Physical Sciences and Mathematics Commons^™

Low-Temperature Crosslinking Of Polycyclopentadiene, Lawrence Peters

Theses

Cyclopentadiene was polymerized via a Diels-Alder mechanism at 174°C under an inert atmosphere. The polymer obtained after ll hrs of reaction had a low bulk viscosity of 8 cps and a viscosity-average molecular weight, Mv, of up to 3000. An unsaturated polyester was synthesized from maleic anhydride and ethylene glycol in the presence of chlorosulfonic acid at room temperature. The polyester had an intrinsic viscosity of 0.024 cps. At 60°C, polycyclopentadiene (PCPD), and the unsaturated polyester were reacted to yield a viscous liquid which was crosslinked at room temperature over 48 hours in the presence of styrene, triethyleneglycol dimethacrylate (TEGDMA), …

Surface Tension Of A Charged And Polarized System, Jerry Goodisman

Chemistry - All Scholarship

Usually, the formula for the surface tension of a planar charged and polarized interface is obtained from that for a system involving only short-range forces, y = - dz [p - px(z)] by replacing the tangential pressure p , by p , + E2/8u. Problems with this include (a) p, is no longer explicitly defined, (b) the electrostatic stress term E2/8 pi is not correct in general but only if polarization is proportional to density of polarizable species, (c) the derivation of the formula in terms of p and p, involves calculating the work to expand a volume containing the …

Liquid Phase Electrochemistry At Ultralow Temperatures, Royce W. Murray, Stanton Ching, John T. Mcdevitt, Stephen R. Peck

Chemistry Faculty Publications

Fluid electrolyte solutions based on mixtures of butyronitrile (PrCN) and ethyl chloride (EtCl) with or as electrolyte freeze below −180°C and provide excellent media for cryogenic electrochemical experiments. A 1:2 mixture of PrCN and EtCl exhibits the best combination of freezing point and ionic conductivity for ultralow temperature electrochemistry. Diffusion coefficients for bis(pentamethylcyclopentadienyl) iron are measurable by potential step chronoamperometry down to −160°C using a conventionally sized electrode, but the resistivity of the solvent mixture is such that potential sweep voltammetry benefits from the use of microdisk (10 and 25 μm diam Pt) or microband (0.2 μm wide Au) electrodes. …

Stabilization Of Β Positive Charge By Silicon, Germanium, Or Tin, Kiet A. Nguyen, Mark S. Gordon, Gen-Tai Wang, Joseph B. Lambert

Mark S. Gordon

Ab initio molecular orbital theory is used to study the β effect of carbon, silicon, germanium, or tin on the carbenium ions in H2R'MCH2CHR+ (R' = H; R = H, CH3). The relative stabilization energies of carbenium ions provided by M (M = C, Si, Ge, Sn) were determined by calculating the energy change in an isodesmic reaction using MP2/3-21G(d) (at SCF /3-21G* geometries) and MP2/6-31G(d) (at SCF /6- 31G(d) geometries) wave functions. The magnitude of the β effect is predicted to increase in the order C < Si < Ge < Sn. For R = H, the nonvertical cyclic structure is favored for the cations, whereas methyl substitution appears to stabilize the vertical acyclic arrangement.

Ab Initio Study Of Some Methylene And Silylene Insertion Reactions, David R. Gano, Mark S. Gordon, Jerry A. Boatz

Mark S. Gordon

The theoretical barriers and reaction energetics have been determined, using ab initio calculations at the MP4/6-3IG(d) level, with 3-2IG* geometries, for the insertions of methylene and silylene into the X-Y bonds of ethane, methylsilane, disilane, and cyclopropane and into the X-H bonds of disilane and ethane. A correlation was observed between barrier heights and lengths of substrate bonds. The largest barriers were observed for methylene and silylene inserting into the C-C bonds of ethane. The barriers became successively lower for the C-Si and Si-Si bonds. Steric interactions thus appear to be a major factor in determining barrier heights. The observed …

Nature Of The Si-N Bond In Silatranes, Mark S. Gordon, Marshall T. Carroll, Jan H. Jensen, Larry P. Davis, Larry W. Burggraf, R. Martin Guidry

Mark S. Gordon

Both ab initio and semiempirical calculations are used to investigate the structure and bonding in substituted silatranes. In agreement with gas-phase experiments, which fmd Si-N distances that are 0.25-0.35 A longer than those in the crystal phase, the Si-N distance (for example, in methylsilatrane) is predicted to be much larger than that observed in the crystal. Nonetheless, a bond critical point is found between Si and N, suggesting the existence of an Si-N bond in these compounds. It is found that the energy cost for constraining the Si-N distance in hydroxysilatrane to a value similar to that observed in the …

Expression Of Biologically Active Human Corticosteroid Binding Globulin By Insect Cells: Acquisition Of Function Requires Glycosylation And Transport, Jayasri Ghose-Dastidar, J. B. Alexander Ross, Reza Green

Chemistry and Biochemistry Faculty Publications

Human corticosteroid binding globulin (hCBG) is a 50- to 55-kDa serum glycoprotein that binds cortisol and progesterone with high affinity. To map the steroid-binding domain and to investigate the folding pathways of hCBG, we have established an expression system based on infection of insect cells with a recombinant baculovirus encoding hCBG. Infected Spodoptera frugiperda (Sf9) cells secrete immunoreactive hCBG at high levels (16-24 pmol per 10⁶ cells per 40 h), and the recombinant protein binds cortisol with an affinity and specificity equivalent to that of human serum-derived hCBG. Thus, this system has the potential to provide large amounts of …

On-Road Remote Sensing Of Co Emissions In The Los Angeles Basin, Donald H. Stedman, Gary A. Bishop, James E. Peterson, Paul L. Guenther

Fuel Efficiency Automobile Test Publications

The University of Denver remote sensor for on-road motor vehicle carbon monoxide emissions was used for eleven days in the Los Angeles Basin in December, 1989. The remote sensor has been incorporated into the 1990 Clean Air Act Amendments as "on-road emissions testing". The device measures the CO/CO₂ ratio for one-half second behind each vehicle, from which the exhaust %CO is calculated. Vehicles were measured in a mix of many driving modes and speeds ranging from deceleration coming up to a red traffic light through idling in heavy congestion up to accelerations and cruises entering a freeway ramp at …

Micellar Catalysis Of Hydrolysis Of Substituted Hydroxamic Acids With Perfluorooctanoic Acid, Zhongyuan He

Masters Theses

The work demonstrated the effects of differently located and substituted phenyl groups, as well as aliphatic groups in the hydroxamic acids, on micellar catalysis with perfluorooctanoic acid as the reactive counterion surfactant in aqueous acetonitrile solution.

Kinetic rate constant-surfactant concentration profiles for the decano-, 2,5-dimethylphenylaceto-, 4-isopropylphenylaceto-, 4-phenylbutano-, and 6-phenyl-hexanohydroxamic acids were examined and analysis on the data obtained were reported.

The pseudo-phase ion exchange (PPIE) model has been satisfactorily applied to explain the observed micellar effects.

Further investigation into more appropriately substituted hydroxamic acids is suggested in order to obtain a more complete set of data and further evaluation.

Anisotropy Of Polarized X-Ray Emission From Molecules, S. H. Southworth, Dennis W. Lindle, R. Mayer, P. L. Cowan

Chemistry and Biochemistry Faculty Research

Strongly anisotropic, polarized Cl K-V x-ray emission from gas-phase CF₃Cl has been observed following resonant excitation with a linearly polarized x-ray beam. Distinctively different angular distributions are observed for x-ray emission involving molecular orbitals of different symmetries. A classical model of the x-ray absorption-emission process accurately describes the observed radiation patterns.

Measurement Of The Ratio Of Double-To-Single Photoionization Of Helium At 2.8 Kev Using Synchrotron Radiation, Jon C. Levin, Dennis W. Lindle, N. Keller, R. D. Miller, Y. Azuma, N. Berrah Mansour, H. G. Berry, Ivan A. Sellin

Chemistry and Biochemistry Faculty Research

We report the first measurement of the ratio of double-to-single photoionization of helium well above the double-ionization threshold. Using a time-of-flight technique, we find He⁺⁺/He⁺=1.6±0.3% at hν=2.8 keV. This value lies between calculations by Amusia (2.3%) and by Samson, who predicts 1.2% by analogy with electron-impact ionization cross sections of singly charged ions. Good agreement is obtained with older shake calculations of Byron and Joachain, and of Åberg, who predict 1.7%.

Biodepuration Of Polynuclear Aromatic Hydrocarbons From A Bivalve Mollusk, Mercenaria Mercenaria L, John T. Tanacredi Ph.D., Raul R. Cardenas

Faculty Works: CERCOM (1977-2016)

Mercenaria mercenaria, exposed in vitro for 48 h to nine parent polynuclear aromatic hydrocarbons (PAHs) found in waste crankcase oil (WCCO) and analysed by multiparametric analysis over a 45- day depuration period in an activated carbon filtration aquaria system, did not depurate PAHs, but rather maintained them at detectable levels. Uptake of PAHs was shown to be directly related to clam weight. A cluster analysis of empirical results reaffirmed a biostabilization in PAH groupings in clam tissue over a 45-day depuration period and exhibited no evidence of a decreasing trend in total PAHs when subjected to ANOVA. Due to the …

Chelation Of 2-Substituted 1-Lithoxides: Structural And Energetic Factors Of Relevance To Synthetic Organic Chemistry., Michael Nichols, Andrew Mcphail, Edward Arnett

Michael A Nichols

No abstract provided.

33rd Rocky Mountain Conference On Applied Spectroscopy

Rocky Mountain Conference on Magnetic Resonance

Program and registration information for the 33rd annual meeting of the Rocky Mountain Conference on Applied Spectroscopy, sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, July 28 - August 1, 1991.

Characterization Of Adsorption By Electrochemical And Spectroscopic Methods, Mark Anderson

Mark R. Anderson

No abstract is available at this time.

Systematic Survey Of Cyclic Silicon-Oxygen Compounds, Michael W. Schmidt, Kiet A. Nguyen, Mark S. Gordon, John A. Montgomery Jr.

Mark S. Gordon

Compounds with 0, 1, 2, or 3 oxygen atoms bridging 2 silicon atoms are investigated by ab initio calculations. Two such series of compounds, with and without a formal central Si-Si bond, are considered. The triplet states of the former set are also examined. For some of these compounds, the present calculations represent the first time they have been examined at a sufficiently rigorous level of theory. For the compounds that are formally bonded, this level is two configuration SCF (TCSCF) for singlets and ROHF for triplet states, using split valence polarized basis sets. The main result is that no …

A Theoretical Study Of Some Reactions Of Hcsi-, Michael W. Schmidt, Mark S. Gordon

Mark S. Gordon

The ions HCSi- and H2CSiH- produced in recent flowing afterglow experiments are characterized structurally. Reactivity of the former ion with four molecules (C02, OCS, CS2, S02) is examined. Three of these species react in a sequence of intermediates of cyclic followed by acyclic structures, before reaching the final products.

Principal Resonance Contributors To High-Valent, Transition-Metal Alkylidene Complexes, Thomas R. Cundiari, Mark S. Gordon

Mark S. Gordon

The results of ab initio calculations are reported for prototypical high-valent, alkylidene complexes. Stationary points on each potential energy surface are characterized and compared to experimental information where available; as long as a suitably flexible valence basis set is used, good agreement between theoretically calculated and experimentally determined geometries is obtained. The complexes of interest include group IVB (Ti, Zr and Hf) and group VB (Nb and Ta) alkylidenes with hydride ligands as well as models for the four-coordinate, olefin metathesis catalysts (Mo-, W-, and Re-alkylidenes) which have been recently synthesized and characterized. In light of the fact that much …

Stable N-Chloraldimines And Other Chlorination Products Of Phenylalanine In Model Solutions And In A Wastewater, Barbara L. Conyers

Chemistry & Biochemistry Theses & Dissertations

Model solutions of the amino acid phenylalanine were chlorinated to seven Cl/N mole ratios. The by-products were characterized using gas chromatography, high performance liquid chromatography, GC/MS, infrared spectroscopy, and nuclear magnetic resonance spectroscopy. At the lower Cl/N ratios N-chlorophenylalanine and phenylacetaldehyde were identified as the main products while phenylacetonitrile and N-chlorophenylacetaldimine were the major products at Cl/N ratios of 2.0 and beyond. The concentration of phenylalanine in a municipal wastewater was determined. Using a radiotracer the chlorination products of phenylalanine in the wastewater at the 7 Cl/N ratios were identified as those seen in the model solutions. The distribution of …

A Diffuse Reflectance Infrared Fourier Transform Spectroscopic Study Of Platinum/Tin (Iv) Oxide Low-Temperature Carbon Monoxide Oxidation Catalysts, Donna Sue Duarte

Chemistry & Biochemistry Theses & Dissertations

Platinum-coated tin(IV) oxide catalysts have been developed for the recombination of carbon monoxide and oxygen at 55°C and 1 atmosphere of pressure in closed-cycle carbon dioxide lasers. A diffuse reflectance infrared fourier transform spectroscopic (DRIFTS) study of four of these catalysts during 5% carbon monoxide pretreatment at temperatures of 30°C, 100°c, 125°c, and 150°C has been performed. Evidence for the development of surface carbonate, bicarbonate, and formate species during pretreatment has been found. Dehydroxylation of the surface and loss of a partially charged hydrogen-bonded hydroxyl species have also been found to result from elevated temperature pretreatment. The four catalysts have …

Ua3/8/1 John Robinson Professorship Report, Wku Ogden College Of Science & Technology

WKU Administration Documents

Report by Dr. John Riley, John Robinson Professor of activities for 1990-1991 funded by Ogden Foundation.

Formation Of Pentosidine During Nonenzymatic Browning Of Proteins By Glucose, Daniel G. Dyer, James A. Blackledge, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

A fluorescent compound has been detected in proteins browned during Maillard reactions with glucose in vitro and shown to be identical to pentosidine, a pentose- derived fluorescent cross-link formed between arginine and lysine residues in collagen (Sell, D. R., and Monnier, V. M. (1989) J. Biol. Chem. 264, 21597- 2 1602). Pentosidine was the major fluorophore formed during nonenzymatic browning of ribonuclease and lysozyme by glucose, but accounted for <1% of nondisulfide cross-links in protein dimers formed during the reaction. Pentosidine was formed in greatest yields in reactions of pentoses with lysine and arginine in model systems but was also formed from glucose, fructose, ascorbate, Amadori compounds, 3-deoxyglucosone, and other sugars. Pentosidine was not formed from peroxidized polyunsaturated fatty acids or malondialdehyde. Its formation from carbohydrates was inhibited under nitrogen or anaerobic conditions and by aminoguanidine, an inhibitor of advanced glycation and browning reactions. Pentosidine was detected in human lens proteins, where its concentration increased gradually with age, but it did not exceed trace concentrations (55 Fmol/mol lysine), even in the 80-year-old lens. Although its precise carbohydrate source in vivo is uncertain and it is present in only trace concentrations in tissue proteins, pentosidine appears to be a useful biomarker for assessing cumulative damage to proteins by nonenzymatic browning reactions with carbohydrates.

The Influence Of Cation Size Upon The Infrared Spectrum Of Carbon Monoxide Adsorbed On Platinum Electrodes, Mark Anderson, Jimin Huang

Mark R. Anderson

No abstract is currently available.

Multifragment Disintegrations Of The 36ar + 197au Systems At E/A=35-110 Mev , Y. D. Kim, R. T. De Souza, L. Phair, D. R. Bowman, N. Carlin, C. K. Gelbke, W. G. Gong, M. A. Lisa, W. G. Lynch, Graham F. Peaslee, M. B. Tsang, C. Williams, F. Zhu, W. A. Friedman, S. Pratt

Faculty Publications

Intermediate mass fragment (IMF: 3≤Z≤20) emission for the 36Ar+197 Au reaction at E/A=35, 50, 80, 110 MeV has been studied with a low‐threshold 4π charged‐particle detector array. Multiplicities of intermediate mass fragments gated on total charged‐particle multiplicities have been extracted with an average multiplicity of 4 intermediate mass fragments for the most central collisions at E/A=110 MeV. Two‐fragment correlation functions are presented for various gates on the fragment energy, and information about the time‐scale of fragment emission is extracted.

Nonlinear Optical Properties Of Bacteriorhodopsin: Assignment Of The Third-Order Polarizability Based On Two-Photon Absorption Spectroscopy, Robert R. Birge, Mark Masthay, Jeffery A. Stuart, Jack R. Tallent, Chian-Fan Zhang

Chemistry Faculty Publications

The third-order (pi) -electron polarizability, (gamma) (pi), of bacteriorhodopsin in the 0.0 - 1.2 eV optical region is assigned based on an analysis of the experimental two-photon properties of the low-lying singlet state manifold. The following selected values of (gamma) (pi) (units of 10-36 esu) are observed: (gamma) (0;0,0,0) equals 2482 +/- 327; (gamma) (-3(omega) ;(omega) ,(omega) ,(omega) ) equals 2976 +/- 385 ((omega) equals 0.25 eV), 5867 +/- 704 ((omega) = 0.5 eV), 14863 +/- 1614 ((omega) = 0.66 eV), 15817 +/- 2314 ((omega) equals 1.0 eV), 10755 +/- 1733 ((omega) equals 1.17 eV). The third-order polarizability of this …

Stability Of E. Coli Atcase And Its Catalytic Subunit Measured By Intrinsic Protein Fluorescence, Ira A. Gurland

Honors Theses

Intrinsic protein fluorescence has been used to monitor the guanidine HCI induced denaturation of E. coli aspartate transcarbamylase (ATCase) and its isolated catalytic subunit (CSU). ATCase is a large oligomeric protein which contains both regulatory subunits and catalytic subunits. Both tryptophans in ATCase are located in a single globular domain of the catalytic subunit. For both ATCase and CSU, increasing concentralions of guanidine HCI caused a red shift of the maximum protein emission (Aex 295 nm) of 15.0 +/- 0.5 nm. CSU showed a concommitant decrease in fluorescence intensity while ATCase showed an increase from 0.0 to 2.0 M and …

The Construction Of An Apparatus To Do Fast Transient Ir Spectroscopy, Eugene Jerome Bernard

Honors Theses

Photocatalytic reactions of metal carbonyl complexes with organic substrates have been studied extensively over the past decade. The reaction mechanisms proposed for most reactions studied have come from varying the concentrations and conditions on the reactants and examining the effects on the prc,ducts. The intermediate steps of the reaction mechanism are inferred from these kinds of experiments, but most intermediates are too short lived to be seen directly with conventional IR spectroscopy. This thesis describes the construction of an apparatus that uses fast transient IR spectroscopy to study the reaction intermediates that are too short lived to be detected by …

Reactivities Of Some Aromatic Compounds At Supercritical Water Conditions, Chun-Cheng Tsao

Masters Theses

The goals of this study are the removal of nitrogen from the extraction products of coal by Supercritical Water and the development of an understanding of the reactions leading to this removal. Six model compounds with structures similar to the intermediates of the coal liquefaction processes were studied. Benzylamine generated toluene through hydrogen abstraction after the C-N bond rupture. To a lesser extent, the oxidation of the benzylic carbon took place leading to benzene formation. Both reaction pathways occurred with equal probability for benzylidenebenzylamine, producing comparable yields of benzene and toluene. Benzaldehyde generated benzene through the oxidation/decarboxylation sequence. Benzyl alcohol …

A Complete Ridge-Line Potential For Complex Fragment Emission, D. N. Delis, Y. Blumenfeld, D. R. Bowman, N. Colonna, K. Hanold, K. Jing, M. Justice, J. C. Meng, Graham F. Peaslee, G. J. Wozniak, L. G. Moretto

Faculty Publications

Cross sections were measured for fragments (4

Decrease In Skin Collagen Glycation With Improved Glycemic Control In Patients With Insulin-Dependent Diabetes Mellitus, Timothy J. Lyons, Karen E. Bailie, Daniel G. Dyer, John A. Dunn, John W. Baynes

Faculty Publications

Glycation, oxidation, and nonenzymatic browning of protein have all been implicated in the development of diabetic complications. The initial product of glycation of protein, fructoselysine (FL), undergoes further reactions, yielding a complex mixture of browning products, including the fluorescent lysine-arginine cross-link, pentosidine. Alternatively, FL may be cleaved oxidatively to form N(epsilon)-(carboxymethyl)lysine (CML), while glycated hydroxylysine, an amino-acid unique to collagen, may yield N(epsilon)-(carboxymethyl)hydroxylysine (CMhL). We have measured FL, pentosidine, fluorescence (excitation = 328 nm, emission = 378 nm), CML, and CMhL in insoluble skin collagen from 14 insulin-dependent diabetic patients before and after a 4-mo period of intensive therapy to …