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The Regioselective 3-Alkylation Of Piperidine, Richard Dunn Todd

Chemistry & Biochemistry Theses & Dissertations

The compounds: 3-allylpiperidine, 3-ethylpiperidine and 3-n-butylpiperidine have been synthesized by regioselectively alkylating the three position of piperidine. Piperidine was converted to N-chloropiperidine and then dehydrohalogenated to produce Δ¹-piperideine. The enamide anion was generated by adding solutions of Δ¹-piperideine to ethylmagnesium bromide or lithium diisopropylamide. Addition of alkylhalides produced 3-alkyl- Δ¹-piperideine which could be reduced or alkyllithiated to give 3-alkylpiperidines or 2,3-dialkylpiperidines respectively.

The yields of products were low and the reaction generated a continuum of mono- and di-alkylpiperidines and there was evidence that several dimeric piperideines were formed. The low yields were discussed in …

High-Temperature Battery Calorimeter, L. D. Hansen, R. H. Hart, D. M. Chen, H. F. Gibbard

Faculty Publications

A battery calorimeter was built for the measurement of thermal energy generation of high-temperature lithium–aluminum/iron sulfide battery cells, which are under development for electric vehicle propulsion and other energy storage applications. The calorimeter was designed with a temperature range of 400˚–500˚C, a detection limit of 1 mW, and an upper limit of heat flow of 50 W. The results of measurements on 200-Ah LiAl/FeS cells were in excellent agreement with the predictions of thermodynamic calculations based on precise measurements of the total cell polarization and the temperature coefficient of the emf. Details of the construction and operation principles of this …

Ortho Cyclization Reactions Of Catecholamines, Robert Lee Hudkins

Chemistry & Biochemistry Theses & Dissertations

A study was undertaken to examine the potential for ortho cyclization associated with the synthesis of 1,2,3,4,-tetrahydroisoquinolines using the Pictet-Spengler reaction. Specif1cally, the condensation of the biogenic amines, dopamine, norepinephrine and epinephrine were carefully examined in light of current literature and the facility and extent of ortho cyclization in each case. The para isomers of these three biogenic amine condensation products were isolated and characterized, while only the ortho isomer derived from dopamine was found stable and could be isolated, and structurally identified. These studies demonstrate that a second cyclization product does, in fact, form in each instance and that …

Structural And Magnetic Properties Of Y(Al₁₋ₓfeₓ)₁₂, Ying-Chang Yang, Gary J. Long, William Joseph James, R. Yeh

Chemistry Faculty Research & Creative Works

In order to investigate the magnetic behavior of 3d atoms in the ThMn₁₂‐type structure, the structured and magnetic properties of Y(Al_1-xFe_x)₁₂ were studied by Mössbauer spectroscopy and magnetization measurements. The Y(Al_1-xFe_x)₁₂ intermetallic compounds crystallize in the ThMn₁₂‐type structure for x in the range of 0.3-0.5. The results can be explained on the basis of the preferential atomic ordering observed in the ternary compounds. The compounds are ferromagnetic with Curie temperatures of 130, 170, and 280 K, respectively, for x values of 0.3, 0.4, and 0.5.

Bond Hybrids And The Structures Of The Lanthanide Metals [Abstract], Richard H. Langley

Faculty Publications

The ideas developed by Altmann, Coulson, and Hume-Rothery to relate bond hybrids to metal structures are extended to include treatment of the f orbitals. A discussion of the possible hybrids along with their application to the lanthanide metals will be considered.

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. …

High‐Resolution Ν1 Spectrum Of Propyne: Application Of A Microcomputer‐Controlled Infrared‐Acoustic Color Center Laser Spectrometer, E. Kyrö, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

Development of a microcomputer‐controlled infrared‐acoustic color center laserspectrometer capable of scanning in 100 cm⁻¹ sections over the wavelength range 2.2–3.3 μm with a resolution of 0.01 cm⁻¹ (300 MHz) is reported. Application of the spectrometer to investigation of the ν₁spectrum of propyne is demonstrated.

Travelling-Wave Sub-Doppler Excited Molecule Energy Transfer Spectroscopy, Khalid Iqbal, Shannon G. Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

A general formulation of traveling‐wave sub‐Doppler excited molecule energy transferspectroscopy is presented. The line profile analysis is applied to that determined experimentally for the R(22) ν3 HCN transition. Pn the noise equivalent power of the detector is demonstrated to be ⩽10−12 W. Finally, the technique is applied to resolve the KsR(7) ν1 transition head in NH3.

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 …

Electrochemical Determination Of The Heterogeneous Electron Transfer Kinetics Of Soluble Spinach Ferredoxin, Charlene D. Crawley

Theses and Dissertations

The application of electrochemical techniques to biological systems has become an attractive method for characterizing the redox and electron transfer behavior of biomacromolecules. This study focuses on the role of soluble spinach ferredoxin (Fd) in photosynthesis where it functions as an electron carrier to membrane bound species in the plant chloroplast. An electrochemical model is used where in Fd now serves as a soluble redox species which undergoes oxidation and reduction via electron transfer at an electrode. This type of model is significant in that both the membrane and electrode reactive sites are characterized by charged bilayer interfacial regions which …

Cleavage And Deoxygenation Of Phenolic Ethers, Derhsing Luu

Masters Theses

Dibromotriphenylphosphorane (DTP) in acetonitrile at 50°C was found to cleave ß-naphthylmethyl phenyl ether in preference to ß-naphthyl benzyl ether, 62% and 30% cleavage, respectively. Reaction of ß-naphthyl benzyl ether in dichloromethane at reflux produced 67% cleavage.

The quasiphosphonium complexes obtained by reaction of phenolic compounds with DTP were found to be reduced by several reducing reagents to give the corresponding aromatic hydrocarbons. Reaction of p-cresol with DTP, followed by lithium aluminum hydride reduction gave 38% toluene; sodium naphthalide reduction in THF gave 32% toluene; sodium in liquid ammonia reduction gave 12% toluene; sodium naphthalide reduction in DMF gave 15% toluene. …

A Laser Interferometric Study Of Electric Field Effects On Methane-Oxygen Flame Plasmas, Mark D. Prairie

Masters Theses

A laser interferometer is developed to study the refractive index field, aerodynamic structure, and three dimensional temperature profile of a methane-oxygen flame system under the influence of D.C. electric fields. A combined graphical-numerical method is used to transform the observed interference patterns into radial temperature distributions. The results indicate that the electric field exerts a marked influence on the flame stability, geometry, and charged particle flow. Experimental evidence shows that these effects are most apparent under fuel rich conditions. It is suggested an electric field may change the concentration gradients of reacting species, leading to an altered course of fuel …

A Comparison Of The Surface Polysaccharides From Rhizobium Japonicum Strains I110ars And 61a76str, And The Isolation Of Soybean Root Proteins Responsible For The Binding Of Eps From R. Japonicum Strain I110ars, Richard F. Koehler

Masters Theses

The surface polysaccharides of Rhizobium are implicated in the symbiotic process. The composition of the surface polysaccharides from two strains of Rhizobium japonicum, I110 ARS and 61A76 str, have been compared. Five polysaccharide fractions are obtained from the I110 ARS strain. They are the EPS (extracellular polysaccharide), CPS-1 and CPS-2 (capsular polysaccharide fractions), LPS (lipopolysaccharide) and Phe (polysaccharide found in the phenol layer from the phenol/water extraction). These polysaccharide fractions have identical sugar compositions. Four polysaccharide fractions are obtained from the 61A76 str strain. These are the EPS, CPS-1, SmPS (small molecular weight polysaccharide), and Phe. Each of these …

A Spectroscopic Study Of Intramicellar Environment With Merocyanine Dye Probes, Elise Jane Daggs

University of the Pacific Theses and Dissertations

The effects of micelle forming surfactants hexadecyltrimethylammonium bromide, sodium dodecyl sulfate and igepal CA~6JO on the visible spectra of merocyanine dyes of the form 1-alkyl-4-[(3', 5'-alkyl oxocyclohexadienylidene)ethylidene]- 1,4-dihydropyridine were studied. In all cases the visible spectrum shifted to the red when the dye was incorporated into the micelles. The magnitude of the shifts was found to be dependent on the substituted groups and the positioning of the chromophore of the dye in the micelle aggregates. The shifts indicate a highly hydrated environment about the surfactant head groups and an environment equivalent to that of pure ethanol solvent at some undetermined …

Flow Injection Atomic Absorption Assay Of Copper And Zinc In The Plasma Of Age Dependent Audiogenic Seizure Susceptible Mice, Neal Dwain Byington

University of the Pacific Theses and Dissertations

Flow injection atomic absorption procedures with less than 10%RSD at 1.0 ppm were developed for the assay of copper and zinc in 10 μL samples of mouse plasma. The flow injection apparatus was designed with a pulseless liquid flow control system, regulated by inert gas pressure. The aspiration liquid is 6% t-butanol in water. After exhaustive parameter optimizations, copper assays were conducted with the conventional air-acetylene flame at 324.754 nm and zinc assays were conducted with the unconventional argon-hydrogen air diffusion flame at 213.856 nm. The argon-hydrogen flame system was chosen because it absorbs very little ultraviolet light.

The developed …

Organic N-Chloramines: Chemistry And Toxicology, Frank E. Scully, Jr., Maxwell A. Bempong

Chemistry & Biochemistry Faculty Publications

The stability of aqueous solutions of organic N-chloramines, suspected of contaminating chlorinated water, has been studied. Two factors influence the decomposition of solutions of N-chloropiperidine and N-chlorodiethylamine: a spontaneous decomposition and photodecomposition. Since solutions of these compounds are relatively long-lived, a need for an analytical method for their identification is discussed. A new method is described which involves reaction of organic N-chloramines with arenesulfinic acid salts. The method gives high yields of stable arenesulfonamides. Several toxicological studies of N-chloropiperidine are described. The compound is mutagenic by Ames assay in Salmonella typhimurium strain TA 100 and does not require metabolic activation …

Synthesis And Evaluation Of Polymeric Ether Glycol Derivatives For Use As Transducer Fluids, Cynthia K. Mccurry

Retrospective Theses and Dissertations

A series of end-capped PAG (n-butyl, n-alkyl substituted polypropylene glycol) and PPGs (bis-di-alkyl-,bis-di-halo-, bis-di-fluoroalkylpolypropylene glycol) were synthesized. Optimum reaction conditions were determined in regard to time, temperature, reaction ratios, and solvents for each of the PAG and PPG derivatives. An investigation of the named PAG and PPG derivatives as potentially new sonar transducer fluids was carried out. Density, viscosity and sound speed measurements with regard to temperature, as well as water solubility measurements, were carried out for several of these derivatives. The desirable properties possessed by several of these derivatives make them of potential value in application as transducer fill-fluids.

Current Concepts Of Cerebrovascular Disease - Stroke: Stroke And Drug Abuse, L. R. Caplan, D. (Daniel) B. Hier, G. Banks

Chemistry Faculty Research & Creative Works

This Review Summarizes Available Information Concerning Cerebral Vascular Complications of the Most Commonly Abused Substances and Discusses Possible Mechanisms of Vascular Injury and Cerebral Damage. Although Alcohol is Frequently Abused and May Have Important Cerebrovascular Effects, its Consideration is Beyond the Scope of This Review.

A Study Of Poly(P‐Xylylene)‐Coated Asf5‐Doped Polyacetylene, J. E. Osterholm, H. Yasuda, L. L. Levenson

Physics Faculty Research & Creative Works

Electrical conductivity measurements and scanning electron microscopy have been used to study uncoated and poly(p‐xylylene)‐coated samples of polyacetylene doped with AsF5. These initial results indicate a considerable reduction in the decay rate of conductivity in the presence of oxygen as well as a decreased rate of thermal decomposition of the dopant when heated between 50°C and 115°C in vacuum by the coating. Copyright © 1982 John Wiley & Sons, Inc.

Measurement Of Synchrotron X-Ray Energies And Line Shapes Using Diffraction Markers, Juana Vivó Acrivos, S.S. P. Parkin, K. Hathaway, J. R. Reynolds, M. P. Klein, A. Thompson, D. Goodin

Faculty Publications, Chemistry

Standard reference markers for accurate, reproducible synchrotron x-ray energies are obtained using a three Si crystal spectrometer. The first two crystals are in the monochromator and the third is used to obtain diffraction markers which monitor the energy. Then for any value of the glancing angle on the reference Si crystal the energy for the (333) diffraction must occur at 3/4 that of the (444) and 3/5 of that for the (555). This establishes for the first time an absolute synchrotron energy scale. Higher-order diffractions are used to determine excitation line profiles. We conclude that the use of reference diffractions …

The Reaction Of 4-Vinylcyclohexene With Palladium (Ii), Kathy Ellen Beeler

University of the Pacific Theses and Dissertations

This program of study was concerned with the elucidation of the causes(s) behind the inability of various workers to reproduce the work of Fyre and Kuljian on the rearrangement of 4-vinylcyclohexene to 1,5-cyclooctadiene by the action of palladium (II).

Protein Synthesis In Rabbit Reticulocytes: Characteristics Of The Protein Factor Rf That Reverses Inhibition Of Protein Synthesis In Heme-Deficient Reticulocyte Lysates, Michael Grace, Robert O. Ralston, Ambica C. Banerjee, Naba K. Gupta

Department of Chemistry: Faculty Publications

During heme deficiency in reticulocyte lysates, the heme-regulated translational inhibitor of protein synthesis (HRI) is activated and shuts off protein synthesis. In partial reactions, HRI phosphorylates the M_r 38,000 subunit (α subunit) of eukaryotic initiation factor 2 (eIF-2), which forms a ternary complex, Met-tRNA_f•eIF-2•GTP. The eIF-2α(P) thus formed is not recognized by two eIF-2 ancillary factors, Co-eIF-2B (which promotes the dissociation of the ternary complex at high Mg²⁺) and Co-eIF-2C (which reverses the inhibition of ternary complex formation), and thus, is presumably inactive in peptide chain initiation. A protein factor, designated RF, which reverses inhibition …

Controlling The Number Of Metal Sites To Which A Poly(Tertiary Phosphine) Coordinates To Group 6 Metal Carbonyls, Nestor Paul Hansen

Masters Theses

The compounds trisdiphenylphosphine(tricarbonyl) metal and trisdiphenylvinylphosphine(tricarbonyl) metal of molybdenum and tungsten were prepared. These compounds were allowed to react with diphenylvinylphosphine and diphenylphosphine, respectively, in the presence of azobis(2-methyipropio)nitrile or potassium t-butoxide to yield the complex containing bis(diphenylphosphino) ethane as a chelated ligand.

The tris-substituted compounds showed a large degree of lability which prevented the isolation of the desired, (OC)₃M(Ph₂PCH₂CH₂PPh₂)₃, compound which contains three ditertiary phosphines acting as monodentate ligands.

Coordinated diphenylphosphine and diphenylvinylphosphine pentacarbonyl compounds of chromium, molybdenum and tungsten were prepared and allowed to react in …

The Interaction Of R. Leguminosarum 128c53 With Pea Root Proteins And A Comparison Of The Surface Polysaccharide With A Mutant Defective In Nodulation, Ru-Po Lee

Masters Theses

The Rhizobium extracellular polysaccharides (EPS) and lipopolysaccharides (LPS) are implicated in the symbiotic process. The interaction between host root protein fractions and symbiont EPS-polyacrylamide affinity support has been investigated. Ten percent root protein fractions had been observed to bind to the affinity support. The compositions of the polysaccharides from the parent R. leguminosarum and its Exo^-1 mutant have also been compared. The Exo^-1 mutant produces diminished amount of EPS and does not nodulate the host pea roots. Five kinds of polysaccharides from the parent were obtained: EPS, capsule polysaccharides (CPS I) washed from the bacteria with saline solution, …

A Comparison Of The Surface Polysaccharides Of Rhizobium Trifolii Su843 With Its Genetically Altered Mutant, 8002, Which Is Defective At Root Hair Curling (Hac-), Elroy Alfredo Turnbull

Masters Theses

Bacteria of the genus Rhizobium are capable of forming a complex nitrogen fixing (fix⁺) symbiotic association with leguminous plants. The surface polysaccharides are believed to be essential in the symbiotic process. The surface polysaccharides of a genetically altered Rhizobium trifolii mutant, 8002--which does not cause root hair curling (HAC^-), forms no nodules (Nod^-) nor fixes nitrogen (Fix^-)--is compared with its parent, SU843, which causes root hair curling (HAC⁺), forms nodules (Nod⁺), and fixes nitrogen (Fix⁺). Three types of surface polysaccharides--extracellular polysaccharide(s) (EPS), capsular polysaccharide(s) (CPS), and …

Mechanism Of Polypeptide Chain Initiation In Eukaryotes And Its Control By Phosphorylation Of The Alpha Subunit Of Initiation Factor 2., John Siekierka, Ljubica Mauser, Severo Ochoa

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Earlier, we isolated eukaryotic initiation factor 2 (eIF-2)-stimulating protein (SP) as a homogeneous complex with eIF-2 (eIF-2-SP) and showed that, in the presence of Mg2+, eIF-2-SP promotes formation of a ternary complex with GTP and eukaryotic initiator methionyl tRNA (Met-tRNAi) (eIF-2-GTP-Met-tRNAi) catalytically. We now show that SP-bound eIF-2 exchanges with eIF-2 (eIF-2 exchange). Furthermore, in the presence of Mg2+, eIF-2-SP catalyzes the exchange of eIF-2-bound [3H]GDP with unlabeled GDP or GTP (GDP exchange) and the release of [3H]GDP when the ternary complex is formed from eIF-2-[3H]GDP, GTP, and [35S]Met-tRNAi. All these reactions are blocked by alpha-subunit, but not by beta-subunit, …

Interfacial Electrochemistry Of Cytochrome C And Myoglobin, Edmond F. Bowden

Theses and Dissertations

The interfacial electrochemistry of horse heart cytochrome c was studied at metal and metal oxide electrodes. Sperm whale myoglobin reactions at metal oxide and surface modified electrodes were also investigated. Emphasis was on the measurement and mechanistic interpretation of the heterogeneous electron transfer kinetic parameters for these electrode reactions.

The motivation for this study stems from the fact that some electron transfer proteins, e.g., cytochrome c, transfer electrons heterogeneously in physiological systems. Specific electrodes may, therefore, serve as suitable models for physiological surfaces. Electrode and membrane interfaces are both electrically charged and both have oriented hydration water layers.

The cyclic …

A Potential Problem With The Tsi Electrostatic Aerosol Classifier, Darryl J. Alofs, Max B. Trueblood

Mechanical and Aerospace Engineering Faculty Research & Creative Works

No abstract provided.

Biomedical Applications Of Plasma Polymerization And Plasma Treatment Of Polymer Surfaces, H. Yasuda, M. Gazicki

Chemistry Faculty Research & Creative Works

Thin polymer films obtained by plasma polymerization usually show good biocompatibility when compared to classical biomaterials such as Silastic. The thicknesses of these films (from several hundreds of Å to several μm) make them suitable for the purpose of changing the surface properties of the substrate without altering its bulk properties. Both the above features together indicate the possible Biomedical use of plasma polymerization as well as plasma treatment of polymer surfaces processes. The purpose of this review is to present the most significant efforts to develop such applications with the specification of particular fields where these efforts are directed. …

Furanosesquiterpenoids Of Commiphora Erythraea And C. Myrrh, Asafu Maradufu

All Peer-Reviewed Publications

The isolation and structure determination of two new furanosesquiterpenoids, 2-O-acetyl-8,12-epoxygermacra-1(10),4,7,11-tetraene and 2-O-methyl-8,12-epoxygermacra-1(10)-4,7,11-tetraene, from gum exudates of Commiphora myrrh are reported. These two compounds, together with the known furanodienone isolated from C. erythraea, were found to have ixodicidal activity against Rhipicephalus appendiculatus tick larvae. © 1982.