Digital Commons Network^™

Neutron-Diffraction And Mössbauer Effect Study Of The Preferential Silicon Site Occupation And Magnetic Structure Of Nd₂Fe₁₄₋ₓsiₓb, Gaya Kanishka Marasinghe, Oran Allan Pringle, Gary J. Long, William Joseph James, Dianne J. Xiao, J. L. Li, William B. Yelon, Fernande Grandjean

Physics Faculty Research & Creative Works

A neutron-diffraction study of Nd₂Fe_14-xSi_xB has shown that silicon preferentially occupies the 4c site in the transition-metal sublattice in Nd₂Fe₁₄B. Silicon also exhibits a moderate preference for the 8j₁ site, is almost excluded from the 16k₂ site, and avoids the 16k₁, 8j₂, and 4e sites. The silicon site occupancy is correlated with a preference for a silicon atom to have rare-earth atoms in its coordination environment. The Mössbauer spectra of Nd₂Fe_14-xSi_xB have been fit with a model which …

Piezomodulated-Raman-Spectroscopy Study Of The Phase Transition In Phenothiazine, J. Sartwell, Craig J. Eckhardt

Craig J. Eckhardt Publications

Single crystals of phenothiazine undergo a displacive order-disorder phase transition near 250 K. The microscopic mechanism of this transition is not clear owing to the complexity of a disordered lattice and the lack of direct mode-anharmonicity data. Unstable optical modes have been observed in phenothiazine and are regarded as coupled, by symmetry, to an acoustic mode that becomes overdamped through the phase transition. The latter is considered to have the primary role in the phase transition. This premise is in doubt, however, based on the optical-mode anharmonicity directly observed by uniaxial-piezomodulation-Raman-spectroscopy results presented here. Anharmonic responses are observed in the …

Nitric Oxide Absorption From Flue Gas With Cumene Hydroperoxide Solution, Chung-Der Chen

Theses

The absorption of nitric oxide from gas streams with cumene hydroperoxide (CHP) in n-hexadecane (cetane) as the scrubbing solution was investigated. The efficiency of the scrubbing solution to remove nitric oxide was evaluated over the temperature range of 90 to 110°C, concentration range of 0.1 to 0.5M, and residence time of 12 to 80 seconds. The products were analyzed by gas chromatography (GC), Fourier transform infrared spectroscopy (FTIR), and ion chromatography (IC). The goal of this research was to determine the NO removing efficiency of cumene hydroperoxide solution, a relatively inexpensive tertiary organic hydroperoxide. Also, a possible reaction mechanism for …

Interaction Of Cationic Porphyrins With Dna, Ulrica Sehlstedt, Pamela Carter, Jerry Goodisman, James C. Dabrowiak, Seog K. Kim

Chemistry - All Scholarship

Utilizing linear dichroism (LD), circular dichroism (CD), and fluorescence energy transfer, the binding geometries of a series of Co3+-porphyrins and their free ligands were examined. The compounds studied were Co-meso-tetrakis(N-methylpyridinium-4-yl)porphyi(nC oTMPyP) and its free ligand (H2- TMPyP), Co-meso-tetrakis(N-n-butylpyridinium-4-yl)porphyrin( CoTBPyP) and its free ligand (H2TBPyP), and Co-meso-tetrakis(N-n-octylpyridinium-4-yl)porphyrin (CoTOPyP). The two non-metalloporphyrins exhibit negative LD, having angles of roughly 75' relative to the DNA helix axis. They also display negative CD and a significant contact energy transfer from the DNA bases. On the other hand, the three metalloporphyrins display orientation angles of roughly 45' between the porphyrin plane and the helix axis …

Purification And Characterization Of A Gamma-Like Dna-Polymerase From Chenopodium Album L., K. Meißner, Sabine Heinhorst, Gordon C. Cannon, T. Börner

Faculty Publications

A DNA polymerase activity from mitochondria of the dicotyledonous angiosperm Chenopodium album L. was purified almost 9000 fold by successive column chromatography steps on DEAE cellulose, heparin agarose and ssDNA cellulose. The enzyme was characterized as a gamma-class polymerase, based on its resistance to inhibitors of the nuclear DNA polymerase alpha and its preference for poly(rA).(dT)12-18 over activated DNA in vitro. The molecular weight was estimated to be 80,000 - 90,000. A 3' to 5' exonuclease activity was found to be tightly associated with the DNA polymerase activity through all purification steps. This is the first report of an association …

Investigation Of The Β-Γ Phase Transition In Single Crystal Malononitrile By Polarized Raman Spectroscopy, S.J. Bonafede, Craig J. Eckhardt

Craig J. Eckhardt Publications

Temperature dependent, polarized Raman spectra in the lattice mode region for sublimed, single crystal malononitrile through the β-γ phase transition (T_c=294.7 K) are reported. Symmetry assignments and frequencies of vibrational modes are made and compared to previous studies. Nine out of 12 possible lattice modes are observed in each phase with three of the observed modes being affected by the phase transition. The temperature dependence of these three affected modes is attributed to cyano group and molecular dipole interactions between molecules in the crystal. The behavior of malononitrile through the β-γ phase transition is analogous to the …

Separation And Characterization Of Components Of Catalytic Cracker Feed Using Centrifugal Partition Chromatography, Randy A. Menges, Daniel W. Armstrong, Larry A. Spino

Chemistry Faculty Research & Creative Works

Centrifugal partition chromatography (CPC) was used to fractionate a catalytic-cracking feedstock (i.e., catalytic cracker feed) into 16 separate fractions in the descending mode and 5 fractions in the inverse or ascending mode. Each fraction was analyzed by UV, fluorescence, and synchronous luminescence (SL) spectroscopy as well as by gas chromatography/mass spectrometry (GC/MS). It appeared that CPC can be used to fractionate larger samples of this type and with a greater degree of selectivity than previously reported preparative HPLC approaches. The SL spectra tended to be much more useful and information rich for these complex mixtures as compared to UV or …

Identification And Quantitation Of Volatile Amines In Chesapeake Bay Sediments, Neeraja Y. Krishna

Chemistry & Biochemistry Theses & Dissertations

Sediments from different parts of the Chesapeake Bay were analyzed to determine the presence of volatile amines. A HF-HCl extraction method was used to extract both exchangeable and fixed amines from the sediments and a purge-and-trap technique was used to concentrate the amines. Following derivatization with heptafluorobutyric anhydride (HFBA), the HFBA-amines were analyzed by gas chromatography with electron capture detection and with mass spectrometric detection. One primary amine, i-amylamine with a concentration ranging from 0. 78 nmoles/g dry weight to < 0.05 nmoles/g dry weight was found in a total of twenty seven samples collected on three different dates in 1993. Another primary amine, 2-methylbutylamine with a concentration ranging from 0.18 nmoles/g dry weight to < 0.05 nmoles/g dry weight was found in a total of twenty three samples collected on three different dates in 1993. A secondary amine, diethylamine was detected but could not be quantified in a total of seven samples collected in September 1993. The concentrations of these amines varied with location in the Bay, depth in the sediment, and time of year the sediments were collected. The origin of i-amylamine and 2-methylbutylamine might be from the biological decarboxylation of amino acids leucine and isoleucine, respectively. The origin of diethylamine is unknown.

Distance Dependence Of Nonadiabaticity In The Branching Between C–Br And C–Cl Bond Fission Following 1[N(O),Π∗(C=O)] Excitation In Bromopropionyl Chloride, P. W. Kash, G.C.G. Waschewsky, L. J. Butler, Michelle M. Francl

Chemistry Faculty Research and Scholarship

These experiments on bromopropionyl chloride investigate a system in which the barrier to C-Br fission on the lowest 1A'' potential energy surface is formed from a weakly avoided electronic configuration crossing, so that nonadiabatic recrossing of the barrier to C-Br fission dramatically reduces the branching to C-Br fission. The results, when compared with earlier branching ratio measurements on bromoacetyl chloride, show that the additional intervening CH2 spacer in bromopropionyl chloride reduces the splitting between the adiabatic potential energy surfaces at the barrier to C-Br fission, further suppressing C-Br fission by over an order of magnitude. The experiment measures the photofragment …

The 2′-Phosphate Of Nadp Is Critical For Optimum Productive Binding To 6-Phosphogluconate Dehydrogenase From Candida Utilis, Anthony J. Berdis, Paul F. Cook

Chemistry Faculty Publications

Initial velocity studies obtained with alternative dinucleotide substrates for the 6-phosphogluconate dehydrogenase reaction suggest that the 2′-phosphate is critical for the optimum productive binding of the dinucleotide substrate. Initial velocity patterns obtained by varying 6-phosphogluconate at different fixed levels of NAD are nearly parallel with apparent competitive substrate inhibition by 6-phosphogluconate at pH 7 and below but intersect to the left of the ordinate at pH 8 and above. Dead-end inhibition studies indicate that the mechanism is random at all pH values. Data are interpreted in terms of a random mechanism with marked antagonism in the binding of NAD and …

Vadose Zone Contamination Measurement And Modeling, Thomas A. Reeder

Theses and Dissertations

This thesis investigated the effects of the slow sorption mechanism on the transport of volatile organic contaminants in the vadose zone. Recent research has shown that slow sorption may have a significant impact on the transport of volatile organic compounds in the subsurface. Specifically, this document examined the effects of slow sorption on the Vapor Extraction System (VES) and the Purge and Trap Measurement System. It was found that the slow sorption of organic molecules on soil may profoundly influence the efficiency of VES and purge and trap. In addition, this thesis investigated possible alternatives to purge and trap, including …

Temporary Negative-Ion Resonances In The Nio(100) High-Resolution Electron-Energy-Loss Spectrum , K.W. Wulser, Marjorie Langell

Marjorie A. Langell Publications

The NiO(100) Fuchs-Kliewer phonon spectrum has been investigated by high-resolution electron-energy-loss spectroscopy (HREELS) at beam energies of 0.8–17 eV and the intensity distribution of the phonons relative to the dielectric properties of the NiO substrate has been considered. Over most of the range, the spectrum is well behaved, with the single-loss phonon energy at -70.5 meV and multiple excitations decreasing according to the predicted Poisson distribution. At 5.0-, 8.5-, and 13.5-eV primary beam energies, however, a substantial resonant enhancement in the phonon cross section is observed. The enhancement is accompanied by a shift from the Poisson intensity distribution to favor …

Sds Non-Acrylamide Polymeric Gel-Filled Capillary Electrophoresis For Molecular Size Separation Of Protein, Devon Andres

Honors Theses

Sodium dodecyl sulfide (SDS) non-acrylamide gel-filled capillary columns are a new technology being used for analysis and separation of biotechnology-derived proteins. This research was to compare this new technology to the current methods of SDS polyacrylamide gel electrophoresis (SDS-PAGE) and high-performance size-exclusion chromatography (HPSEC). The molecular mass of four different recombinant proteins were determined by two commercialized SDS non-acrylamide gel-filled capillary columns, SDS-PAGE, and HPSEC. The data obtained showed that the SDS non-acrylamide gel-filled capillary columns were compatible with the SDS-PAGE technique for molecular mass determination. HPSEC was shown to be unreliable for molecular weight determination. SDS non-acrylamide gel-filled capillary …

Olinioside, 5-(4′-O-Β-D-Glucopyranosyl)-Caffeoyloxy-5,6- Dihydro-4-Methyl-(2h)-Pyran-2-One From Olinia Usambarensis, Edward Nyandat, Emil Rwekika, Corrado Galeffi, Giovanna Palazzino, Marcello Nicoletti

All Peer-Reviewed Publications

From an extract of root bark of Olinia usambarensis, which showed antifeedant activity, 5-(4′-O-β-d- glucopyranosyl)-caffeoyloxy-5,6-dihydro-4-methyl-(2H)-pyran-2-one, named olinioside, caffeic acid, and 4-O-β-D- glueopyranosylcaffeic acid were isolated. The structure of orinioside was assigned by chemical and spectroscopic methods. © 1993.

Thermal Analysis Of Bismaleimide/Graphite Fiber Composite By Tg/Ftir, Qi Zhang

Masters Theses & Specialist Projects

The purpose of this project was to study the thermal and oxidative stability of a specific polymer composite. A TG/FTIR combined technique was employed to characterize this polymer/graphite fiber composite. The polymer composite sample was decomposed in nitrogen, air, and 3% oxygen atmospheres in a Seiko thermogravimetric analyzer. The use of a gas cell Fourier-transform IR spectrometer downstream from the TGA allowed for the identification of evolved gas products.

The thermal oxidative stability (TOS) of this composite was compared to its thermal stability. Also, comparison of the TOS in different atmospheres was made. In addition, the effects of specimen geometry …

Observation Of Non-Isotropic Auger Angular Distribution In The C(1s) Shape Resonance Of Co, Oliver Hemmers, Franz Heiser, J. Eiben, R. Wehlitz, U. Becker

Environmental Studies Faculty Publications

Angle-resolved high-resolution C(KVV) Auger spectra of CO were taken in the vicinity of the C(1s) σ^* shape resonance. These spectra show clear evidence for the theoretically predicted anisotropic K-shell Auger emission in molecules. Complementary results from angle-resolved photoion spectroscopy show that the small size of the observed effect is, besides the varying intrinsic anisotropy of the Auger decay, also due to a smaller anisotropy in the primary absorption process than originally predicted but in good agreement with more recent calculations. Contrary to this, satellite Auger transitions show unexpectedly large anisotropies.

Radially Symmetrical Flow Of Reacting Liquid With Changing Viscosity, S.E. Solovyov, V.A. Volpert, S.P. Davytan

Faculty Publications

Frontal regimens for one-dimensional flow of reacting liquid with changing viscosity are studied. Stationary solutions are investigated for the case of narrow reaction zones that shrink to a front. The results of numerical solution of the nonstationary problem are presented. Complex oscillations resulting from period-doubling bifurcations are found.

Symmetrically H-Bridged Dimer Of 2-Carboxylatobenzenediazonium. The 1:1 Complex Between 2-Carboxybenzenediazonium Chloride And Benzenediazonium-2-Carboxylate, Christopher J. Horan, Paul E. Haney, Charles Leslie Barnes, Rainer Glaser

Chemistry Faculty Research & Creative Works

The two zwitterions in the H-bridged dimer of 2-carboxylatobenzenediazonim (1) are linked by a crystallographically symmetric O⋯Hctdot;O hydrogen bond with an O⋯O distance of 2.436 (3) Å. Comparison of the (1) with the other benzenediazonium salts shows that the phenyl ring distortions in (1) are determined primarily by the diazonium substituent with only modest additional effects by the carboxylato group. Intramolecular neighboring goup interactions between the N₂ group and the orthoCOO(H) group are indicated and are discussed. The terminal N atom of the diazonium group is bent away from the neighboring carboxylato group. The N₂ and the …

Orientational Phase Transition In Na_{X}C_{60} (1, T. Yildirim, J. E. Fischer, A. B. Harris, Peter W. Stephens, Dengfa Liu, Laurent Brard, Robert M. Strongin, Amos B. Smith Iii

Chemistry Faculty Publications and Presentations

X-ray diffraction and calorimetry data on cubic Na_xC₆₀(1<x60, e.g., T_m(x=1.3)=325 K. The ordered phases are the same as in pure C₆₀: simple cubic, space group Pa3¯, but the orientations in the disordered phase are more restricted. We explain how Na stabilizes the ordered phase to rather high T, while K and Rb do not, in terms of Coulomb interactions between C₆₀ molecules and and Na ions which we calculate from the local charge density of C₆₀.

35th Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Program, abstracts, and information about the 35th annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-sponsored by the Colorado Section of the American Chemical Society and the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, July 25-29, 1993.

Microemulsion Characterization By The Use Of A Noninvasive Backscatter Fiber Optic Probe, Rafat R. Ansari, Harbans S. Dhadwal, Michael Cheung, William V. Meyer

Chemical, Biomolecular, and Corrosion Engineering Faculty Research

This paper demonstrates the utility of a noninvasive backscatter fiber optic probe for dynamic light-scattering characterization of a microemulsion comprising sodium dodecyl sulfate/1-butanol/brine/heptane. The fiber probe, comprising two optical fibers precisely positioned in a stainless steel body, is a miniaturized and efficient self-beating dynamic light-scattering system. Accuracy of particle size estimation is better than +/- 2%.

Characterization Of Combustion Profiles Of Co-Fired Coal/Biomass/Limestone Samples By Tg And Tg/Ftir, Erik Jon Hutchinson

Masters Theses & Specialist Projects

Recent concerns over declining landfill space and a renewed interest in waste-to-energy technologies have increased the possibilities of co-firing different types of fuels in fluidized bed combustion systems. Fluidized bed combustion systems are idea for co-firing because of their ease in heat conversion and ability to burn a wide range of fuels. Additionally, thermal analytical techniques can be used to screen fuel blends for the fluidized bed combustion systems at a lower cost than directly firing the fuel blends in pilot systems. Three coals, three different municipal solid wastes (MSW), one limestone were combined into nine series of binary fuel …

Electronegativity And Bond Type 2. Evaluation Of Electronegativity Scales, Gordon Sproul

Natural Sciences Faculty Publications

No abstract provided.

A Neutron Diffraction And Mössbauer Effect Study Of The Magnetic Properties Of Pr₂Fe₁₇ And Pr₂Fe₁₇N₂.₆, Gary J. Long, Oran Allan Pringle, Fernande Grandjean, William B. Yelon, K. H. Buschow

Chemistry Faculty Research & Creative Works

The neutron diffraction powder patterns of Pr₂Fe₁₇ and Pr₂Fe₁₇N_2.6 have been measured at 295 K and refined within the Th₂Zn₁₇ structure type to give the structural changes which occur upon nitrogenation; changes which include a 6.4% expansion of the unit cell volume. The Mössbauer spectra of Pr ₂Fe₁₇ and Pr₂Fe₁₇N_2.6 have been measured between 85 and 295 K and analyzed with a model which is based on the Wigner-Seitz cell environment of each iron site, the basal orientation of the magnetization, and …

A Study Of The Chlorination Products Of Methionine In Model Solutions And In Wastewater, D. Scott Winters

Chemistry & Biochemistry Theses & Dissertations

Model solutions of the amino acid methionine were chlorinated to seven chlorine-to-nitrogen (Cl₂/N) molar ratios. After 30 minutes, the solutions were analyzed by high performance liquid chromatography (HPLC). At a Cl₂/N molar ratio of 1, methionine sulfoxide was found to be the main product. At Cl₂/N molar ratios ≥ 2, a mixture of methionine sulfoxide, methionine sulfone, an unidentified sulfoxide (product 1), and N-chloro-3-(methylsulfonyl) propionaldimine are formed. These products were identified by comparison to synthesized standards which were characterized by ¹H-NMR and ¹³C-NMR nuclear magnetic resonance spectroscopy, ion trap mass spectroscopy, …

The Isolation And Identification Of Polyphenolics From Grape Seeds And Their Activity Towards Specific Cell Lines, Joseph A. Reddy

Chemistry & Biochemistry Theses & Dissertations

Grape seed extract is being marketed in France for cardiovascular use and skin care. The active constituents of both these drugs are certain polyphenols called procyanidins. A similar seed extract has now been obtained from Virginia Chardonnay grape seeds. Ten of the major components in this extract have been isolated in their pure form by the semi-preparative HPLC separation on a YMC ODS-AQ (Octadecylsilane-AQ) column. The ODS-Aq column has been shown to have a better resolving capacity compared to the Spherisorb ODS (Octadecylsilane) column previously described in the literature. This has been attributed to the ODSAQ support which has both …

Formation Of O-Tyrosine And Dityrosine In Proteins During Radiolytic And Metal-Catalyzed Oxidation, Thomas G. Huggins, Mary C. Wells-Knecht, Nicholas A. Detorie, John W. Baynes, Suzanna R. Thorpe

Faculty Publications

To evaluate their usefulness as chemical indicators of cumulative oxidative damage to proteins, we studied the kinetics and extent of formation of ortho-tyrosine (0-Tyr), dityrosine (DT), and dityrosine-like fluorescence (Ex = 3 17 nm, E,,, = 407 nm) in the model proteins RNase and lysozyme exposed to radiolytic and metalcatalyzed (H20z/Cu2+) oxidation (MCO). Although there were protein-dependent differences, o-Tyr, DT, and fluorescence increased coordinately during oxidation of the proteins in both oxidation systems. The contribution of DT to total dityrosine-like fluorescence in oxidized proteins varied from 2-10070, depending on the protein, type of oxidation, and extent of oxidative damage. In …

Oxidized Amino Acids In Lens Protein With Age: Measurement Of O-Tyrosine And Dityrosine In The Aging Human Lens, Mary C. Wells-Knect, Thomas G. Huggins, Daniel G. Dyer, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

The concentrations of ortho-tyrosine (o-Tyr) and dityrosine (DT) were measured in noncataractous human lenses in order to assess the role of proteinoxidation reactions in the aging of lens proteins. The measurements were conducted by selected ion monitoring-gas chromatography/mass spectrometry using deuterium-labeled internal standards, which provided both high sensitivity and specificity for the quantitation of o-Tyr and DT. Between ages 1 and 78 years, the o-Tyr concentration in lens proteins varied from 0.3 to 0.9 mmol of o-Tyr/mol of Phe (n = 19), while DT ranged from 1 to 3 mumol of DT/mol of Tyr (n = 30). There were no …

The Cytotoxic Effect Of Tropical Plants On Human And Rat Hepatoma Cells, Mark Tafazoli

Honors Capstone Projects and Theses

No abstract provided.

Synthesis Of N-Boc-3-Azabicyclo[3.3.0]Octan-7-One Via Reductive Pauson-Khand Cyclization And Subsequent Conversion To A Novel Diazatricyclic Ring System, Daniel Becker, Daniel L. Flynn

Chemistry: Faculty Publications and Other Works

An intramolecular reductive Pauson-Khand reaction of the hexacarbonyldicobalt complex of N-(tert-butyloxycarbonyl)allylpropargylamine under dry-state adsorption conditions directly afforded the saturated N-BOC-3-azabicyclo[3.3.0]octan-7-one when the reaction was performed under an inert atmosphere. This bicyclic ketone was converted in several steps to the novel octahydro-1-azeto[2′,3′:3,4]cyclopenta[1,2-C]pyrrole ring system as confirmed by single crystal X-ray analysis.