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Quantitative Measurement Of Guest–Host Interactions In Supramolecular Systems: A Comparative Brillouin Scattering Study Of The Dianin’S Compound Clathrand And Two Of Its Isostructural Clathrates, C.A. Sandstedt, D. Michalski, Craig J. Eckhardt

Craig J. Eckhardt Publications

Single, isomorphous crystals of the guest-free clathrand of Dianin’s compound and two of its clathrates containing two ethanols and a heptanol, respectively, have been studied by Brillouin scattering to obtain their complete elastic constant tensors. The values found for individual elastic constants are related to microscopic interactions of the guests and host cage using the clathrand as the reference. Direct correlation of the interference of the guest heptanol molecule with the hexamer hydrogen-bonded network of the host cage to reduced stiffness of this clathrate is demonstrated. In contrast, the ethanol-containing clathrate is demonstrated to have negligible interaction of the guests …

Fundamental Capillary Electrophoresis: An Evaluation Of Electrokinetic Sampling, Cindy Ann Mleziva Blake

Seton Hall University Dissertations and Theses (ETDs)

Capillary electrophoresis has become a powerful separation technique in fields of biochemical separations, inorganic ions, and chiral separations. The technique has experienced exponential growth since the historic publication of Zone Electrophoresis in Open-Tubular Glass Capillaries by Lukacs and Jorgenson in 1981. However, the use of capillary electrophoresis as a primary research analysis tool still remains to be seen in many pharmaceutical laboratories. One of the main reasons for this is that it remains difficult to validate CE methods using the criteria of quantitation and accuracy posed by the current government regulating agencies, as developed for high performance liquid chromatography and …

Phorboxazole Synthetic Studies: The C3–C15 Bis-Oxane Segment, Patrick Bernard Greer, William A. Donaldson

Chemistry Faculty Research and Publications

The enantioselective synthesis of the C3–C15 bis-oxane segment of the phorboxazoles has been accomplished from 3-t-butyldiphenylsilyloxypropanal in 9 steps (>90% ee).

Studies On The Roles Of Atp In Nitrogenase Catalysis, Wei Wu

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Nitrogenase is the enzyme that catalyzes the reduction of nitrogen to ammonia in a reaction requiring MgATP hydrolysis. Two component proteins of nitrogenase are the iron protein (Fe protein) and the molybdenum-iron protein (MoFe protein).

Nitrogenase contains two nucleotide binding sites. During catalysis, the Fe protein binds two MgATP first. The conformational changes induced upon MgATP binding allow the Fe protein to associate with the MoFe protein. After the formation of the Fe protein-MoFe protein complex, a single electron is transferred from the Fe protein to the MoFe protein, an event that is coupled to MgATP hydrolysis in the Fe …

Rotational Structure Of Extremely Floppy Van Der Waals Complexes: Adiabatic Separation Of Angular And Radial Motion, P. Daniel Ward

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The adiabatic or Born-Oppenheimer approximation is often used in molecular calculations to simplify the solution to the Schrödinger equation. The basis of the approximation is the large difference in the relative motions of the nuclei and electrons in the molecule—the electrons are able to respond almost instantly to the movements of the nuclei. Thus, the nuclei may be regarded as being fixed in a certain position and the Schrödinger equation can then be solved using the potential obtained by solving the electronic problem at fixed nuclear configuration.

A similar argument can be used to decouple the angular and radial motions …

Carbon Nanotube Atomic Force Microscopy Tips: Direct Growth By Chemical Vapor Deposition And Application To High-Resolution Imaging, Chin Li Cheung, Jason H. Hafner, Charles M. Lieber

Barry Chin Li Cheung Publications

Carbon nanotubes are potentially ideal atomic force microscopy probes because they can have diameters as small as one nanometer, have robust mechanical properties, and can be specifically functionalized with chemical and biological probes at the tip ends. This communication describes methods for the direct growth of carbon nanotube tips by chemical vapor deposition (CVD) using ethylene and iron catalysts deposited on commercial silicon-cantilever-tip assemblies. Scanning electron microscopy and transmission electron microscopy measurements demonstrate that multiwalled nanotube and single-walled nanotube tips can be grown by predictable variations in the CVD growth conditions. Force-displacement measurements made on the tips show that they …

Jeffress Research Grant Awards

Virginia Journal of Science

Announcements of the Jeffress Research Grants that have been awarded in 1999.

Thermolysis Of Semicarbazones To The Corresponding Azines Through Reactive N-Substituted Isocyanate Intermediates, Shailesh N. Shah, N.K. Chudgar

Faculty Publications

Thermolysis of semicarbazones (I) to azines (II) occurs through reactive N-substituted isocyanate intermediates (Ia) which can be converted in situ to carbamates and N-substituted ureas.

Photodegradation Of Pcbs In Natural Waters, Adriana R. Nicolaescu

Masters Theses

PCBs are widely distributed in the environment and they are biologically refractory and toxic compounds. There is great interest in understanding their fate in the environment, and also for finding safe and effective degradation methods.

This study is concerned with the photodegradation of four PCB congeners: PCB 5, PCB 18, PCB 77, PCB 128 in natural waters. Natural waters contain humic substances which can greatly influence the environmental fate of the PCBs. The different degradation of the four congeners was studied in standardized systems and in humic acid or nitrate solutions, under environmental conditions. DMDE and Methoxyclor (whose environmental half-lifetimes …

The Noesy Jigsaw: Automated Protein Secondary Structure And Main-Chain Assignment From Sparse, Unassigned Nmr Data, Chris Bailey-Kellogg, Alik Widge, John J. Kelley Iii, Marcelo J. Berardi, John H. Bushweller, Bruce Randall Donald

Dartmouth Scholarship

High-throughput, data-directed computational protocols for Structural Genomics (or Proteomics) are required in order to evaluate the protein products of genes for structure and function at rates comparable to current gene-sequencing technology. This paper presents the Jigsaw algorithm, a novel high-throughput, automated approach to protein structure characterization with nuclear magnetic resonance (NMR). Jigsaw consists of two main components: (1) graph-based secondary structure pattern identification in unassigned heteronuclear NMR data, and (2) assignment of spectral peaks by probabilistic alignment of identified secondary structure elements against the primary sequence. Jigsaw's deferment of assignment until after secondary structure identification differs greatly from traditional approaches, …

X-Ray Structure Of The Quinoprotein Ethanol Dehydrogenase From Pseudomonas Aeruginosa: Basis Of Substrate Specificity, Thomas Keitel, Annette Diehl, Tobias Knaute, John J. Stezowski, Wolfgang Hohne, Helmut Görisch

John J. Stezowski Publications

The homodimeric enzyme form of quinoprotein ethanol dehydrogenase from Pseudomonas aeruginosa ATCC 17933 crystallizes readily with the space group R3. The X-ray structure was solved at 2.6 Å resolution by molecular replacement. Aside from differences in some loops, the folding of the enzyme is very similar to the large subunit of the quinoprotein methanol dehydrogenases from Methylobacterium extorquens or Methylophilus W3A1. Eight W-shaped β-sheet motifs are arranged circularly in a propeller-like fashion forming a disk-shaped superbarrel. No electron density for a small subunit like that in methanol dehydrogenase could be found. The prosthetic group is located in the centre …

Development Of Organoiron Methodology For Preparation Of The Polyene Natural Product Macrolactin A, Heiko Bärmann, Vadapalli Prahlad, Chunlin Tao, Young K. Yun, Zhi Wang, William A. Donaldson

Chemistry Faculty Research and Publications

Methodology for the synthesis of the C7–C13 segment (19) and C14–C24 segment (41) of macrolactin A have been developed. Dicarbonyl(methyl 7-nitro-2E,4Z-heptadienoate)triphenylphosphineiron (19) is prepared by nucleophilic addition to a (1-methoxycarbonylpentadienyl)iron cation. The C23 stereocenter of 41 is established by introduction of a C20 stereocenter, chirality transfer from C20 to C23 followed by (diene)iron mediated selective ionic reduction of the C20 hydroxyl. The C15 stereocenter may be established by nitrile oxide–olefin cyclocondensation.

In Situ Treatment Of Chlorinated Ethene-Contaminated Groundwater Using Horizontal Flow Treatment Wells, Derek R. Ferland

Theses and Dissertations

The limitations of conventional containment technologies for groundwater contaminated with chlorinated solvents have motivated development of innovative technologies to achieve national groundwater remediation objectives. One inn9vative technology that is currently under development involves metal reductants or catalysts to chemically destroy the dissolved chlorinated solvent. Models are important tools that can be used to help transition this technology to the field. Model studies can be used to gain understanding about the technology, help determine when the prospective technology might work for a given site, and design full-scale field applications.

Methyl-Substituted Dispiro-1,2,4,5-Tetraoxanes:  Correlations Of Structural Studies With Antimalarial Activity, Kevin J. Mccollough, James K. Wood, Walter Reed Army Institute Of Research, Yuxiang Dong, Jonathan L. Vennerstrom

Chemistry Faculty Publications

Two tetramethyl-substituted dispiro-1,2,4,5-tetraoxanes (7,8,15,16-tetraoxadispiro[5.2.5.2]- hexadecanes) 3 and 4 were designed as metabolically stable analogues of the dimethylsubstituted dispiro-1,2,4,5-tetraoxane prototype WR 148999 (2). For a positive control we selected the sterically unhindered tetraoxane 5 (7,8,15,16-tetraoxadispiro[5.2.5.2]hexadecane), devoid of any substituents. Tetraoxanes 3 and 4 were completely inactive in contrast to tetraoxanes 2 and 5. We hypothesize that the two inactive tetraoxanes possess sufficient steric hindrance about the tetraoxane ring due to the two additional axial methyl groups to prevent their activation to presumed parasiticidal carbon radicals by inhibiting electron transfer from heme or other iron(II) species. For each of the tetraoxanes 2-4, …

Modeling Chlorinated Ethene Removal In Constructed Wetlands: A System Dynamics Approach, Colby D. Hoefar

Theses and Dissertations

The purpose of this study is to gain understanding of the dynamics of the processes that degrade Perchloroethene (PCE) to ethylene, or carbon dioxide (CO₂), within the confines of a constructed wetland. A system dynamics approach will be used. This model is focused on identifying and optimizing the naturally occurring processes in stratified wetland sediment that reduce mass, toxicity, mobility, volume or concentration of contaminants in groundwater. Contaminant fate and transport within a wetland system is extremely complex and the mechanisms that drive wetland behavior are dynamic. Confidence in the model was built through verification and testing. Reasonable …

Chromate Dissociation From Primer Paint In Simulated Lung Fluid, Tiffany J. R. Morgan

Theses and Dissertations

OSHA has proposed a new strontium chromate exposure standard that would potentially cause Air Force paint facilities to be in violation of the proposed standard if adopted. This proposed reduction make the continued use of chromate containing primer paints very difficult. There is currently no acceptable replacements for chromate containing primer paints on AF aircraft. This study suggests that paint particles with chromate bound in primer paint may be unavailable for bodily absorption if inhaled and a reduced standard for painting applications may be unnecessary. Primer paint overspray was collected into simulated lung fluid (SLF) and allowed 6 hr, 24 …

Design, Synthesis, And Evaluation Of A Novel Serine Protease Inhibitor Based On Monocyclic Β-Lactams, Ian M. Paquette

All Theses And Dissertations

Serine proteases are a large family of proteolytic enzymes which utilize a serine residue as a reactive nucleophile in the active site. Some of the more common serine proteases are chymotrypsin, trypsin, thrombin, human leukocyte elastase (HLE), human cathepsin G, and human cytomegalovirus protease (HCMV protease). Unregulated serine protease activity has been implicated in several common ailments, including rheumatoid arthritis, emphysema, pancreatitis, atherosclerosis, cystic fibrosis, and Alzheimer’s disease. Since serine proteases are responsible for the onset of such a wide range of diseases, there is an equivalent need for a large library of synthetic serine protease inhibitors to selectively counteract …

High-Performance Liquid Chromatographic Separation Of The Enantiomers Of Unusual Α-Amino Acid Analogues, Antal Péter, Edit Olajos, Richard Casimir, Dirk Tourwé, Quirinus B. Broxterman, Bernard Kaptein, Daniel W. Armstrong

Chemistry Faculty Research & Creative Works

The direct and indirect stereochemical resolution of the enantiomers of ring- and α-methyl-substituted phenylalanines and phenylalanine amides was attempted by high-performance liquid chromatographic methods. The direct separation was carried out on two chiral stationary phases, the crown-ether- based Crownpak CR (+), and the teicoplanin-based Chirobiotic T, while the indirect resolution was performed by applying pre-column derivatization with 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl isothiocyanate (GITC) and Nα- (2,4-dinitro-5-fluorophenyl)-L-alanine amide (Marfey's reagent, FDAA). The Chirobiotic T column was efficient in the separation of ring- and α-methyl- substituted phenylalanine analogues but was ineffective for the amides of these analogues. The Crownpak CR (+) column separated the ring-substituted …

Hydrogen Bonding In Alcohol Clusters: A Comparative Study By Infrared Cavity Ringdown Laser Absorption Spectroscopy, Robert A. Provencal, Raphael N. Casaes, Katja Roth, Joshua B. Paul, Chris N. Chapo, Richard J. Saykally, Gregory S. Tschumper, Henry F. Schaefer

Chemistry Faculty Research & Creative Works

Infrared cavity ringdown laser absorption spectroscopy has been used to study the O-H stretching vibrations of jet-cooled ethanol and butanol clusters. Three bonded O-H stretches were attributed to the ethanol dimer, indicating the presence of more than one conformer in the molecular beam. One unresolved feature was measured for both the trimer and tetramer. To facilitate spectral assignment, the vibrational frequencies and intensities have been calculated for the ethanol dimer using second-order Moller-Plesset perturbation theory. Three bonded O-H stretches have also been measured for the butanol dimer, suggesting that more than one conformer is present in the molecular beam. Vibrational …

Degradation Of N-Hexadecane And Its Metabolites By Pseudomonas Aeruginosa Under Microaerobic And Anaerobic Denitrifying Conditions, Chawala Chayabutra, Lu-Kwang Ju

Chemical, Biomolecular, and Corrosion Engineering Faculty Research

A strategy for sequential hydrocarbon bioremediation is proposed. The initial O-2-requiring transformation is effected by aerobic resting cells, thus avoiding a high oxygen demand. The oxygenated metabolites can then be degraded even under anaerobic conditions when supplemented with a highly water-soluble alternative electron acceptor, such as nitrate. To develop the new strategy, some phenomena were studied by examining Pseudomonas aeruginosa fermentation. The effects of dissolved oxygen (DO) concentration on n-hexadecane biodegradation were investigated first. Under microaerobic conditions, the denitrification rate decreased as the DO concentration decreased, implying that the O-2-requiring reactions were rate limiting. The effects of different nitrate and …

Abstracts Of Student-Faculty Publications

The Corinthian

Abstracts of Student-Faculty Publications

Ground-State Properties And Excited-State Reactivity Of 8-Quinolate Complexes Of Ruthenium(Ii), Dean Johnston

Chemistry Faculty Scholarship

In an effort to explore new systems with highly reducing excited states, we prepared a series of Ru(II) complexes of the type Ru(L)(2)quo(+) (L = bpy (2,2'-bipyridine), phen (1,10-phenanthroline), dmphen (4,7-dimethyl-1,10-phenanthroline), tmphen (3,4,7,8-tetramethyl-1,10-phenanthroline); quo(-) = 8-quinolate) and investigated their photophysical and redox properties. The absorption and emission spectra of the Ru(L)(2)quo(+) are significantly red-shifted relative to those of the parent complexes Ru(L)(3)(2+), with emission maxima in the 757-783 nm range in water. The Ru(L)(2)quo(+) systems are easily oxidized with E(1/2)(Ru(III/II)) values ranging from +0.62 to +0.70 V vs NHE, making the emissive Ru --> phen MLCT (metal-to-ligand charge transfer) excited …

Double Cysteine Mutations In Staphylococcal Nuclease: The Effect Of Artificially Introduced Disulfide Bonds On Protein Structure And Stability, Anna Terry

Inquiry: The University of Arkansas Undergraduate Research Journal

Since a protein's function depends on its structure, basic research in protein structure facilitates the solution of many practical problems, such as the synthesis of more effective medicines. With this larger goal in sight, the purpose of this research project is to understand better the chemical principles that underlie protein structure and stability. Disulfide bonds are a potentially stabilizing feature of many proteins. They may form between cysteine residues in close proximity to one another if the orientation is favorable. Often found in proteins produced by organisms that grow at high temperatures, disulfide bonds may anchor side chains together, making …

Characterization Of Chimeric Lipopolysaccharides From Escherichia Coli Strain Jm109 Transformed With Lipooligosaccharide Synthesis Genes (Lsg) From Haemophilus Influenzae, Nancy J. Phillips, T. J. Miller, J. J. Engstrom, William Melaugh, R. Mclaughlin, M A. Apicella, B W. Gibson

Chemistry Faculty Publications

Previously, we reported the expression of chimeric lipopolysaccharides (LPS) in Escherichia coli strain JM109 (a K-12 strain) transformed with plasmids containing Haemophilus influenzae lipooligosaccharide synthesis genes (lsg) (Abu Kwaik, Y., McLaughlin, R. E., Apicella, M. A., and Spinola, S. M. (1991) Mol. Microbiol. 5, 2475–2480). In this current study, we have analyzed the O-deacylated LPS and free oligosaccharides from three transformants (designated pGEMLOS-4, pGEMLOS- 5, and pGEMLOS-7) by matrix-assisted laser desorption ionization, electrospray ionization, and tandem mass spectrometry techniques, along with composition and linkage analyses. These data show that the chimeric LPS consist of the complete E. coli LPS core …

Preparation Of An Electrophilic 3-Methylindole Derivative: Difficulties In Forming A Stable, Suitable Material For The Preparation Of Tryptophan, Jason Boggs, Mariah Mcmasters, Robert W. Curley Jr., Michael J. Panigot

Journal of the Arkansas Academy of Science

In an attempt to prepare stereoselectively beta-deuterated tryptophan, N-protected indole-3-methanol compounds were prepared with model studies being done on undeuterated material. Conversion of these compounds to electrophilic species proved exceptionally difficult and resulted in very low yields or recovered starting material only. A summary of the current results utilizing N-tosyl indole-3-methanol will be presented as well as efforts using N-Boc indole-3-methanol.

Spin-Exchange Term In The Solvent Equation Of State Near The Critical Point For Electron Transfer Reactions, Juana Vivó Acrivos

Faculty Publications, Chemistry

Phenomenological Equations of State (EOS) for fluids near their critical point have been obtained using literature compression factor data, Zc = Pc Vc/(n R Tc) = 0.40 to 0.10 in Table I (Pc, Vc/n, Tc are the pressure, volume per n mole, and the absolute temperature of the fluid at the critical point). The objective is to explain the deviations from the van der Waals value, Zc(vdW) = 3/8 (-70 % for molten Se and alkali metals up to 6 % for molten Pb, Hg, and In) by including in the commonly used phenomenological thermodynamic relations a term which explicitly …

Studies Of Tryptophans In Membrane- Spanning "Walp" Peptides By Deuterium Nmr Spectroscopy, Nichole Reed

Inquiry: The University of Arkansas Undergraduate Research Journal

WALP pep tides of sequence acetyl-Gly-Trp-Trp-(Leu-Ala)-Trp-Trp-Ala-ethanolamine insert into lipid bilayers as membrane-spanning a-helices and modulate the lipid phase behavior as functions of n and the lipid acyl chain length. A key feature of the WALP peptides is the positioning of tryptophan (Trp) indole rings at the membrane/water interface. For the examples WALP19 with n = 6.5 and WALP23 with n = 8.5, we have labeled individual indoles with deuterium and incorporated the labeled peptides in oriented, hydrated bilayers of Dimyristoyl-phosphatidylcholine (DMPC). Deuterium NMR spectra from these samples show sharp resonances when the membrane normal is aligned either parallel (Beta = …

Cytotoxic Mab From Rheumatic Carditis Recognizes Heart Valves And Laminin, Jeffrey E. Galvin, Mark E. Hemric, Kent Ward, Madeleine W. Cunningham

Faculty Publications and Presentations

Anti-streptococcal antibodies cross-reactive with N-acetyl-bD-glucosamine (GlcNAc) and myosin are present in the sera of patients with rheumatic fever (RF). However, their role in tissue injury is not clear. In this study, we show that anti-GlcNAc/anti-myosin mAb 3.B6 from a rheumatic carditis patient was cytotoxic for human endothelial cell lines and reacted with human valvular endothelium and underlying basement membrane. Reactivity of mAb 3.B6 with the valve was inhibited by human cardiac myosin > laminin > GlcNAc. The mAb 3.B6 epitopes were localized in fragments of human cardiac myosin, including heavy meromyosin (HMM), the S1 subfragment, and two light meromyosin (LMM) peptides containing …

Determination Of Thermal Maturity And Organic Matter Type By Principal Components Analysis Of The Distributions Of Polycyclic Aromatic Compounds, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The thermal maturity and organofacies sensitivity of polycyclic aromatic compound (PAC) distributions was explored by examination of the aromatic fractions of solvent extracts from a diverse set of 53 shales, coals and kerogen macerals which have undergone either natural or artificial maturation and which represent all three principal sedimentary organic matter (OM) types. Systematic changes with maturation were observed in the following groups of isomers: tri- and tetramethylnaphthalenes, methyl- and dimethylphenanthrenes, methyl- and dimethyldibenzothiophenes, methylpyrenes, and methylchrysenes. The maturity differences were quantified by mathematical ratios of the relative concentrations of the more thermally stable isomers to the less stable, on …

Applicability Of Ozone In Small Drinking Water Systems, Craig D. Adams, Justin Sutherland

Civil, Architectural and Environmental Engineering Faculty Research & Creative Works

The use of ozone in water treatment plants is expanding rapidly in the United States. Ozone offers excellent disinfection properties (including chlorine-resistant pathogens) and does not form trihalomethanes. Additionally, ozone can be used to achieve or control many other water quality parameters such as color, taste and odor, and inorganic and organic contaminant concentrations. Control of ozone's disinfection byproducts such as bromate (formed in high bromide waters) is required. This presentation will review the synergistic effects of ozone applicable to use in small water treatment plants.