–Debye equation for molecular reorientation breaks down in this system. The Rayleigh relaxation time of pyridine molecules is not determined by the macroscopic shear viscosity of the solution. The specific interaction due to the formation of hydrogen bonds between pyridine and water molecules plays a very important role in affecting the relaxation time. At a fixed temperature the plot of …

Adaptative Alteration In Phospholipid Composition Of Plasma Membranes From A Somatic Cell Mutant Defective In The Regulation Of Cholesterol Biosynthesis, Michael Sinensky

Faculty Publications, Biological Sciences

A somatic cell mutant (CR1) of a Chinese hamster ovary cell (CHO-K1) which has previously been shown to be defective in the regulation of cholesterol biosynthesis accumulates more cholesterol than the parental cell line in plasma membranes. Although such an increase in membrane cholesterol should lead to an increase in the order parameter of these membranes, as measured with an electron spin resonance spin probe, the order parameters of mutant and wild-type plasma membranes are identical--apparently because of an adaptive alteration in membrane phospholipid composition. The phospholipid compositions of mutant and wild-type cell plasma membranes are compared and the mutant …

The Limnological Status Of Lake Mead And Lake Mohave Under Present And Future Powerplant Operations Of Hoover Dam, Larry J. Paulson, John R. Baker, James E. Deacon, U.S. Water And Power Resources Service

Publications (WR)

The ever-increasing demand for energy in the southwest has led to a search for additional sources of power generation. Coal-fired powerplants currently provide most of the baseline energy in the southwest, but this must be supplemented with hydroelectric power during periods of peak demand. In order to provide additional peaking power, the U.S. Bureau of Reclamation is considering a number of projects to modify existing hydroelectric facilities, or add new facilities in the Lake Mead Recreation Area. The Hoover Powerplant Modification Feasibility Investigation was authorized by Congress on December 16, 1975 to determine the feasibility of: (i) adding one or …

A Study Of Ylide Extractions Of Mercury In Fish And Water Using Cold Vapor Flameless Atomic Absorption Techniques, Howard Vail

Masters Theses & Specialist Projects

Cold vapor flameless atomic absorption spectrophotometry is an analytical method used in the determination of mercury. Its sensitivity is less than one part per billion using a 100 milliliter sample, and there are virtually no interferences from other metal ions. The method is best carried out making use of a permanganate-persulfate oxidation step with heat.

The ylide, triphenylphosphoniumcyclopentadienylide (CpPPh₃), which extracts mercury almost quantitatively from water, was used in attempts to remove mercury from exposed goldfish. Though not toxic to the fish, CpPPh₃ did not significantly lower mercury levels. Evaluation of CpPPh₃ as a possible phase …

The Association Of 5.8 S With 28s Ribosomal Rna, Nandita Banerjee

Chemistry & Biochemistry Theses & Dissertations

5.8S rRNA is a low molecular weight ribosomal RNA which is noncovalently bonded to the larger ribosomal subunit 28S rRNA; through its 3' end and through its 5' end. This interaction is an integral part of the ribosome, and plays an important role in the ribosome structure and function.

There is a high degree of homology between the 5.8S rRNA primary structures of rat, turtle and chicken. The base sequence of rat 5.8S rRNA differs only in one position from that of turtle and in three positions fr.om that of cl1.icken. Tl1ere is a single purine substitution at the 5' …

Inhibition Of N⁸-Acetylspermidine Deacetylation Activity Of Rat Liver, Michael J. Santacroce

University of the Pacific Theses and Dissertations

An enzyme activity located in the soluble fraction of rat liver which is known to deacetylate N⁸-acetylspermidine is studied. Using a crude cytosol preparation from rat liver, tritium-labelled N⁸-acetylspermidine [acetyl-³H] was shown to undergo deacetylation which was dependent upon both time of incubation and protein concentration. The Michalis constant for this deacetylation of N⁸-acetylspermidine is approximately 4.4 μM.

N¹-Acetylspermidine showed a competitive inhibition of this N⁸-acetylspermidine deacetylation activity, and was found to be the most potent inhibitor tested. Diamine and polyamine compounds were also shown to inhibit the …

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 …

Enhanced Nonenzymatic Glucosylation Of Human Serum Albumin In Diabetes Mellitus, C. Earl Guthrow, Mary Ann Morris, James F. Day, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

Use of an ion exchange chromatographic method and a colorimetric method with thiobarbituric acid showed that levels of nonenzymatically glucosylated serum albumin were increased in patients with poorly controlled diabetes mellitus compared to controls. The two methods correlated well (r = 0.99) and clearly discriminated between normal and poorly controlled diabetic populations. The levels of glycosylated hemoglobin were also measured in both populations. Several patients apparently in good control based on glycosylated hemoglobin measurements were found to have increased levels of glycosylated albumin. Because albumin has a shorter circulating half-life than does the human erythrocyte, the plasma concentration of glucosylated …

Heating-Effect Minimization In Dye Lasers, Kenneth Lee Matheson, James M. Thorne

Faculty Publications

Optical pumping of dye lasers deposits heat nonuniformly in the active medium. Because the refractive index of a liquid or gas is a function of temperature, gradients are created which refract the laser beam. This effect is sometimes serious enough to quench laser action. In this paper, we evaluate the effects caused by optical pumping with a coaxial flashlamp and suggest ultraviolet absorbers and wavelength shifters as materials for minimizing the problem

Preparation And Properties Of Benzotropones And Benzohomotropones, Robert E. Suder

Dissertations

No abstract provided.

21st Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Abstracts and meeting program from the 21st annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy and the Rocky Mountain Chromatography Discussion Group. Held in Denver, Colorado, July 30 - August 1, 1979.

The Concentration And Speciation Of Sugars In Natural Waters, Minoo Shakerin Sweet

Dissertations and Theses

Due to the importance of carbohydrates in biological systems, many efforts have been made to develop a quantitative method for analysis of carbohydrates in natural waters. The low concentrations of dissolved sugars in natural waters require a sensitive analytical method. In this study, gas chromatography of alditol acetate derivatives of sugars was investigated for quantitative and qualitative analysis of individual dissolved sugars in natural waters. The alditol acetate derivatives of sugars give only one derivative for each sugar, yielding qualitative and quantitative results.

The detection limit was 25 nM for each sugar. Because of this very low detection limit, only …

Analytical Applications Of Ultrasonic Velocity Using Three-Transducer Phase-Shift Detection, Chuan Chen

Chemistry and Chemical Biology ETDs

A new method for determining ultrasonic velocity and its appli­cation as a high-performance liquid chromatography (H.P.L.C.) detector is developed. The method involves in using a three­transducer phase-shift device where two transducers alternately transmit 1-MHz continuous wave signals to the same receiver. Ultra­sonic velocity can be calculated from the phase-shift difference between the two cell paths. When the device is used as an H.P.L.C. detector, the reciprocal of the phase-shift difference between the two cell paths is converted to an electrical signal and recorded on a chart paper with respect to retention time. The theoretical principles are discussed and the appropriate …

Site Specificity In The Intercalation Of Antitumor Antibiotics With Dna, Martin Bradford Jones

Chemistry and Chemical Biology ETDs

Many planar molecules or molecules with planar moieties have been shown to bind to DNA by intercalation, which can be defined as the insertion of a planar moiety between adjacent bases on the DNA strand, reading in the 3'-5' direction, accompanied by a partial unwinding and elongation of the helix in the immediate vicinity of the intercalation site. Intercalation raises the question of specificity of binding of the drug to DNA, since there are 16 possible intercalation sites in normal double-stranded DNA. The conformational changes (elongation and unwinding) associated with intercalation make circular dichroism (CD) an excellent technique for studying …

Bulletin 3992 - Nitrogenous Fertilisers For Cereal Production, M. G. Mason

Bulletins - 3000 - 3999

Because fertiliser prices continue to rise, it is becoming increasingly important to understand what affects the response to fertilisers by crops.

Among the many factors influencing crop response to nitrogen applications, the most important are the season, soil type, paddock history, time of application and source of nitrogen. Before deciding whether to use nitrogen on a cereal crop, which source to use and at what rate, the farmer needs some understanding of how these factors work.

The Synthesis Of C₄ And C₅ 13c-Labeled Benzo[A]Pyrene, Benzo[A]Pyrene-4, 5-Oxide And Derivatives. Studies Of The Reactions Of Benzo[A]Pyrene-4, 5-Oxide Using 13cnmr, Mark David Hylarides

Chemistry and Chemical Biology ETDs

Benzo[a]pyrene (BAP), BAP-4,5-oxide, and other derivatives which are 13c-labeled in the 4-and 5-positions were synthesized. The synthetic scheme involves an initial reaction of the lithioenolate of ethyl acetate-1-13c or ethyl acetate-2-13c with l,2-dihydrochrysen4(3H)-one. Subsequent dehydration and dehydrogenation gave ethyl 4-chryseneacetate-1-C (or 2-C). Partial reduction to the aldehyde 13 13 followed by cyclization gave BAP-5-C (and 4-C). Toe synchesis of 13 BAP-4,5-oxide-4-13c (and 5-c) involved saponification of ethyl 4-chryseneacetate-1-13c (and 2-13c), an intermediate in the synthesis of BAP, followed by cyclization of the resultant acid to BAP-5-ol13 s-c (and 4-13c). The crude phenol was oxidized to the o-quinone. Further reduction of …

Kinematics And Thermodynamics Of Nickel(Ii)-Glycine Complexes Using Carbon Magnetic Resonance, Donald Frederick Shepard

Chemistry and Chemical Biology ETDs

1-¹³C glycine was studied in nickel(II) solutions using carbon magnetic resonance (CMR). The carboxy bound nickel(II)-glycine complex and the kinetics of complexation between aquated nickel(II) ion and aquated glycine are described. It has been hypothesized that solutions containing no complexation higher than the chelated mono nickel(II)-glycine complex contain five magnetically different glycine species. The effects of these five magnetically different glycine species on the CMR spectra of the nickel(II)-glycine solutions are discussed. The lifetime of the carboxy bound complex is 7.87 x 10^-4 sec at 272 K with an activation energy of 9.74 kcal/mole, an activation enthalpy …

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 …