Digital Commons Network^™

An Improved Synthesis Of 2-(Hydroxymethyl)Indene, Hasan Palandoken, William T. Mcmillen, Michael H. Nantz

Chemistry and Biochemistry

No abstract provided.

An Nmr Investigation Of The Effect Of Hydrogen Bonding On The Rates Of Rotation About The C-N Bonds In Urea And Thiourea, Karl A. Haushalter, Janice Lau, John D. Roberts

All HMC Faculty Publications and Research

The interaction between urea and tetrabutylammonium acetate was investigated in dimethylformamide/ dimethyl sulfoxide solutions using ¹H and 15^N NMR. The chemical-shift behavior of the urea protons is consistent with a urea-acetate hydrogen-bonded complex involving both carboxylate oxygens and the urea hydrogens trans to the carbonyl oxygen with K_assoc = 120 ± 10. Line shape analysis of the temperature-dependent ¹H NMR spectra show that ∆G^‡ for rotation about the C-N bond of urea changes only slightly from 11.0 ± 0.1 to 11.2 ± 0.1 kcal/mol on 1:1 molar addition of tetrabutylammonium acetate to a dilute solution of urea. A parallel investigation …

Highly Reactive Form Of Copper And Reagents Thereof, Reuben D. Rieke

Department of Chemistry: Faculty Publications

A novel Zerovalent copper species and an organocopper reagent are disclosed. The Zerovalent copper species is directly produced by reaction of a reducing agent with a combination of copper(I) cyanide or halide and an alkali metal halide salt. The organocopper reagent resulting from the reaction of the zerovalent copper species and an organic compound having one or more stable anionic leaving groups is a stable reagent that will not significantly homocouple and under controlled conditions tolerates the presence of nitrile, epoxide, imine, enone, ketone, ester, allyl and benzyl groups within the organo radical. The reagent can be controlled so that …

Characterization Of Ground And Excited Electronic State Deprotonation Energies Of Systems Containing Double Bonds Using Natural Bond Orbital Analysis, J. K. Badenhoop, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Natural bond orbital analysis is applied to the ground and excited states of a set of neutral, cationic, and anionic doubly bonded species H_nC=XH_n (X=C, N, O) isoelectronic with ethylene. The character of the excitation is correlated with calculated charge shifts and geometry changes upon relaxation. For these planar molecules, depopulation of the π bond or population of the π∗ antibond causes an out‐of‐plane twist or pyramidalization upon relaxation correlated to the amount of charge shift. These nonplanar distortions generally lower the energy more than changes in bond lengths and angles. Population of a σ_XH^{∗ …}

Artificial Maturation Of Alginite And Organic Groundmass Separated From Torbanites, Michael A. Kruge, Patrick Landais, David F. Bensley

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The two principal organic constituents — Botryococcus-related alginite and organic groundmass — were isolated by density separation from two torbanite samples (from the Stellarton Fm., Nova Scotia, Canada and the King Cannel, Utah, USA). The groundmass consisted of degraded algal, bacterial and terrestrial plant debris. Aliquots of alginite and groundmass were separately heated in gold tubes for 24 hr. with 70 MPa confining pressure, at fixed temperatures ranging between 250 and 375°C. The 250, 300 and 325°C experiments run on the alginite produced very low yields of CHCl3-extractable organic matter (EOM), indicating that very little of the generation potential …

Preparation Of Trifluoromethyl Lactol Derivatives Via Base Initiated Cyclobutanol Ring Opening To A Laterally Lithiated Trifluoromethyl Ketone, Daniel Becker, Daniel L. Flynn

Chemistry: Faculty Publications and Other Works

Benzocyclobutenone derivatives 4 are converted to the corresponding trifluoromethylcyclobutanols 5 by treatment with trifluoromethyltrimethylsilane in the presence of tetra-n-butylammonium fluoride. These trifluoromethylcyclobutanol derivatives are then treated with LiTMP in the presence of aromatic aldehydes to afford trifluoromethyllactols 6 via a laterally-lithiated trifluoromethylketone intermediate.

A New High Pressure Sapphire Nuclear Magnetic Resonance Cell, Shi Bai, Craig M. Taylor, Charles L. Mayne, Ronald J. Pugmire, David M. Grant

Faculty Publications

A new version of a single-crystal sapphire high pressure nuclear magnetic resonance (NMR) cell is described that is capable of controlling the sample pressure independent of the temperature. A movable piston inside the cell adjusts and controls the sample pressure from ambient conditions to 200 atm within plus or minus 0.3 atm. The linewidth at half-height for a 13C spectrum of carbon dioxide at 15degrees C and 57.8 atm is found to be 0.5 Hz. The carbon dioxide gas/liquid phase transition is clearly observed by measuring 13C chemical shifts as the sample pressure approaches equilibrium. The time required for this …

Biodegradation Of Nonionic Surfactants And Effects Of Oxidative Pretreatment, Craig D. Adams, S. Spitzer, R. M. Cowan

Civil, Architectural and Environmental Engineering Faculty Research & Creative Works

The aerobic biodegradability of nonionic, ethoxylated surfactants and model compounds, and the effect of advanced oxidation pretreatment on the biodegradability of the biorefractory surfactants were examined. Bioassays conducted using a mixed microbial seed showed that the linear primary alcohol ethoxylates, the fatty acid ethoxylates, and also polyethylene glycol were all degradable. The biomineralization of the linear secondary alcohol ethoxylate, ethylene oxide/propylene oxide block copolymer, and alkylphenol ethoxylate was observed to be inhibited to varying degrees. Additional bioassays were conducted on model compounds to examine the effect of specific structural components on biodegradability. Advanced oxidation pretreatment using hydrogen peroxide in combination …

Remote Marine Aerosol In The Gulf Of Maine: An Sem Study, Eric S. Gordon

Honors Theses

Eight aerosol samples were collected from a height of 34 meters atop Petit Manan Light located 16 miles East of Bar Harbor, Maine between July 25, 1995 and August 1, 1995. Both coarse and fine fractions were collected on 8.0 and 0.2 micron polycarbonate membrane filters, respectively. The sampling station consisted of a sampling box as well as a weather station (with various instruments) to record weather data for help in the analysis. The samples were analyzed using a scanning electron microscope and energy dispersive x-ray spectroscopy. Cluster analysis was perforned on the particles, grouping particles together with similar chemical …

Treatability Of S-Triazine Herbicide Metabolites Using Powdered Activated Carbon, Craig D. Adams, Tammy L. Watson

Civil, Architectural and Environmental Engineering Faculty Research & Creative Works

Widespread use of s-triazine herbicides such as atrazine, simazine, and cyanazine has led to the contamination of many ground-water and surface-water supplies with the parent compounds as well as by primary metabolites (e.g., deethylatrazine, deisopropylatrazine, and deethylcyanazine). Ozonation has been shown to produce many of the same byproducts. Activated carbon adsorption has been designated by the U.S. Environmental Protection Agency as the best available technology (BAT) for the treatment of herbicides in drinking water. Little data is available, however, on the applicability of activated carbon treatment for the control of the primary degradation products of herbicides. In this study, the …

Mile-A-Minute Weed, (Polygonum Perfoliatum L.), An Invasive Vine In Natural And Disturbed Sites, J. Douglas Oliver

Faculty Publications and Presentations

Polygonum perfoliatum L. (Polygonaceae) or mile-a-minute weed, from eastern Asia, has been spreading through wild and disturbed areas of the mid-Atlantic United States. It has a wide ecological amplitude and is found on stream banks, moist thickets, roadsides, nurseries, wood-piles, clearings, and ditches. Polygonum perfoliatum presents serious problems for reforestation because it thrives where forests are clear-cut. A southward direction of spread indicates that the species will probably proliferate in at least some southern states. Mechanical control is not likely to be completely effective because seeds are often left behind. No appropriate biocontrols are known. The plant poses a threat …

Characterization Of The Structural And Electronic Properties Of Spin-Coupled Dinuclear Copper(Ii) Centers By Proton Nmr Spectroscopy, Julie M. Brink, Rachel A. Rose, Richard C. Holz

Chemistry Faculty Research and Publications

The ¹H NMR spectra of a series of well-characterized μ-phenoxo and μ-alkoxo spin-coupled dicopper(II) complexes have been investigated. The complexes studied were [Cu₂(BPMP)(OH)]²⁺ (1) (BPMP = 2,6-bis[[bis(2-pyridylmethyl)amino]methyl]-4-methylphenol), [Cu₂(CH₃HXTA)(OH)]^2- (2) (CH₃HXTA = N,N ‘-(2-hydroxy-5-methyl-1,3-xylylene)bis(N-carboxymethylglycine), [Cu₂(m-XYL)(OH)]²⁺ (3) (m-XYL = 2,6-bis[[bis(2-pyridylethyl)amino]methyl]phenol), and [Cu₂(TBHP)(OAc)]²⁺ (4) (TBHP = N,N,N ‘,N  ‘-tetrakis[(2-benzimidazolyl)methyl]-2-hydroxy-1,3-diaminopropane). The magnetic interactions of these complexes range from strongly antiferromagnetically to weakly ferromagnetically coupled. Both …

Capillary Electrophoretic Enantiomeric Separations Using The Glycopeptide Antibiotic, Teicoplanin, Kimber L. Rundlett, Mary P. Gasper, Eve Y. Zhou, Daniel W. Armstrong

Chemistry Faculty Research & Creative Works

Teicoplanin is the third in a series of macrocyclic glycopeptide antibiotics that has been evaluated as a chiral selector in capillary electrophoresis (CE). It was used to resolve over 100 anionic racemates at low selector concentrations. Like the other related glycopeptide antibiotics, its enantioselectivity tends to be opposite to that of the ansa-type antibiotics which prefers cationic compounds-particularly amines. Factors that affect teicoplanin-based enantioseparations include the selector concentration, pH, and the concentration of the organic modifier. The temperature and the nature and strength of the buffer are also known to affect the stability of the chiral selector as well as …

Enantiomeric Composition And Prevalence Of Some Bicyclic Monoterpenoids In Amber, Daniel W. Armstrong, Eve Y. Zhou, Janusz Zukowski, Barbara Kosmowska-Ceranowicz

Chemistry Faculty Research & Creative Works

Among the more prevalent chiral monoterpenoid compounds in conifers are α-pinene, β-pinene, and smaller amounts of camphene and limonene. The most prevalent chiral monoterpenoid compounds in fossilized resin (referred to as amber in this paper) appear to be borneol, isoborneol, and camphene. Most of these compounds have easily measured enantiomeric excesses. The borneol and isoborneol in some amber samples have pronounced enantiomeric excesses despite the fact that they are tens of millions of years old. The enantiomeric ratios of the monoterpenoids in different ambers vary tremendously and often are distinct. However, in any single amber sample, the stereochemistry (absolute configuration) …

Alternatives To Nitroprusside As Hypotensive Agents, Timothy Casey Mccullough

Honors Theses

The drug sodium pentacyanonitrosylferrate(2-)dihydrate, more commonly known as nitroprusside or nipride (Fig. 1), is a common vasodilating agent given clinically to patients with hypertension.12.22 Nitroprusside is effective in emergency rooms as it quickly reduces high blood pressure, but dosages are limited because of fear that cyanide could be released also. Nitroprusside is effective because the vasodilating agent nitric oxide, NO, is released. Nitric oxide is also recognized as an important biochemical messenger molecule.22 Our research involves a search for different species that could introduce nitric oxide into the body without cyanide. Transition metal complexes involving ruthenium, iron, and cobalt that …

Mechanistic Studies On Malate Dehydrogenase From Escherichia Coli, S. Kirk Wright

Masters Theses

Kinetic studies and chemical modification studies were performed on malate dehydrogenase from Escherichia coli (eMDH). Chemical modification studies using diethylpyrocarbonate and iodoacetic acid, along with log V/K profiles indicate that one ionizing group with a pK_a between 7.9 and 8.5 acts as a general acid/base in the catalytic mechanism. Log V profiles suggest that malate binds to the correctly protonated form of the enzyme. These results imply that a histidine residue is required for catalysis.

A primary deuterium kinetic isotope effect of 1.43 (±0.14) was observed on V/K using malate-2-d, while no isotope effect was measured on V_{max …}

The Development, Molecular Characterization And Application Of A Model Stratum Corneum Lipid System, Rita M. Hatfield

Dissertations

No abstract provided.

Molecular Studies Of Human Erythrocyte Spectrin: Head To-Head Interactions, Nasser Qtaishat

Dissertations

No abstract provided.

The Synthesis Of Azure B Derivatives: Potential Pro-Drugs For Photodynamic Therapy, Carla M. Edwards

Dissertations

No abstract provided.

Na+-H+ Exchange And Na+-Li+ Exchange In Human Erythrocytes: An Nmr Investigation, Yuling Chi

Dissertations

No abstract provided.

Acidic Marine Biotoxins Implicated In Diarrhetic Shellfish Poisoning, Eoin P. Carmody

Theses

An okadaic acid (OA) etiology has been demonstrated for most outbreaks of diarrhetic shellfish poisoning (DSP) in Europe, An isomer of OA, dinophysistoxin-2 (DTX-2), has recently been found in Irish waters and, in 1991 and 1994, was the major toxin during prolonged infestations in cultivated mussels (Mytilus edulis) along the south-west coast of Ireland.

The OA class of DSP toxins have been analysed by HPLC using modified versions of three established fluorescent derivatisation methods. A ‘dual tag’ method for the confirmation of specific toxins has also been developed.

Survey work has been carried out over the past four years on …

Study Of The Long-Term Desorption Of Trichloroethylene From Clay Soils Using Infrared Spectroscopy, Mary P. Stager

Theses and Dissertations

Slow desorption of contaminants from soil presents one of the greatest challenges to modeling contaminant fate and transport and implementing effective remediation technologies. The kinetics of long-term desorption of trichloroethylene (TCE) from powdered clay soils were studied to determine the desorption rates and mechanism. Infrared absorption spectroscopy was used to monitor the concentration of TCE desorbed from contaminated flint clay for 71 hours. Observed gas phase TCE concentrations as a function of time were compared to that predicted by a one-site Langmuir desorption mechanism. The Langmuir model, with a single type of bonding site, did not account for the release …

Effects Of Insulin And Insulin Mimetics On Antioxidant Enzyme Levels: In Vivo And In Vitro, Shikha Varma

Masters Theses

Tissue antioxidation status is considered to be an important factor for elucidating the etiology of diabetes and its physiological complications. This study was aimed to determine the in vivo antioxidant enzyme levels in the altered antioxidant status of diabetic rat liver with the treatment of two potent insulin mimetics, vanadium and selenate. The direct effects of vanadate, selenate, and zinc (another insulin mimetic) on the antioxidant enzyme levels in primary rat hepatocytes in culture was also determined. Levels of superoxide dismutase (SOD), catalase (CAT) and gluthahione peroxidase (GPX) were determined in both model systems.

In the vivo model, insulin treatment …

Regulation Of The Expression Of Lipogenic Enzymes By Insulin-Mimetics, Juiyu Wu

Masters Theses

Many researchers have shown that selenate (SeO₄^2-) and vanadate (VO₄^2-) have insulin-mimetic effects in certain biological processes. These mimetic effects include increasing glucose transport, regulating glycolytic enzymes, normalizing plasma glucose levels and activities of insulin regulated enzymes in diabetic rats. To clarify the functions and roles of these insulin-mimetics in different insulin-regulated metabolic pathways, the expression of the genes for glucose-6-phosphate dehydrogenase (G6PDH) and fatty acid synthase (FAS) were investigated. G6PDH is a key enzyme in the pentose phosphate pathway and is also involved in lipogenic metabolism by providing 55-70% of the NADPH utilization …

The Separation Of Aqueous Iron Species Found In Stepwise Complexation By Capillary Electrophoresis With Atomic Absorption Spectroscopy Detection, Robert E. Sutton

Dissertations

A capillary zone electrophoresis system was interfaced to an atomic absorption spectrom eter to permit the separation and detection o f various species of iron found in step wise complexation in aqueous solutions. The samples were introduced at the anodic end of the column employing the electroosmotic flow to drive all the species to the detector at the cathodic end. Aqueous solutions of iron(II) and iron (III) chloride salts were among the compounds studied. The buffer employed w as a 20 millimolar (2-[N-morpholino]ethanesulfonic acid adjusted to a pH of 6 with 6 .6 millimolar potassium hydroxide. The detection limit was …

Factors Effecting Calcification Of Bioprosthetic Heart Valves, Sumei Yu

Theses

Calcification is the most frequent cause of clinical dysfunction of glutaraldehyde treated bioprosthetic heart valves. In this study, we compared calcification of bioprostheses of the No-ReactTM and the conventional glutaraldehyde treated pericardium by both in-vivo and in-vitro methods, and to further delineate the role of the host's inflammatory response in implant degeneration.

In the in-vitro study, the two types of pericardial samples were placed in individual polystyrene tubes containing physiological concentrations of calcium and phosphate and incubated for 21 days at 37°C. In the in-vivo study, the two types of pericardial samples were implanted subcutaneously in rats and subsequently retrieved …

Tunable Picosecond Infrared Laser System Based On Parametric Amplification In Ktp With A Ti:Sapphire Amplifier, D. E. Gragson, D. S. Alavi, G. L. Richmond

Chemistry and Biochemistry

A picosecond laser system that will generate high-power tunable IR pulses with bandwidths suitable for spectroscopic applications is discussed. The system is based on white-light continuum generation in ethylene glycol and optical parametric amplification in potassium titanyl phosphate. The nonlinear-optical processes are driven by a regeneratively amplified Ti:sapphire laser that produces 1.7-ps pulses at a repetition rate of 1 kHz. Energies as high as 40 and 12 µJ have been achieved over the signal (1.02–1.16-µm) and idler (2.6–3.7-µm) tuning ranges, respectively. The IR beam temporal and spatial characteristics are also presented.

Three-Phase Intersection Points In Monolayers, John P. Hagen, Harden M. Mcconnell

Chemistry and Biochemistry

Some phospholipid/dihydrocholesterol Langmuir monolayers form coexisting liquid phases. Gas domains form at the interface between the phospholipid-rich and dihydrocholesterol-rich liquid phases when these monolayers undergo expansion to low surface pressure. Analysis of the domain shapes thus formed yields the relative line tensions of the gas/phospholipid, gas/dihydrocholesterol, and phospholipid/dihydrocholesterol phase interfaces.

Nutrient Limitation In A Southwestern Desert Reservoir: Eutrophication Of Las Vegas Bay, Lake Mead, Nevada, Davine M. Lieberman

Publications (WR)

Algal bioassay tests were conducted with Selenastrum capricornutum and natural algae on inner Las Vegas Bay, Lake Mead, Nevada, from December 1992 through September 1993, to identify any nutrient limitation in an area of the reservoir that has experienced problems associated with severe nutrient enrichment. Three areas were sampled based on a gradient of water quality conditions that existed in Las Vegas Bay (LVB). Disodium ethylenedinitrilotetraacetate (EDTA) significantly stimulated algal growth compared to non-EDTA treatment. Algal bioassays indicated that phosphorus (P) was the primary limiting nutrient at all stations for most of the test dates. Chl a response with EDTA …

Detection Of Alzheimer's Disease And Other Diseases Using An Improved Photoaffinity Labeling Method, Boyd E. Haley

Chemistry Faculty Patents

An improved method for diagnosing a disease comprising detecting a disease-specific biochemical marker macromolecule within a sample of extracted cerebral spinal fluid or serum is disclosed. In particular, a radioactively labeled photoaffinity probe is used to diagnose a disease. For instance, Alzheimer's disease can be diagnosed by detecting a disease-specific protein having a molecular weight of about 42,000 daltons, i.e., glutamine synthetase. Also included is a method for detecting other disease states, such as cancer, by detecting the presence or absence of specific nucleotide binding proteins.