Chemistry Commons^™

Open-Path Fourier Transform Infrared Studies Of Large-Scale Laboratory Biomass Fires, Robert J. Yokelson, David W. T. Griffith, Darold E. Ward

Chemistry and Biochemistry Faculty Publications

A series of nine large-scale, open fires was conducted in the Intermountain Fire Sciences Laboratory (IFSL) controlled-environment combustion facility. The fuels were pure pine needles or sagebrush or mixed fuels simulating forest-floor, ground fires; crown fires; broadcast burns; and slash pile burns. Mid-infrared spectra of the smoke were recorded throughout each fire by open path Fourier transform infrared (FTIR) spectroscopy at 0.12 cm⁻¹ resolution over a 3 m cross-stack pathlength and analyzed to provide pseudocontinuous, simultaneous concentrations of up to 16 compounds. Simultaneous measurements were made of fuel mass loss, stack gas temperature, and total mass flow up the …

High-Power Broadly Tunable Picosecond Ir Laser System For Use In Nonlinear Spectroscopic Applications, D. E. Gragson, B. M. Mccarty, G. L. Richmond, D. S. Alavi

Chemistry and Biochemistry

We developed a high-power tunable picosecond IR laser system suitable for nonlinear spectroscopic investigations. We employ a Ti:sapphire regenerative amplifier that produces 1.9-ps, 17-cm⁻¹, 800-nm pulses at 1 kHz as a pump source. White-light generation in ethylene glycol and optical parametric amplification in potassium titanyl phosphate are used to produce the IR pulses. The tuning range extends from 2.4 to 3.8 μm in the idler and 1.0 to 1.2 μm in the signal. A total efficiency (signal plus idler) as high as 20% was achieved. The spatial, spectral, and temporal characteristics of the IR beam are presented along …

Critical Pressures In Multicomponent Lipid Monolayers, John P. Hagen, Harden M. Mcconnell

Chemistry and Biochemistry

Epifluorescence microscopy has been used previously to study coexisting liquid phases in lipid monolayers of dihydrocholesterol and dimyristoylphosphatidylcholine at the air/water interface. This binary mixture has a critical point at room temperature (22°C), a monolayer pressure of approx. 10 mN/m, and a composition in the vicinity of 20-30 mol% dihydrocholesterol. It is reported here that this critical pressure can be lowered, raised, or maintained constant by systematically replacing molecules of this phosphatidylcholine with molecules of a phosphatidylethanolamine, or an unsaturated phosphatidylcholine, or mixtures of the two, while maintaining the dihydrocholesterol concentration at 20 mol%. Thus, even complex mixtures of lipids …

The Lipooligosaccharides Of Haemophilus Ducreyi Are Highly Sialylated, William Melaugh, A A. Campagnari, B W. Gibson

Chemistry Faculty Publications

The major lipooligosaccharides of the sexually transmitted pathogen Haemophilus ducreyi 35000 have been previously found to terminate in N-acetyllactosamine and sialyl-N-acetyllactosamine, Neu5Ac alpha 2-->3Gal beta 1-->4GlcNAc (W. Melaugh, N. J. Phillips, A. A. Campagnari, M. V. Tullius, and B. W. Gibson, Biochemistry 33: 13070-13078, 1994). In this study, mass spectrometry and composition analyses have shown that the lipooligosaccharides from three other H. ducreyi strains also contain N-acetyllactosamine and are highly sialylated (approximately 30 to 50%), although one African strain was found to contain neither of these structural features.

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

Chemistry and Biochemistry

No abstract provided.

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 …

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 …}

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 …

Environments Of The Four Tryptophans In The Extracellular Domain Of Human Tissue Factor: Comparison Of Results From Absorption And Fluorescence Difference Spectra Of Tryptophan Replacement Mutants With The Crystal Structure Of The Wild-Type Protein, C. A. Hasselbacher, E. Rusinova, R. Rusinova, R. A. Kohanski, W. Lam, A. Guha, J. Du, T. C. Lin, I. Polikarpov, C. W. G. Boys, Y. Nemerson, W. H. Konigsberg, J. B. A. Ross

Chemistry and Biochemistry Faculty Publications

The local environments of the four tryptophan residues of the extracellular domain of human tissue factor (sTF) were assessed from difference absorption and fluorescence spectra. The difference spectra were derived by subtracting spectra from single Trp-to-Phe or Trp-to-Tyr replacement mutants from the corresponding spectrum of the wild-type protein. Each of the mutants was capable of enhancing the proteolytic activity of factor Vila showing that the mutations did not introduce major structural changes, although the mutants were more susceptible to denaturation by guanidinium chloride. The difference spectra indicate that the Trp residues are buried to different extents within the protein matrix. …

Structural Characterization Of A Novel Inhibitor Of Hiv Reverse Transcriptase (Hiv Rt), Greggory Jon Woitte

Chemistry & Biochemistry Theses & Dissertations

Human immunodeficiency virus (HIV) infections have become a leading cause of death among young people in the United States today. As the number of HIV infections increases, so too does the cost of treatment. Together, these numbers have prompted an increase in the development of pharmaceutical interventions. HIV reverse transcriptase (HIV RT) has become a suitable target for drug therapy because it is the sole enzyme responsible for HIV replication.

Fucoidan, a sulfated polysaccharide isolated from the brown algae Fucus vesiculosus, has been shown to block a variety of cell adhesion related events including metastasis. In addition, fucoidan has also …

Conversion Of Bovine Pancreatic Phospholipase A At A Single Site Into A Competitor Of Neurotoxic Phospholipases A By Site-Directed Mutagenesis, Mu-Chin Tzeng, Chon-Ho Yen, Ming-Jhy Hseu, Cynthia M. Dupureur, Ming-Daw Tsai

Educator Preparation & Leadership Faculty Works

A 45-kDa polypeptide preferentially present in neuronal membranes was previously identified as a subunit of a binding (or receptor) protein for several phospholipase A2 variants with neurotoxicity, including crotoxin, by chemical cross-linking experiments (Yen, C.-H., and Tzeng, M.-C.(1991) Biochemistry 30, 11473-11477). The binding of crotoxin to this receptor protein was completely suppressed by sufficient F22Y, a mutated bovine pancreatic phospholipase A2 generated by site-directed mutagenesis of Phe of the wild-type enzyme to Tyr. The IC of this inhibition was estimated to be 1 μM. In sharp contrast, the wild-type enzyme gave no effect even at 50 μM. This …

New Optical Cell Design For Laser Flash Photolysis Studies In Supercritical Fluids, Steven R. Goates, Milton L. Lee, Qin Ji, Edward M. Eyring, Rudi Van Eldik, Kedika Bal Reddy

Faculty Publications

A high-pressure optical cell has been designed that achieves an effective separation between the chemical sample and the pressurizing medium and system. This design limits possible sample contamination and catalytic effects under supercritical fluid sample conditions. Laser flash photolysis experiments were carried out on molybdenum hexacarbonyl dissolved in supercritical CO2. The thermal ring closure reaction of the species Mo(CO)5L, where L is 2,2- bipyridine was found to proceed at rates comparable to those measured previously in liquid benzene or toluene. Much larger activation volumes were found for the reaction in supercritical CO2 than in liquid toluene.

Baseline Water Quality Data Inventory And Analysis: Lake Mead National Recreation Area, Volume Ii Of Ii, National Park Service

Publications (WR)

This document presents the results of surface-water-quality data retrievals for Lake Mead National Recreation Area (LAME) from five of the United States Environmental Protection Agency's (EPA) national databases: (1) Storage and Retrieval (STORET) database management system; (2) River Reach File (RF3); (3) Industrial Facilities Discharge (IFD); (4) Drinking Water Supplies (DRINKS); and (5) Flow Gages (GAGES). This document is one product resulting from a cooperative contractual endeavor between the National Park Service's Servicewide Inventory and Monitoring Program, the National Park Service's Water Resources Division (WRD), and Horizon Systems Corporation to retrieve, format, and analyze water quality data for all units …

Baseline Water Quality Data Inventory And Analysis: Lake Mead National Recreation Area, Volume I Of Ii, National Park Service

Publications (WR)

This document presents the results of surface-water-quality data retrievals for Lake Mead National Recreation Area (LAME) from five of the United States Environmental Protection Agency's (EPA) national databases: (1) Storage and Retrieval (STORET) database management system; (2) River Reach File (RF3); (3) Industrial Facilities Discharge (IFD); (4) Drinking Water Supplies (DRINKS); and (5) Flow Gages (GAGES). This document is one product resulting from a cooperative contractual endeavor between the National Park Service's Servicewide Inventory and Monitoring Program, the National Park Service's Water Resources Division (WRD), and Horizon Systems Corporation to retrieve, format, and analyze water quality data for all units …

A Study Of Euplotes Crassus Telomere Proteins And Related Genes, John Scott Perez

Department of Chemistry: Dissertations, Theses, and Student Research

A novel PCR technique used to amplify Euplotes crassus macronuclear chromosomes was developed to provide scientific proof that an Euplotes crassus 1.0 kb gene is not genetically related to an Oxytricha nova 1.8 kb β-telomere protein gene. Theories and experimental procedures associated with the development of this PCR technique were the product of research that will have a profound impact on future studies of telomere protein genes and telomeric DNA in a multitude of eukaryotic cells. The hypothesis that a β-telomere protein does not exist in Euplotes crassus was supported by the result of this study.

Expression of the recombinant …

Semiclassical Quantization Of A Nonintegrable System: Pushing The Fourier Method Into The Chaotic Regime, Karl Sohlberg, Randall B. Shirts

Faculty Publications

Semiclassical Einstein–Brillouin–Keller (EBK) quantization of the nonintegrable Hénon–Heiles Hamiltonian succeeds using the Fourier transform method of Martens and Ezra. Two innovations are required for this success: (1) the use of tunneling corrected quantizing actions obtained from an approximate, one-dimensional Hamiltonian and (2) exploitation of intermediate-time approximate quasiperiodicity or "vague tori'' wherein the Fourier transform of chaotic motion over 10–100 vibrational periods allows the determination of frequencies and amplitudes which approximate motion during the time interval. Approximate tori, actions, and EBK energy levels are then straightforward. We use an interpolation method to smooth over small resonance zones that are not expected …

Sensitivity Of Second Harmonic Generation To Space Charge Effects At Si(111)/Electrolyte And Si(111)/Sio2/Electrolyte Interfaces, P. R. Fischer, J. L. Daschbach, D. E. Gragson, G. L. Richmond

Chemistry and Biochemistry

The potential dependence in the surface second harmonic response from hydrogen terminated n‐Si(111) and oxidized n‐Si(111) surfaces has been examined in aqueous NH₄F and H₂SO₄ solutions. The relative phase of the nonlinear response as measured by rotational anisotropy experiments is found to be highly sensitive to the presence of the oxide and the field applied across the Si(111)/oxide/electrolyte interface. These observations are attributed to field effects within the space–charge region of the semiconductor which vary with the presence and thickness of the insulating oxide layer on the Si(111) surface.

Use Of An Oriented Transmembrane Protein To Probe The Assembly Of A Supported Phospholipid Bilayer, Paul Brian Contino, Carol A. Hasselbacher, J. B. Alexander Ross, Yale Nemerson

Chemistry and Biochemistry Faculty Publications

Planar-supported phopholipid bilayers formed by te adsorpton of vesicles are increasingly used in the investigation of lipK-ependent reactis. We have studied the way in which these bilayers are forned with phopholipid vesicles coaining the btranembrane protein Tssue Factor (TF). TF complexed with te senne protease, factor Vlla, is the primary initiator of bklod coagulation by way of activation of the zymogen factor X. TF has been shown to orient randomly on the inner and outer leaflets of vesicles. We used proteolytic digestion to produce vesicles in which the exracellular domain of TF is located on the inner leaflet These vesicles …

The Structure And Dynamics Of The Cs2 Molecular Ion, Karl Sohlberg, Chan Yibai

Faculty Publications

Several common elementary methods of computing molecular properties, prerequisite to molecular dynamics studies, are tested for their validity for CS+2. Judged sufficiently accurate, these methods are then used to aid in investigating the collisionally activated dissociation of CS+2 upon impact with xenon. Rice–Ramsperger–Kassel–Marcus (RRKM) unimolecular decay rate calculations are presented and compared to experimental studies employing collisional activation. RRKM theory is shown to reproduce the experimental results for collision energies near threshold. When corrected for vibrational anharmonicity, the RRKM calculation shows agreement with the experimental results over a slightly wider range of energies. A discussion is given on the applicability …

Dissection Of An Antibody-Catalyzed Reaction, Jon D. Stewart, Joseph F. Krebs, Gary Siuzdak, Anthony J. Berdis, David B. Smithrud, Stephen J. Benkovic

Chemistry Faculty Publications

Antibody 43C9 accelerates the hydrolysis of a p-nitroanilide by a factor of 2.5 x 10(5) over the background rate in addition to catalyzing the hydrolysis of a series of aromatic esters. Since this represents one of the largest rate accelerations achieved with an antibody, we have undertaken a series of studies aimed at uncovering the catalytic mechanism of 43C9. The immunogen, a phosphonamidate, was designed to mimic the geometric and electronic characteristics of the tetrahedral intermediate that forms upon nucleophilic attack by hydroxide on the amide substrate. Further studies, however, revealed that the catalytic mechanism is more complex and involves …

Determination Of Pancreatic And Salivary Amylase By Enzyme Immunoassay And Their Prevalence In Hyperamylasemic Patients, Sabdra Borgens Ward

Theses and Dissertations in Biomedical Sciences

Currently, amylase determinations are nonspecific for the organ source and are based entirely on the enzymatic properties of amylase to produce a measurable product or byproduct. The determination of pancreatic amylase is important in the diagnosis of acute pancreatitis. Most commercially available tests for amylase employ the measurement of the change in NADH absorbance at 280 nm or of the p-nitrophenol released from a maltotetrose substrate. These are nonspecific measurements of pancreatic amylase and often necessitate other tests to be run such as a serum lipase.

The two predominant isoenzymes of amylase are pancreatic (p-amylase) and salivary (s-amylase); the most …

Use Of Pyocin To Select A Haemophilus Ducreyi Variant Defective In Lipooligosaccharide Biosynthesis, A A. Campagnari, R Karalus, M A. Apicella, William Melaugh, A J. Lesse, B W. Gibson

Chemistry Faculty Publications

Haemophilus ducreyi, a cause of genital ulcer disease in developing countries, appears to facilitate the heterosexual transmission of the human immunodeficiency virus in Africa. Despite an increase in studies of this gram-negative human pathogen, little is known about the pathogenesis of chancroid. Our studies have shown that the lipooligosaccharides (LOS) of H. ducreyi may play an important role in ulcer formation. Monoclonal antibody and mass spectrometric analyses identified a terminal trisaccharide present on H. ducreyi LOS that is immunochemically similar to human paragloboside. This epitope is present on the LOS of Neisseria gonorrhoeae, and it may be the site of …

Expression Of Prelamin A Confers Sensitivity Of Dna Biosynthesis To Lovastatin On F9 Teratocarcinoma Cells, Michael Sinensky, T. Mclain, K. Fantle

Faculty Publications, Biological Sciences

No abstract provided.

The Processing Pathway Of Prelamin A, Michael Sinensky, K. Fantle, M. Trujillo, T. Mclain, A. Kupfer, M. Dalton

Faculty Publications, Biological Sciences

The conversion of mammalian prelamin A to mature lamin A proceeds through the removal of 18 amino acids from the carboxyl terminus. The initial step in this processing is the isoprenylation of a CAAX box cysteine. This proteolytic event is distinctive for prelamin A among the known prenylated mammalian proteins. Since the carboxyl terminus of prelamin A is removed during maturation, it is not obvious that this protein would undergo the two reactions subsequent to prenylation observed in other CAAX box proteins-the endoproteolytic removal of the carboxyl-terminal 3 amino acids and the subsequent methylation of the now carboxyl-terminal cysteine. To …

Effective, Reliable, Inexpensive Cryofixation Device, Lawrence A. Mink, Roger A. Buchanan

Journal of the Arkansas Academy of Science

No abstract provided.

Thermal Decomposition Studies Of Selected Transition Metal Polysulfide Complexes. Ii. Effect Of Atmosphere On Decomposition, Benjamin Rougeau, Mark Draganjac

Journal of the Arkansas Academy of Science

Initial studies involved the thermal decomposition profile of five polysulfide complexes in air up to 550 °C. Since our first report to the Academy in 1990, we have obtained the capability to run samples up to 1500°C under various gases. Thermal Gravimetric Analysis (TGA) and Differential Thermal Analysis (DTA)of a series of transition metal polysulfide complexes are presented. Compounds analyzed included Cp2TiS5 ,MoS9 2",MoOS8 2", Zn(S x ) 2", Cd(S x ) 2-, Fe2S122 - and NiS82.

A Characterization Of Extractable, Hydroxylated Fatty Acid Bearing Components In Legionella Pneumophila, Jonathan R. Lane

Electronic Theses and Dissertations

Extraction of the lipids of Legionella pneumophila yields phases unlike those produced from other Gram-negative bacteria. A viscous interface forms between the aqueous (wash) and organic phases. More than half of the hydroxylated fatty acids were found distributed between the aqueous phase and the interfacial material, fractions in which such constituents have not been reported in other Gram-negative species. It was further observed that after the material from the aqueous/interfacial phase was dissolved in methanol or chloroform/methanol (2:1 (V/V)), the addition of acetone would create a white, flocculent precipitate. Analyses showed that the supernatant contained fatty acids that were nonhydroxylated …

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 …