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Ua66/7/2 Hilltopper News, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

Infrared Spectroscopy Of H-Bonded Bridges Stretched Across The Cis-Amide Group: I. Water Bridges, Joel R. Carney, A. V. Fedorov, John R. Cable, Timothy S. Zwier

Chemistry Faculty Publications

The water-containing clusters of oxindole (OI) and 3,4-dihydro-2(1H)-quinolinone (DQ) have been studied in the hydride stretch region of the infrared by the technique of resonant ion-dip infrared spectroscopy (RIDIRS). Both OI and DQ are constrained cis-amides with adjacent N-H and C=O groups between which water can form H-bonded bridges. The hydride stretch fundamentals of OI-W-n with n = 1-3 and DQ-W-n with n = 1, 2 without exception divide up into free OH stretch fundamentals near 3700 cm(-1) and a set of H-bonded bridge fundamentals in the 3200-3450 cm(-1) region. The bridge fundamentals show a distribution of intensities that reflects …

Solution Structure Of B. Subtilis Acyl Carrier Protein, Guang-Yi Xu, Amy Tam, Laura Lin, Jeffrey Hixon, Christian C. Fritz, Robert Powers

Robert Powers Publications

Background: Acyl carrier protein (ACP) is a fundamental component of fatty acid biosynthesis in which the fatty acid chain is elongated by the fatty acid synthetase system while attached to the 4’-phosphopantetheine prosthetic group (4’- PP) of ACP. Activation of ACP is mediated by holo-acyl carrier protein synthase (ACPS) when ACPS transfers the 4’-PP moiety from coenzyme A (CoA) to Ser36 of apo-ACP. Both ACP and ACPS have been identified as essential for E. coli viability and potential targets for development of antibiotics.

Results: The solution structure of B. subtilis ACP (9 kDa) has been determined using two-dimensional and three-dimensional …

Dissolution Of Chromium From Inhalable Primer Paint Particles Into A Simulated Lung Fluid, David A. Kauth

Theses and Dissertations

The use of chromate as a corrosion inhibitor in primer paint is an essential component for the protection of aluminum-skinned aircraft and the primary source of hexavalent chromium (Cr (VI)) exposure to USAF aircraft painters. The objective of this research was to quantify the dissolution of chromate from freshly sprayed paint particles into a simulated lung fluid (SLF). Two primer paints were sprayed with a paint spray gun to generate overspray particles for collection into impingers filled with SLF. Particles were allowed to soak in SLF for 24 and 48 hours and then the particles were removed by centrifugation. The …

Optimization Of Palladium-Catalyzed In Situ Destruction Of Trichloroethylene-Contaminated Groundwater Using A Genetic Algorithm, Manuel Fernandez

Theses and Dissertations

Conventional technologies for the treatment of groundwater contaminated with chlorinated solvents have limitations that have motivated development of innovative technologies. One such technology currently under development involves using palladium-on-alumina (Pd/Al) as a catalyst to promote dechlorination. Pd/Al catalyst may be used in-well as part of a re-circulating horizontal flow treatment well (HFTW) system. An HFTW system involves two or more dual-screened wells, with in-well reactors, to capture and treat contaminated groundwater without the need to pump the water to the surface. In this study, objective and fitness functions, based on system costs and TCE concentration requirements, were developed to optimize …

Surface-Enhanced Raman Spectroscopy Of Metallotetraphenyl Porphyrins Adsorbed On Ag2O And Silver Colloids, Ying-Hui Zhang, Dong-Ming Chen, Tian-Jing He, Fan-Chen Liu

Journal of Electrochemistry

The biological significance of porphyrins and metalloporphyrins has stimulated intensive investigations on these compounds for many years. On the other hand, porphyrins and metalloporphyrins also have extensive applications in many other fields such as chemical modified electrodes, organic photovoltaic devices and biomimetic catalysis. The adsorption behavior and chemical reactions of metalloporphyrins on surfaces or interfaces are very important for these applications.

Study On Electrofusion Of Barley Protoplasts Using Fluorescent Dextra, Min-Yan Wang, Ye-Fang Gong, Zhi-Yu Jiang

Journal of Electrochemistry

The influence of interfacial active substance on the electrofusion of barley protoplasts was investigated using fluorescent dextra (F DX) as an anion additive. It was found that fluorescent dextra could inhibit the electrofusion process. The adsorption of fluorescent dextra on the membrane of protoplasts was detected by fluorescent microscopy technique. It was observed that after being stored in a solution containing fluorescent dextra a fluorescent ring appeared on the membrane of the protoplast, reflecting the adsorption of fluorescent dextra. The results of electrophoresis experiment also proved the adsorption of F DX on the surface of protoplasts, because the relative mobility …

Raman Spectroelectrochemical Study On Bioactive Molecules, Xiao-Wei Cao, Hai-Feng Yang, Zhe Su Meng Xiao Yun Wang, Xia-Qin Wu, Zong-Rang Zhang

Journal of Electrochemistry

Electron-transfer reaction is known to be one of the key reactions for generating biological functions. Mechanism revelation at a molecular level of such kind reactions is to be very helpful for us to understand life essence. In fact, surface enhanced Raman scattering (SERS) is one of the most powerful tools for the study on metal-electrolyte and metal-vacuum interfaces since 1970's. Moreover, Raman spectroscopic study in enzymology has provided attractive results during last twenty-five years.

Dansylation Of Hydroxyl And Carboxylic Acid Functional Groups, Ronald Bartzatt

Chemistry Faculty Publications

Fluorescent labeling of primary and secondary amines using dansyl chloride has been widely used in the past. Its application provides an extremely sensitive means to detect amine functional groups to amounts of less than 1 mg of material. This work describes a method for the dansylation of hydroxyl (–OH) and carboxylic acid (–COOH) functional groups. This technique is demonstrated with ethanol, gamma hydroxy butyric acid (GHB), benzoic acid, and p-chloroaniline. Sensitivity of detection for all compounds are microgram or microliter. For the compounds ethanol and GHB which are liquids at room temperature, as little as 1 ml quantity can be …

Calculation Of 13C Chemical Shifts In Rna Nucleosides: Structure-13C Chemical Shift Relationships, Paolo Rossi, Gerard S. Harbison

Gerard S. Harbison Publications

Isotropic ¹³C chemical shifts of the ribose sugar in model RNA nucleosides are calculated using SCF and DFT-GIAO ab initio methods for different combinations of ribose sugar pucker, exocyclic torsion angle, and glycosidic torsion angle. Idealized conformations were obtained using structures that were fully optimized by ab initio DFT methods starting with averaged parameters from a collection of crystallographic data. Solid-state coordinates of accurate crystal or neutron diffraction structures were also examined directly without optimization. The resulting ¹³C chemical shifts for the two sets of calculations are then compared. The GIAO-DFT method overestimates the shifts by an average …

Process For Immobilizing Waste Using Bagasse (Us Patent 6174275), Michael A. Janusa

Faculty Publications

No abstract provided.

Tectorna: Modular Assembly Units For The Construction Of Rna Nano-Objects, Neocles B. Leontis, Luc Jaeger, Eric Westhof

Chemistry Faculty Publications

Structural information on complex biological RNA molecules can be exploited to design tectoRNAs or artificial modular RNA units that can self-assemble through tertiary interactions thereby forming nanoscale RNA objects. The selective interactions of hairpin tetraloops with their receptors can be used to mediate tectoRNA assembly. Here we report on the modulation of the specificity and the strength of tectoRNA assembly tin the nanomolar to micromolar range) by variation of the length of the RNA subunits, the nature of their interacting motifs and the degree of flexibility of linker regions incorporated into the molecules. The association is also dependent on the …

High-Performance Liquid Chromatographic And Capillary Electrophoretic Enantioseparation Of Plant Growth Regulators And Related Indole Compounds Using Macrocyclic Antibiotics As Chiral Selectors, F. Hui, K. H. Ekborg-Ott, Daniel W. Armstrong

Chemistry Faculty Research & Creative Works

Enantioseparation of plant growth regulators, such as 3-(3-indolyl)-butyric acid, abscisic acid and structurally related molecules including a variety of substituted tryptophan compounds, has been achieved by HPLC and/or CE. The covalently bonded macrocyclic antibiotics, teicoplanin, ristocetin A and vancomycin, were used as chiral stationary phases (CSPs) in HPLC. Most of the racemates were baseline resolved in the reversed-phase mode (EtOH-H2O) using the teicoplanin CSP. The chiral recognition mechanism is discussed in regard to the structure of the analytes. In CE, the three aforementioned macrocyclic antibiotics were used as chiral additives in a phosphate run buffer. The effect of pH and …

Atomically Resolved Single-Walled Carbon Nanotube Intramolecular Junctions, Min Ouyang, Jin-Lin Huang, Chin Li Cheung, Charles M. Lieber

Barry Chin Li Cheung Publications

Intramolecular junctions in single-walled carbon nanotubes are potentially ideal structures for building robust, molecular-scale electronics but have only been studied theoretically at the atomic level. Scanning tunneling microscopy was used to determine the atomic structure and electronic properties of such junctions in single-walled nanotube samples. Metal-semiconductor junctions are found to exhibit an electronically sharp interface without localized junction states, whereas a more diffuse interface and low-energy states are found in metal-metal junctions. Tight-binding calculations for models based on observed atomic structures show good agreement with spectroscopy and provide insight into the topological defects forming intramolecular junctions. These studies have important …

Cooperativity Of Dna Object Self-Assembly, Ava Caudill Dykes

Theses, Dissertations and Capstones

In this study, the temperature dependence of self-assembling DNA structures was investigated. Specially designed two-dimensional DNA nanoarrays offer not only structural stability not normally associated with DNA, but also provide several possible sites of interaction, referred to as free ends, which can be easily exploited through conventional Watson-Crick base pairing. The ability to synthesize two-dimensional DNA nanoarrays was corroborated by confirming the presence of the nanoarrays by AFM imaging in air. The physical characteristics of two-dimensional DNA nanoarrays were also studied. DNA nanoarray synthesis occurs via a self-assembly process based on Watson-Crick base pairing. This self-assembly occurs through an annealing …

Preliminary X-Ray Diffraction Studies Of The Transcriptional Inhibitory Antibody Fab41.4, Johanna Mazlo, Robyn L. Stanfield, Ian A. Wilson, Steven H. Hinrichs, John J. Stezowski

Department of Chemistry: Faculty Publications

The binding of transcription factor ATF-1 to DNA contributes to gene expression and regulation of cell growth. Antibody Mab41.4, raised against ATF-1, and its derivatives Fab41.4 and scFv41.4 inhibit specific DNA binding in vitro and induce apoptotic death of tumor cells in vivo. Structural studies of Fab41.4 were performed to gain insight into the mechanism of action of this potentially therapeutic antibody. The optimal conditions for crystallization of Fab41.4 were determined. Crystals were needle-like in appearance, displayed C2 space-group symmetry and diffracted to a resolution of 1.6 Å. The unit-cell parameters were determined to be a = 186.64, b = …

Multiple Separations Facilitate Identification Of Protein Variants By Mass Spectrometry, Zhongli Zhang, David L. Smith, Jean B. Smith

Department of Chemistry: Faculty Publications

Identification of variant proteins from complex biological samples promises to contribute much to our understanding of the etiology of pathological states. Characterization of variants, due either to genetic mutations in protein sequences or to post-translational modifications, is considerably more difficult than the simple protein identifications typical of most current proteomic investigations. Identification of a few peptides by database retrieval is not adequate when the goal is to have a complete understanding of the modifications of the protein. Although one advantage of mass spectrometry is its ability to obtain specific responses to several components, the complexity of biological samples is often …

Halogen Oxidation Reactions Of (C5ph5)Cr(Co)3 And Lewis Base Addition To [(C5ph5)Cr(Μ-X)X]2: Electrochemical, Magnetic, And Raman Spectroscopic Characterization Of [(C5ph5)Crx2]2 And (C5ph5)Crx2(Thf) (X = Cl, Br, I). X-Ray Crystal Structure Of [(C5ph5)Cr(Μ-Cl)Cl]2, Marc A. Hutton, James C. Durham, Robert W. Grady, Brett E. Harris, Carter S. Jarrell, J. Matthew Mooney, Michael Castellani, Arnold L. Rheingold, Ulrich Kölle, Brenda J. Korte, Roger D. Sommer, Gordon T. Yee, J. Matthew Boggess, Roman S. Czernuszewicz

Chemistry Faculty Research

The 17-electron complex (C5Ph5)Cr(CO)3 reacts with halogens (C6H5I•Cl2, Br2, and I2) in C6H6 to yield the dimeric oxidation products [(C5Ph5)Cr(m-X)X]2 as thermally stable solids. Reactions with other chlorinating agents similarly yield [(C5Ph5)CrCl2]2. An X-ray crystal structure of [(C5Ph5)Cr(m-Cl)Cl]2 was obtained. The magnetic properties of the Cl₂ bridged dimer have been determined and modeled using the usual isotropic hamiltonian which yields J/k = –30 K. Low-temperature (77 K) Raman spectra of solid [(C5Ph5)CrX2]2 (X = Cl, I) allow assignments to be made for the metal-ring and metal halogen stretching modes in the low frequency region (< 600 cm-1). Tetrahydrofuran (THF) cleaves these dimers to yield complexes of the form (C5Ph5)CrX2(THF).

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

Chemistry and Biochemistry Faculty Publications

Electronic structure and bonding in metal phthalocyanines (Metal=Fe, Co, Ni, Cu, Zn, Mg) is investigated in detail using a density functional method. The metal atoms are strongly bound to the phthalocyanine ring in each case, by as much as 10 eV. The calculated orbital energy levels and relative total energies of these D_4h structures indicate that Fe and Co phthalocyanines have ³A_2g and ²E_g ground states, respectively, but that these states are changed upon interaction with strong-field axial ligands. The valence electronic structures of Fe and Co phthalocyanines differ significantly from those of …

Intrinsically Bent Dna In The Promoter Regions Of The Yeast Gal1–10 And Gal80 Genes, Ralph C. Bash, Jeff Vargason, P. Shing Ho, D. Lohr

Faculty Publications - Department of Biological & Molecular Science

Circular permutation analysis has detected fairly strong sites of intrinsic DNA bending on the promoter regions of the yeast GAL1–10 and GAL80 genes. These bends lie in functionally suggestive locations. On the promoter of the GAL1–10 structural genes, strong bends bracket nucleosome B, which lies between the UASG and the GAL1 TATA. These intrinsic bends could help position nucleosome B. Nucleosome B plus two other promoter nucleosomes protect the TATA and start site elements in the inactive state of expression but are completely disrupted (removed) when GAL1–10 expression is induced. The strongest intrinsic bend (;70°) lies at the downstream edge …

Cerumen Composition By Flash Pyrolysis-Gas Chromatography/Mass Spectrometry, Craig N. Burkhart, Michael A. Kruge, Craig G. Burkhart, Curtis Black

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Objective: To assess the chemical composition of cerumen by flash pyrolysis-gas chromatography/mass spectrometry.

Study Design: Collected earwax specimens were fractionated into residue and supernatant by means of deoxycholate. This natural bile acid produces significantly better disintegration of earwax in vitro than do presently available ceruminolytic preparations, and also has demonstrated excellent clinical results in vivo to date.

Patients: The sample for analysis was obtained from a patient with clinical earwax impaction.

Results: The supernatant is composed of simple aromatic hydrocarbons, C₅-C_{l 7} straight-chain hydrocarbons, a complex mixture of compounds tentatively identified as diterpenoids, …

Production Of A Novel Copper-Binding Ligand By Marine Synechococcus (Cyanobacteria) In Response To Toxic Concentrations Of Copper, Arunsi C. Brown, Andrew S. Gordon

Virginia Journal of Science

Marine Synechococcus spp. are extremely sensitive to copper toxicity. Some strains have been shown to produce high-affinity, extracellular ligands of unknown structure which form complexes with free cupric ion. They are also known to produce metallothioneins (MT) in response to cadmium and zinc stress. In the present study, marine Synechococcus PCC 73109 (Agmenellum quadruplicatum BG-1) (Van Baalen) was exposed to three concentrations of CuSO₄ for various times. Size exclusion chromatography, atomic absorption spectrophotometry, and reverse phase HPLC were used to isolate an intracellular copper binding ligand of low molecular weight (< 6,500 Da). The ligand was detected after exposure to ≥ 8 μM CuSO₄ for 2 hr in BG-11 medium. …

Use Of Py-Gc/Ms Analysis Techniques In Animal Waste Management: A Preliminary Survey Of Dairy Manures, Daniel L. Vaughn, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The increasing practice of industrial-scale agriculture tends to concentrate large masses of animal waste in relatively compact areas, potentially leading to excessive release of polluting nutrients into waterways during major storms. Anaerobic treatment conditions are generally favored to conserve nitrate N as an agricultural commodity. However, overall N contents in waste are often in excess of crop fertilization needs: storing excess N in soluble nitrate form increases pollution potential. Thus the perceived needs of agriculture and society-at-large become at odds. Organic nitrogen forms (e.g., proteins) are more environmentally stable and are less subject to unintentional release. Although U.S. farmers tend …

Photochemical Degradation Of 2,4-D And Atrazine In Well-Defined Media, Asher D. Ghertner

Honors Theses

Atrazine and 2,4-D are common herbicides used for crop, lawn, and rangeland management. Photochemical degradation has been proposed as one safe and efficient remediation strategy for both 2,4-D and Atrazine. In the presence of iron(llI) and hydrogen peroxide these herbicides decay by both thermal and light induced oxidation. Past studies have focused primarily on sun light as an energy source. This work provides a mechanistic description of herbicide degradation incorporating intermediate degradation products produced in the dark and under well-defined light conditions.

Study Of The Effects Of Co2(G) On The Fe(Ii)-Luminol Chemiluminescence System: Application To Ultra-Trace Analysis Of Fe(Ii), Sara Beth Lovitz

Honors Theses

The Fe(II)-catalyzed oxidation of luminol has been a well-accepted chemiluminescence method for the trace and ultra-trace analysis of Fe(II) and Fe(III) in natural waters. Investigation into this chemiluminescence system has shown that COlg) is essential to Fe-catalyzed luminol chemiluminescence. In absence of CO2(g) there is no chemiluminescent signal. These reactions worked well in the past because CO2 is present in most laboratory H20 supplies. Intentional saturation of CO2 results in a 5-fold increase for this conventional system. We propose a mechanism for CO 2(g) enhancement that includes formation of a CO2-superoxide intermediate, which serves as the oxidant of luminol to …

Exploratory Chemistry In Route To Aromatic Natural Products, Nicholas P. Bizier

Honors Theses

The focus of this research was the synthesis of two natural products, 1-methyl-s-(1,2,2-trimethy1cyclopentyl)-benzene (formally cuparene), and 3-(1,2dimethylcyclopenty1)-5-methylbenzene-l,2-diol (formally herbertene diol). Cuparene possesses anti-fungal and anti-arthritic properties. This molecule has been the target of a number of syntheses. Herbertene diol, a natural product itself, represents one retrosynthetic step back from mastigophorane; a compound isolated form the liverwort Mastigophora diaclolades. Mastigophorane has been shown to have neural network forming capabilities and has warranted complete synthetic efforts. Through the same chemistry involve in the formation of cuparene, we sought a route to herbertene diol in two steps. We report a successful route to …

Computational Studies Of Regularities In Bond Dissociation Enthalpies And Interactions Of Acetylthiocholine With Solvent Molecules, Wencui Zheng

Masters Theses

This thesis reports the results of two different research projects. One project is an evaluation of the feasibility of applying constant bond dissociation enthalpy ratios to neutral molecules for which one atom is from group 13 or group 17 and the other atom is from group 16. The other project attempts to validate the proposal that the aromatic residues lining the acetylcholinesterase (AChE) gorge will induce entry of acetylthiocholine (ATCh) into the gorge in a manner similar to that of the neural transmitter acetylcholine.

A total of thirty AB₂ and AB molecules have been examined, where A = B, …

Accumulation Of Heavy Metals In Freshwater Organisms: Assessment Of Toxic Interactions, Neylan Di̇ri̇lgen

Turkish Journal of Chemistry

Heavy metals are continuously released into the terrestrial environment by natural sources and human activities. The uptake and accumulation of heavy metals by plants promotes a mechanistic understanding of the biological significance of particular metal concentrations and distributions in biota. The toxicity of chromium, zinc, copper and cobalt ions and their binary mixtures are studied at varying test levels using duckweed as the test organism. The accumulation of metal ions are determined by atomic absorption spectroscopy. The type of toxic interactions in binary mixtures is assessed as `synergistic', `antagonistic' and `additive' by a statistical approach.

The Composition Of Essential Oils From Two Varieties Of Sideritis Erythrantha Var. Erythrantha And Var. Cedretorum, Nurhayat Tabanca, Neş'E Kirimer, K. Hüsnü Can Başer

Turkish Journal of Chemistry

Water distilled essential oils from two varieties of Sideritis erythrantha: var. erythrantha} and var. cedretorum, both endemic in Turkey, were analysed by GC/MS. The main components were characterized as \alpha -pinene (16.3-19.5%) and sabinene (6.1- 10.4%) for var. erythrantha; myrcene (21.9-24.3%) and \alpha -pinene (11.4- 12.4%) for var. cedretorum.

Incorporation Of Edta For The Elimination Of Metal Inhibitory Effects In An Amperometric Biosensor Based On Mushroom Tissue Polyphenol Oxidase, Arzum Erdem, Di̇lşat Özkan, Burcu Meri̇ç, Kağan Kerman, Mehmet Özsöz

Turkish Journal of Chemistry

Enzyme based biosensors are highly selective devices which rely on the specific binding of the target analyte (the substrate) to the active-site regions of the enzyme. The enzymatic reaction between mushroom tissue polyphenol oxidase and its substrate phenol is coupled with the use of potassium ferrocyanide (K_{4}Fe(CN)_{6}) as the mediator in ammonia buffer solution (pH 8.80). The response of devices is often affected by the presence of inhibitors, which combine with the free enzyme in a manner that prevents substrate binding. The objective of this study is to describe an efficient and yet simple strategy to eliminate the interference of …