Digital Commons Network^™

Separation Of Enantiomers With Chiral Dendrimer, Jie Zhuang

Masters Theses

Chiral dendrimers with .unique ordered structures are especially attractive for the recognition of chiral molecules based on the three point contact model. We have successfully synthesized first generation chiral dendrimers containing L- and D- tryptophan methyl ester moieties and characterized them by NMR, IR, UV-Visible, MS, and optical activity. L-tryptophan methyl ester dendrimer was converted to its acid form in order to attach it to aminopropyl silica for the HPLC separation of enantiomers. The aminopropyl silica containing 1.52mmols/g of NH₂ groups binds about 0.3mmols of dendrimer per gram and has about 0.4mmols of free NH₂ groups per gram. …

Application Of Horizontal Flow Treatment Wells For In Situ Treatment Of Perchlorate Contaminated Groundwater, Jeffrey C. Parr

Theses and Dissertations

Groundwater contamination by perchlorate has recently been recognized as a significant environmental problem across the United States, and especially at Department of Defense facilities. In this study, a model is used to evaluate the potential of a innovative in situ bioremediation technology using Horizontal Flow Treatment Wells (HFTWs) to manage perchlorate-contaminated groundwater. The technology uses HFTWs to mix an electron donor into perchlorate-contaminated groundwater in order to promote reduction of the perchlorate by indigenous microorganisms in bioactive zones within the aquifer, as well as recirculate the contaminated water between treatment well pairs to achieve multiple passes of contaminated water through …

Two-Phase Decay Of Aerobic Sludge Shown By Online Fluorescence And Modeled With Interaction Of Heterotrophs And Nitrifiers, Xu Li, Lu-Kwang Ju

Chemical, Biomolecular, and Corrosion Engineering Faculty Research

Both heterotrophs and autotrophic nitrifiers are present in aerobic sludge digestion systems. The endogenous heterotrophic metabolism releases ammonium that, via oxidation to nitrite and nitrate, serves as the energy substrate for growth and survival of nitrifiers. The population interaction was used to explain the two-phase decay behavior observed in this study for the biosolids collected from rotating biological contactors (RBC) as well as the mixed primary and secondary sludge. Separated by an intermediate transition, the two phases followed different first-order decay kinetics, with the first phase being much faster. The two-phase phenomenon was supported by the on-line fluorescence profile monitored …

Removal Of Antibiotics From Surface And Distilled Water In Conventional Water Treatment Processes, Craig D. Adams, Yang Wang, K. Loftin, M. Meyer

Civil, Architectural and Environmental Engineering Faculty Research & Creative Works

Conventional drinking water treatment processes were evaluated under typical water treatment plant conditions to determine their effectiveness in the removal of seven common antibiotics: carbadox, sulfachlorpyridazine, sulfadimethoxine, sulfamerazine, sulfamethazine, sulfathiazole, and trimethoprim. Experiments were conducted using synthetic solutions prepared by spiking both distilled/ deionized water and Missouri River water with the studied compounds. Sorption on Calgon WPH powdered activated carbon, reverse osmosis, and oxidation with chlorine and ozone under typical plant conditions were all shown to be effective in removing the studied antibiotics. Conversely, coagulation/flocculation/sedimentation with alum and iron salts, excess lime/soda ash softening, ultraviolet irradiation at disinfection dosages, and …

An Anion Characterization Of A Constructed Wetland Used For Chlorinated Ethene Remediation, Bradley M. Bugg

Theses and Dissertations

Chlorinated ethenes physical properties as well as its ubiquitous state at DOD installations makes it a priority for innovative remediation efforts. Current techniques are expensive and time consuming to maintain. Constructed wetlands suggest an inexpensive and operational alternative to conventional technologies. Sub-surface flow wetlands provide the anaerobic zones necessary to reduce the recalcitrant chlorinated solvents prior to anaerobic or aerobic mineralization of its daughter products. A vertical flow cell to include sequential sedimentary layers of two hydric soil lifts and a mix of hydric soil and woody compost was the subject of this investigation. This study focused on the statistical …

The Determination Of The Best Modified Way And Microscopical Analysis For Enzyme/Immunoelectrodes, Sa-Ying Dong, Hong-Ren Wang, Yu-Zhu Gao, Guang-Zhang Chen, Ming-Xiang Lv, Bo-Yi Tian

Journal of Electrochemistry

In this paper, the electrochemical response characteristics of enzyme and immuno electrodes were studied by cyclic voltammetry under different conditions. Our goals were to determine the best modified way of bioelectrode, which was the base of biosensor's application. 30U GOD and 0.8 mg/mL SEC1 antibody were suitable to bioelectrode preparation and detection. The microscopical analysis was finished with scan microscopy.

The Influence Of Gold Substrate Topography On The Voltammetry Of Cytochrome C Adsorbed On Carboxylic Acid Terminated Self-Assembled Monolayers, Michael C. Leopold, Edmond F. Bowden

Chemistry Faculty Publications

Interfacial investigations of a protein monolayer electrochemical system, equine cytochrome c (cyt c) adsorbed to carboxylic acid terminated self-assembled monolayer (COOH SAM) modified gold electrodes, were performed. Electrochemical, spectroscopic, and scanning probe microscopy techniques were utilized to explore the influence of gold topography in the cyt c/COOH SAM/gold system. COOH SAMs were prepared from 14-mercaptotetradecanoic acid and 11-mercaptoundecanoic acid on a variety of substrates including evaporated, bulk, single crystal, and epitaxially grown gold on mica. These substrates encompassed a wide range of surface roughness. As the topography of the gold became smoother, SAMs exhibited an increased ability to …

A Post-Amadori Inhibitor Pyridoxamine Also Inhibits Chemical Modification Of Proteins By Scavenging Carbonyl Intermediates Of Carbohydrate And Lipid Degradation, Paul A. Voziyan, Thomas O. Metz, John W. Baynes, Billy G. Hudson

Faculty Publications

Reactive carbonyl compounds are formed during autoxidation of carbohydrates and peroxidation of lipids. These compounds are intermediates in the formation of advanced glycation end products (AGE) and advanced lipoxidation end products (ALE) in tissue proteins during aging and in chronic disease. We studied the reaction of carbonyl compounds glyoxal (GO) and glycolaldehyde (GLA) with pyridoxamine (PM), a potent post-Amadori inhibitor of AGE formation in vitro and of development of renal and retinal pathology in diabetic animals. PM reacted rapidly with GO and GLA in neutral, aqueous buffer, forming a Schiff base intermediate that cyclized to a hemiaminal adduct by intramolecular …

Potent Enantioselective Auxin: Indole-3-Succinic Acid, Daniel W. Armstrong, Yan Song Liu, Lingfeng He, K. Helen Ekborg-Ott, Charles L. Barnes, Charles F. Hammer

Chemistry Faculty Research & Creative Works

Low levels of synthetic auxins are used as root growth promoters for a wide variety of botanicals. When properly used, they can produce earlier and more prolific root growth. Indole-3-succinic acid (ISA) is a chiral compound that can be synthesized as a racemate. Its enantiomers were resolved by both chromatography and diastereomeric crystallization. The absolute configuration of each enantiomer was determined by X-ray crystallography and then tested for auxin activity. The relative effectiveness of the ISA enantiomers was determined and compared to the achiral synthetic auxin indole-3-butyric acid and to the natural auxin indole-3-acetic acid.

Anchoring The Water Dimer Potential Energy Surface With Explicitly Correlated Computations And Focal Point Analyses, Gregory S. Tschumper, Matthew L. Leininger, Brian C. Hoffman, Edward F. Valeev, Henry F. Schaefer, Martin Quack

Chemistry Faculty Research & Creative Works

The extensive ab initio quantum chemical study of ten stationary point on the water dimer potential energy surface (PES) was discussed. The geometry optimizations were carried out using the CCSD(T) method in conjunction with the [TZ2P(f,d) + dif] basis set. The study showed that the optimized structures of (H₂O)₂ PES were quite similar to those obtained at the MP2 level with much smaller basis sets and the number of imaginary vibrational frequencies or hessian index of each stationary point was unchanged despite fairly significant geometrical differences for some of the optimized structures.

Familial Als-Associated Mutations Decrease The Thermal Stability Of Distinctly Metallated Species Of Human Copper/Zinc Superoxide Dismutase, Daryl K. Eggers, J. A. Rodriguez, J. S. Valentine, J. A. Roe, A. Tiwari, R. H. Brown, L. J. Hayward

Faculty Publications, Chemistry

We report the thermal stability of wild type (WT) and 14 different variants of human copper/zinc superoxide dismutase (SOD1) associated with familial amyotrophic lateral sclerosis (FALS). Multiple endothermic unfolding transitions were observed by differential scanning calorimetry for partially metallated SOD1 enzymes isolated from a baculovirus system. We correlated the metal ion contents of SOD1 variants with the occurrence of distinct melting transitions. Altered thermal stability upon reduction of copper with dithionite identified transitions resulting from the unfolding of copper-containing SOD1 species. We demonstrated that copper or zinc binding to a subset of “WT-like” FALS mutants (A4V, L38V, G41S, G72S, D76Y, …

Calorimetric Study Of Block-Copolymers Of Poly(N-Butyl Acrylate) And Gradient Poly(N-Butyl Acrylate-Co-Methyl Methacrylate), A I. Buzin, M Pyda, P Costanzo, K Matyjaszewski, B Wunderlich

Chemistry and Biochemistry

The nanophase separation in diblock and triblock copolymers consisting of immiscible poly(n-butyl acrylate) (block A) and gradient copolymers of methyl methacrylate (MMA) and n-butyl acrylate (n BA) (block M/A) were investigated by means of their heat capacity, C_p, as a function of the composition of the blocks M/A and temperature. In all copolymers studied, both blocks are represented by their C_p and glass transition temperature, T_g, as well as the broadening of the transition-temperature range. The low-temperature transition of the blocks A is always close to that of the …

Time-Dependent Density Functional Theory Investigation Of The Ground And Excited States Of Coumarins 102, 152, 153, And 343, Robert J. Cave, Edward W. Castner Jr.

All HMC Faculty Publications and Research

We present calculations of various properties of the ground and excited electronic states of coumarins 102, 152, 153, and 343. Using density functional theory (DFT) and time-dependent density functional theory (TDDFT), we examine the excitation energies to the S₁ and S₂ states, the ground and excited-state dipole moments, and the lowest ionization potentials of these coumarins. In the case of C153, we locate two distinct S₀ minima due to differing conformations of the julolidyl ring structure and compare properties for the syn and anti conformers. For C343, we examine the possibility of proton transfers in the ground …

An On-Line Acid-Base Titration Applet In The Generic Tutorial System For The Sciences Project, Thomas Lee Gummo

Theses Digitization Project

The purpose of this Master's Project was to develop an Acid-Base Titration Simulator. It was also to be a part of the California State University - San Bernardino's GTSS, Generic Tutorial System for the Sciences, project. The main benefit is that students will be able to conduct titration experiments over the Internet without being in the laboratory and without costly equipment or dangerous chemicals. Instructors at the high school and college level can demonstrate the key principles of titration.

Synthesis And Chemistry Of Naphthalene Annulated Trienyl Iron Complexes: Potential Anticancer Dna Alkylation Reagents, Traci Means

Inquiry: The University of Arkansas Undergraduate Research Journal

Iron complex chemistry that opens a new door to the medicinal and pharmaceutical worlds is the aim of this research. Specifically, ortho-quinone methide moieties are intermediates in several antitumor drugs and have been identified as bioreductive alkylators of DNA. In our research, a class of iron compounds has been targeted to resemble these quinone methides. It is hoped that these new compounds could be modified to provide a window of opportunity toward the discovery of a selective mode of drug delivery. We have focused our efforts on generating a reactive transition metal complexed 5-membered ring analog of o-quinone methide based …

Electronic Structure And Bonding In Unligated And Ligated Feii Porphyrins, M.-S. Liao, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The electronic structure and bonding in a series of unligated and ligated Fe^II porphyrins (FeP) are investigated by density functional theory (DFT). All the unligated four-coordinate iron porphyrins have a ³A_2g ground state that arises from the (d_xy)²(d_z²)²(d_π)² configuration. The calculations confirm experimental results on Fe tetraphenylporphine but do not support the resonance Raman assignment of Fe octaethylporphine as ³E_g, nor the early assignment of Fe octamethyltetrabenzporphine as ⁵B_2g. For the six-coordinate Fe–P( …

Electronic Structure And Bonding In Metal Porphyrins, Metal=Fe, Co, Ni, Cu, Zn, M.-S. Liao, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

A systematic theoretical study of the electronic structure and bonding in metal meso-tetraphenyl porphines MTPP, M=Fe, Co, Ni, Cu, Zn has been carried out using a density functional theory method. The calculations provide a clear elucidation of the ground states for the MTPPs and for a series of [MTPP]^x ions (x = 2+, 1+, 1−, 2−, 3−, 4−), which aids in understanding a number of observed electronic properties. The calculation supports the experimental assignment of unligated FeTPP as ³A_2g, which arises from the configuration (d_xy)²(d_{z …}

Recent Applications Of Flame Atomic Absorption Spectrometry To Environmental Measurements, Michael A. Janusa

Faculty Publications

Atomic absorption spectroscopy is very useful for the determination of a large number of elements, especially at trace levels. It is a widely used technique for analysis of a wide variety of sample matrices including biota, soils, and water. Atomic absorption spectroscopy is a very reputable technique that is inexpensive and delivers accurate results even in a complex matrix. This review focuses on the applications of flame atomic absorption spectroscopy to environmental measurements, and is mainly based on papers published from 1999–2002.

Pyridoimidazolium Cationic Dyes: Theory, Synthesis, And Sub-Cellular Localization, Robert William Rambacher

Theses, Dissertations and Capstones

(PICs, Figure 1) are a new class of fluorescent dyes which are prepared by an exceedingly flexible methodology. Using computational chemical methods, the excitation and emission maxima of these dyes were simulated. This was best accomplished through geometry optimization (MM+) followed by calculating the electronic spectrum with ZINDO/S. This protocol has been found to be effective and has the potential to greatly streamline the design of new longer wavelength dyes. Several new longer wavelength dyes have now been identified as synthetic targets.

The presence of amino groups on a known fluorescent ring system is well established to markedly affect the …

Stimulation And Modeling Of Pond Formations On The Asteroid 433 Eros, Justin Thompson

Inquiry: The University of Arkansas Undergraduate Research Journal

"Ponds" are surface features that appear to be the result of the deposition of finer material on the asteroid's regolith, the layer of loose sediment that blankets the entire asteroid. Ponds were discovered by the NEAR Shoemaker spacecraft in January, 2001, on the asteroid 433 Eros. The objective of experimentation is to simulate the development of these ponds in the Andromeda planetary sciences environmental chamber. The Andromeda Chamber offers a unique ability to simulate surface environments that occur on Eros. The chamber was used to simulate the processes that occur as Eros emits gas through its outer surface, including the …

Theoretical Investigation Of The Ground And Excited States Of Coumarin 151 And Coumarin 120, Robert J. Cave, Kieron Burke, Edward W. Castner Jr.

All HMC Faculty Publications and Research

We present calculations of various properties of the ground and excited states of Coumarins 151 and 120. These and related coumarins are important in investigating ultrafast solvation processes in liquids and complex solutions as well as being important acceptors in model electron-transfer systems. We calculate the following:  (1) the electronic excitation energies to several low-lying singlet states, (2) ground and excited-state dipole moments, (3) solvation effects on excitation energies, and (4) the properties of single Coumarin 151-water complexes. We test our Time-Dependent Density Functional Theory (TDDFT) calculations against CASSCF, CASPT2 (both single and multistate versions), CIS, and ZINDO. Using TDDFT, …

Synthesis, Spectral And Fungicidal Studies On Dioxobridged Binuclear Niobium(V) And Tantalum(V) Complexes Of N-Alkylphenothiazines, Boregowda Keshavan, Hunasegala Kempe Gowda

Turkish Journal of Chemistry

Six new dioxobridged binuclear complexes of the type [MO(L)Z]_{2}Z, where M=niobium(V) or tantalum(V), L=N-alkylphenothiazines (NAPs) and Z=tartrate and oxalate for niobium and tantalum respectively, were synthesized. The stoichiometry of the complexes was proposed on the basis of elemental analyses, molar conductance, magnetic and thermal data. The coordination behaviour of the ligands was determined with the help of spectroscopic studies. The fungicidal activity of the complexes was evaluated.

Efficient Synthesis Of 1-Alkoxycarbonyl-Methyl-2-Alkylpyrroles From Dichloro- And Methoxychloropropylalkyl Ketones, Raik A. Gadzhili, Raya A. Nadzhafova, Özge Şeşenoğlu

Turkish Journal of Chemistry

The condensation reaction of 2,3-dichloropropyl- and 2-methoxy-3-chloropropyl alkyl ketones with alkyl 2-aminoacetate salts leads to 1-alkoxy-carbonylmethyl-2-alkylpyrroles. These compounds, with various bases, gave 1-carbamoylmethyl-, 1-dialkylaminocarbonylmethyl-, 1-carbazoyl methyl-2-alkylpyrroles and potassium salt of 2-alkyl-pyrrolyl-1-acetic acid.

Synthesis, Characterization And Thermal Analysis Of Organotin(Iv) Derivatives Of 4-(N-Maleoyl)Butanoate, Khadija Shahid, Saqib Ali, Moazzam H. Bhatti, Muhammad Mazhar, Sohail Mahmood, Sadiqur Rehman

Turkish Journal of Chemistry

Organotin(IV) derivatives of the type R_{4 - n}SnL_{n} where R = Me, n-Bu, Ph, L = 4 - (N-maleoyl)butanoate and n = 1 or 2 were synthesized by refluxing R_{3}SnCl and R_{2}SnCl_{2} with (4-(N-maleoyl)butanoate in the presence of triethylamine using dry toluene as solvent. These compounds were characterized by IR, multinuclear NMR and mass spectrometry. We also studied their thermal behavior and calculated the degradation pattern, energy of activation (E_{a}) and order of reaction (n).

Conformational Analysis Of Pol-Rfamide Ii (Glu}^{1}-Trp^{2}-Leu^{3}-Lys^{4}-Gly^{5}-Arg^{6}-Phe^{7}-Nh_{2}) Heptapeptide, Lütfü Demi̇r, Niftali Mihrali Godjaev

Turkish Journal of Chemistry

The geometrical structure of the sea anemone and sea pansies neuropeptide Pol-RFamide II Glu^{1}-Trp^{2}-Leu^{3}-Lys^{4}-Gly^{5}-Arg^{6}-Phe^{7}-NH_{2} was carried out by molecular mechanics (MM). The linkage bonds are characterised by the torsional angles \phi, \psi and \omega and the side groups characterised by the torsional angles \chi_{1}, \chi_{2}, \chi_{3},... subsequently. The energy-map for each monopeptide of the Pol-RFamide II was drawn in the range of -180° to 180° with increments of 20°. Conformation facilities for monopeptides were decided from these maps. These results were used in the analysis of the dipeptide Glu^{1}-Trp^{2}. Then, the Glu^{1}-Trp^{2}-Leu^{3} tripeptide was examined by using the calculated results …

Reproduction In West Virginia Populations Of The Southern Two-Lined Salamander (Eurycea Cirrigera), Timothy R. Brophy, Thomas K. Pauley

Faculty Publications and Presentations

We describe reproduction in West Virginia populations of the southern two-lined salamander (Eurycea cirrigera) and provide insights into the behavioral ecology of this wide-ranging urodele. The first signs of reproduction are evident well before the arrival of Spring. Sexually mature adults inhabit the cold, rocky streams of southwestern West Virginia in early February. Females arc known by the presence of large oocytes visible through the body wall and males by their extremely swollen heads. Breeding occurs in the stream during late March and is marked by the presence of gravid females with sperm caps in their posterior cloacae. Eggs are …

Combinatorial Chemistry: A Guide For Librarians, Philip Barnett

Publications and Research

No abstract provided.

Induction Of Myocarditis And Valvuluitis In Lewis Rats By Different Epitopes Of Cardiac Myosin And Its Implications In Rheumatic Carditis, Jeffrey E. Galvin, Mark E. Hemric, Stanley D. Konsanke, Stephen M. Factor, Anthony Quinn, Madeleine W. Cunningham

Faculty Publications and Presentations

Immune responses against cardiac myosin and group A streptococcal M protein have been implicated in the pathogenesis of rheumatic heart disease. Although cardiac myosin is known to produce myocarditis in susceptible animals, it has never been investigated for its role in production of valvular heart disease, the most serious sequelae of group A streptococcal infection in acute rheumatic fever. In our study, cardiac myosin induced valvulitis in the Lewis rat, and epitopes responsible for production of valvulitis were located in the rod region. Human and rat cardiac myosins induced severe myocarditis in the Lewis rats as expected. A purified S2 …

Parameters Affecting Partitioning Of 6 Pcb Congeners In Natural Sediments, Eid A. Alkhatib, Carl Weigand

Chemistry & Physics Faculty Publications

Polychlorinated biphenyls (PCBs) released by bottom sediments were determined by experiments in which the sediments were artificially resuspended using sediment contaminated with PCBs in a particle entrainment simulator (PES). Sediment cores, spiked with PCBs, were collected from the Housatonic River in Connecticut and run in the PES at simulated shear stresses from 0 to 0.6 N m(-2). Experimental results from these simulations have shown that mean concentration of PCBs in the solid phase for sites with high volatile organic carbon (VOC) were significantly greater than samples with low VOC; the reverse was true for the water phase. In addition, on …

Site-Specific Modification Of De Novo Designed Coiled-Coil Polypeptides With Inorganic Redox Complexes, Anna Fedorova, Michael Y. Ogawa

Chemistry Faculty Publications

A stepwise procedure for preparing of site-specific binuclear metallopeptides is described. The modification procedure involves the alkylation of a cysteine side chain by reaction with [Ru(bpy)(2)(phen-ClA)](2+), where bpy = 2,2'-bipyridine and phen-ClA = 5-chloroacetaniido-1,10-phenanthroline, followed by the coordination of a ruthenium pentammine complex to a histidine residue located elsewhere along the sequence. The apo and metalated versions of the peptides C10H21(30-mer) and H10C21(30-mer) display circular dichroism spectra having minima at 208 and 222 nm, with theta(222)/theta(208) = 1.04 to indicate that these peptides exist as a-helical coiled-coils in aqueous solution. When the ruthenium polypyridyl complex is attached to C10H21(30-mer), the …