Physical Sciences and Mathematics Commons^™

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. …

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.

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.

Picosecond Laser Pulse Irradiation Of Crystalline Silicon, K. L. Merkle, H. Baumgart, R.H. Uebbing, F. Phillipp

Electrical & Computer Engineering Faculty Publications

Morphology changes introduced by picosecond laser pulses at λ = 532 nm and 355 nm in (111) and (100) silicon samples are studied by means of optical and high-voltage electron microscopy. Depending on energy fluence, orientation and wavelength, amorphous or highly defective regions may be created. From an analysis of damage thresholds and damage depth distributions it is concluded that melting and energy confinement precedes the formation of the structural changes.

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 …

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 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).

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 …

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 …

The Preparation Of The Coordination Compounds Of Palladium (Ii) And Spermine And Spermidine, Wenli Grace Lee

University of the Pacific Theses and Dissertations

The purpose of this study was to prepare and characterize complexes produced by the reactions of spermine and spermidine with palladium(II) chloride. A first analysis of the problem seemed to indicate that preparation of the complexes should be straightforward and not difficult. Bonding of the nitrogen atoms to the metals allows sterically for formation of two six-membered rings separated by a tetramethylene chain in a spermine complex, and by a six-membered chelate ring in a spermidine complex.

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 …

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 …

Hydroxide Binding Equilibrium In Hemerythrin, John David Mccallum

Dissertations and Theses

The measurement of the equilibrium constant and the thermodynamic parameters of the binding of hydroxide ions to the active site of hemerythrin, an invertebrate iron containing protein, was done by a new difference spectroscopic method. The method enables accurate measurements of equilibrium constants without accurate knowledge of molar absorptivities or protein concentrations and is novel in that it takes the difference between the two equilibrium mixtures, thus enabling the measurement of equilibrium constants when it is not convenient or possible to produce either substance as a pure reference material.

An Investigation Of Cadmium And Sulfur Reactions In Dimethylsulfoxide, Howard W. Hogle

Dissertations and Theses

The study of the reaction of cadmium and sulfur in dimethylsulfoxide (DMSO) is presented. Specifically, the reaction of dissolved molecular sulfur in DMSO at temperatures greater than 90°C with freshly precipitated metallic cadmium is followed by UV-visible spectrometry, atomic absorption spectrometry, and Raman spectrometry. Evidence for the formation of a new cadmium-sulfur species and S₃- is discussed. In a second reaction, an equilibrium sodium polysulfide solution in DMSO is titrated with a solution of cadmium ion at room temperature and the reaction progress is followed by means of UV-visible spectrometry. A calculation of the average number of polysulfide …

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 …

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 …

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. …

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 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 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 …

Centers Of Polymer Research; Polymer Science In Tokyo, Japan, Part I: Central Area, Otto Vogl, A. Nakajima

Otto Vogl

No abstract provided.

The Anodic Stripping Voltammetry Determination Of Trace Elements In Coal Ash, Jesus Montoya

Masters Theses & Specialist Projects

The application of anodic stripping voltammetry (ASV) to the determination of several trace metals in coal ash was studied.

An ashing and ash digestion method was developed which limited the total salt and acid concentration of the analyte solutions, a necessary step for routine analysis. The simultaneous determination of cadmium, copper, lead, and zinc in eight Pennsylvania State University Coal Bank Samples and in the National Bureau of Standards SRM 1632a coal sample were made. Chromium was separated from the prepared coal ash solutions and determined independently in the form of chromate(VI).

All values determined by ASV methods were in …

Chemistry Of Chromium Oxyfluorides And Group Vib Perfluoroglutarates, Bruce Michael Johnson

Dissertations and Theses

Pure chromium oxide trifluoride was prepared for the first time by reaction of CrO₃ and ClF with subsequent multiple fluorine treatments at 120°C. On the basis of its infrared spectrum, the purple CrOF₃ was assigned as a fluorine-bridged polymer with terminal oxygen groups. Chromium oxide trifluoride was found to be stable to 300°C, where it decomposes with the loss of oxygen to CrF₃.

Piezomodulation Spectroscopy Of Molecular Crystals. Ii. The Pyromellitic Dianhydride Anthracene Electron Donor–Acceptor Complex, J. Merski, Craig J. Eckhardt

Craig J. Eckhardt Publications

Piezomodulated reflection spectra are presented for the crystalline complex of pyromellitic dianhydride–anthracene. Two differently polarized charge transfer transitions are found and their strain sensitivities are obtained. The role of the charge transfer interaction in determining the magnitude of the piezomodulation is assessed. The piezomodulation spectra are found to have the response expected for an oriented gas. Significant enhancement of structure is also observed and is correlated with structure observed at 20 K.

Piezomodulation Spectroscopy Of Molecular Crystals. I. Methods And Principles, J. Merski, Craig J. Eckhardt

Craig J. Eckhardt Publications

The effects of piezomodulation on the spectra (particularly reflectivity spectra) of molecular crystals for the strong, weak, and no coupling regimes are considered. The stress or strain modulation of the crystal is shown to affect the dispersion energy and exciton resonance interaction. The experimental approach is outlined. Methods of data analysis are described for obtaining differential changes in the real and imaginary parts of the dielectric function, for determining deformation potentials for vibronic transitions, and for applying the Seraphin coefficients. Previous microscopic theory for interaction of excitons with static lattice deformations is adapted for the modulated case. Application of classical …

Piezomodulation Spectroscopy Of Molecular Crystals. Iii. The First Singlet System Of Anthracene, J. Merski, Craig J. Eckhardt

Craig J. Eckhardt Publications

The polarized piezoreflection spectra of the first singlet system of anthracene and their Kramers-Kronig transforms are reported. Exciton energy strain shifts are reported for the b-polarized and for the ac-polarized factor group components. These values are shown to be in good agreement with related experimental data and with theoretical calculations. The piezomodulation spectra significantly enhance structure and are also sensitive to the extent of crystal coupling. Deviations in the measured spectra are observed in the a-polarized spectra from that calculated for the logarithmic derivative. These variances are attributed to coupling with the second singlet of anthracene or …

Piezomodulation Spectroscopy Of Molecular Crystals. Iv. The First Singlet Systems Of Tcnq And Bdp, J. Merski, Craig J. Eckhardt

Craig J. Eckhardt Publications

The polarized modulated piezoreflection spectra of the first singlet system of TCNQ and BDP are reported. Kramers-Kronig transformations are obtained and polariton energy strain shifts are determined. In contrast to systems with negligible to intermediate coupling, the piezomodulation spectrum for the mixed transverse-longitudinal polaritons show strong deviations from the logarithmic frequency derivative of the corresponding reflection spectra. Progressions in the piezomodulation spectra in the energy region of the stop band are related to multiparticle states. Piezomodulation spectroscopy is shown to exhibit greatest deviation from derivative behavior when solid state effects become extensive.

Synthesis And Evaluation Of Polymer Supported Homogenous Oxidation Catalysts, Raymond J. Riley

Retrospective Theses and Dissertations

Polystyrene bis(salicylaldehyde)-propylene-1,3-diiminato Cobalt (II) [salen] and Polystyrene bis(2,4-pentanedione)-propylene-1,3-diiminato Cobalt (II) [BAE] were prepared stepwise from chloromethylated polystyrene. In addition, a new preparation of a Schiff base was attempted resulting in Polystyrene bis(salicylaldehyde)-isobutylene-1,3-diiminoato Cobalt (II) being produced. Optimum reaction conditions were determined with regard tot ime, temperature, reaction ratios and solvent for each step for the reaction. The ability of the above named Cobalt (II) Schiff bases to oxidize 3-methyl indole to give the corresponding o-formylaminoacetophenone was also studied. One polymer-bound Schiff base cobalt catalyst (co-salen) demonstrated a very small amount of catalytic activity resulting in a minimum amount of o-formylaminoacetophenone …

Synthesis Of Dihydroisoquinolines And Tetrahydroisoquinolines, John J. Schlager

Chemistry & Biochemistry Theses & Dissertations

Dihydroisoquinolines and tetrahydroisoquinolines are compounds which possess a variety of pharmacological activities. New easier methods of synthetic manipulations of these structures is of constant interest in the pharmaceutical industry.

This paper describes a new three step method of preparing 1-alkyl- and 1-aryl-tetrahydroisoquinolines from a tetrahydroisoquinoline. The synthesis involves the N-chlorination of tetrahydroisoquinoline followed by dehydrohalogenation with potassium superoxide. The reaction products are the dihydroisoquinolines. Overall yields range from 85-96%. The unsubstituted, 1-methyl-, and 1-phenyl-J,4-dihydroisoquinolines have been formed. Organometallation of the unsubstituted dihydroisoquinoline provides the 1-substituted tetrahydroisoquinoline. The 1-benzyl-, 1-n-butyl-, 1-ethyl-, 1-methyl-, and 1-phenyl-1,2,J,4-tetrahydroisoquinolines were prepared. The use of Grignard and …