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Evaluation Of Chlorinated Solvent Removal Efficiency Among Three Wetland Plant Species: A Mesocom Study, Jun Yan

Theses and Dissertations

Different species of plants need to be studied individually to compare the remediation efficiency of each species. This research will study three different wetland plants species and an unplanted control, under a laboratory setting. Each plant has a different characteristic favorable for chlorinated solvent degradation. Eleocharis erythropoda (Spike Rush) are plants with thin tube like leaves and large root mass. Carex comosa (Bearded Sedge) has broad leaves and Scirpus atrovirens (Green Bulrush) are broad leafed wetland plants with a long flowering stem during reproduction. PCE will be injected into the plant mesocosm and any possible PCE degradation will be observed. …

Macrocyclic Antibiotics As Separation Agents, Daniel W. Armstrong

Chemistry Faculty Research & Creative Works

Macrocyclic antibiotics having ring structures with at least 10 members act as separation agents in crystallization, precipitation, filtration, electrophoresis, and chromatography. The macrocyclic antibiotics include ansamacrolides, macrolides, macrocyclic peptides, polyenes and derivatives thereof. The process has been found to be especially advantageous for separation of optical isomers by electrophoresis and chromatography.

Preparation Of Silica-Coated Lanthanum-Strontium Manganite Particles With Designable Curie Point, For Application In Hyperthermia Treatments, Vuk Uskoković, Aljoša Košak, Miha Drofenik

Pharmacy Faculty Articles and Research

Silica-coated lanthanum–strontium manganite particles with La_0.76Sr_0.24MnO_3+δ stoichiometric formula, exhibiting Curie temperature at ∼40°C, were prepared by using a traditional solid-state method of synthesis of magnetic ceramic particles, followed by milling and a low-temperature coating procedure in an aqueous alcoholic alkali medium. The properties of the obtained material establish it as a potential candidate for self-regulated power-absorbing and temperature-controlling materials in hyperthermia treatments. Moreover, core-comprising LaSr–manganites with different stoichiometries, ranging from La_0.5Sr_0.5MnO_3+δ to LaMnO_3+δ, were synthesized, with magnetic and structural properties examined thereof. Herein reported findings can potentially be …

Nmr Studies Of Escherichia Coli Acyl Carrier Protein: Dynamic And Structural Differences Of The Apo- And Holo-Forms, Yangmee Kim, Evgenii L. Kovrigin, Ziad Eletr

Chemistry Faculty Research and Publications

Two indicators of conformational variability of Escherichia coli acyl carrier protein (ACP) have been investigated, namely backbone dynamics and chemical shift variations of ACP. Hydrophobic interactions between the 4′-PP prosthetic group and the hydrophobic pocket enclosed by the amphipathic helices resulted in chemical shift perturbations in the residues near the prosthetic group binding sites and contact sites in the hydrophobic pockets upon conversion from apo- to holo-forms. At pH 7.9, destabilization of ACP due to negative charge repulsions and the deprotonated state of His 75 resulted in observed chemical shift changes in the C-terminal region. Model-free analysis showed that the …

Kinetic And Spectroscopic Characterization Of The E134a- And E134d-Altered Dape-Encoded N-Succinyl-L,L-Diaminopimelic Acid Desuccinylase From Haemophilus Influenzae, Ryan S. Davis, David L. Bienvenue, Sabina I. Swierczek, Danuta M. Gilner, Lakshman Rajagopal, Brian Bennett, Richard C. Holz

Physics Faculty Research and Publications

Glutamate-134 (E134) is proposed to act as the general acid/base during the hydrolysis reaction catalyzed by the dapE-encoded N-succinyl-l,l-diaminopimelic acid desuccinylase (DapE) from Haemophilus influenzae. To date, no direct evidence has been reported for the role of E134 during catalytic turnover by DapE. In order to elucidate the catalytic role of E134, altered DapE enzymes were prepared in which E134 was substituted with an alanine and an aspartate residue. The Michaelis constant (K _m) does not change upon substitution with aspartate but the rate of the reaction changes drastically in the following order: glutamate (100% …

High-Resolution Studies Of Tropolone In The S 0 And S 1 Electronic States: Isotope Driven Dynamics In The Zero-Point Energy Levels, John C. Keske, Wei Lin, Wallace C. Pringle, Stewart E. Novick, Thomas A. Blake, David F. Plusquellic

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Rotationally resolved microwave (MW) and ultraviolet (UV) spectra of jet-cooled tropolone have been obtained in S0 and S1 electronic states using Fourier-transform microwave and UV-laser/molecular-beam spectrometers. In the ground electronic state, the MW spectra of all heavy-atom isotopomers including one O18 and four C13 isotopomers were observed in natural abundance. The OD isotopomer was obtained from isotopically enriched samples. The two lowest tunneling states of each isotopomer except O18 have been assigned. The observed inversion splitting for the OD isotopomer is 1523.227(5) MHz. For the asymmetric C13 structures, the magnitudes of tunneling-rotation interactions are found to diminish with decreasing distance …

Measurement, Characterization, And Source Apportionment Of The Major Chemical Components Of Fine Particulate Material, Including Semi-Volatile Species, Brett D. Grover

Theses and Dissertations

The promulgation of revised standards for atmospheric fine particles (PM2.5) by the US EPA has sparked renewed interest in the ability to accurately measure and characterize suspended atmospheric particulate matter. Semi-volatile material (SVM), consisting of ammonium nitrate and semi-volatile organic material (SVOM), is not accurately measured by EPA accepted methods such as the Federal reference method (FRM) or Tapered Element Oscillating Microbalance (TEOM). However, SVM is often a major fraction of urban aerosols. Recent advances in atmospheric sampling instrumentation allowed for the semi-continuous characterization of urban PM2.5, including SVM. The Filter Dynamic Measurement System (FDMS) was shown to measure total …

Rhodium-Catalyzed Asymmetric Hydrogenation Using Self-Assembled Chiral Bidentate Ligands, James M. Takacs, Kittichai Chaiseeda, Shin A. Moteki, D. Sahadeva Reddy, Di Wu, Kusumlata Chandra

James M. Takacs Publications

The chirality-directed self-assembly of bifunctional subunits around a structural metal-typically, zinc(II)-is used to form a heteroleptic complex in which a second set of ligating groups are suitably disposed to bind a second metal, forming a heterobimetallic catalyst system. We find that subtle changes in the structural backbone (i.e., ligand scaffold) of such chiral bidentate self-assembled ligands (SALs) can be used to manipulate the ligand topography and chiral environment around catalytic metal; thus, the scaffold can be optimized to maximize asymmetric induction. Using this combinatorial strategy for ligand synthesis, a preliminary study was carried out in which a library of 110 …

A Topology-Constrained Distance Network Algorithm For Protein Structure Determination From Noesy Data, Yuanpeng Janet Huang, Roberto Tejero, Robert Powers, Gaetano T. Montelione

Robert Powers Publications

This article formulates the multidimensional nuclear Overhauser effect spectroscopy (NOESY) interpretation problem using graph theory and presents a novel, bottom-up, topology-constrained distance network analysis algorithm for NOESY cross peak interpretation using assigned resonances. AutoStructure is a software suite that implements this topology- constrained distance network analysis algorithm and iteratively generates structures using the three-dimensional (3D) protein structure calculation programs XPLOR/CNS or DYANA. The minimum input for AutoStructure includes the amino acid sequence, a list of resonance assignments, and lists of 2D, 3D, and/or 4D-NOESY cross peaks. AutoStructure can also analyze homodimeric proteins when X-filtered NOESY experiments are available. The quality …

Changes In Dna Bending And Flexing Due To Tethered Cations Detected By Fluorescence Resonance Energy Transfer, Sarah L. Williams, Laura K. Parkhurst, Lawrence J. Parkhurst

Lawrence Parkhurst Publications

Local DNA deformation arises from an interplay among sequence-related base stacking, intrastrand phosphate repulsion, and counterion and water distribution, which is further complicated by the approach and binding of a protein. The role of electrostatics in this complex chemistry was investigated using tethered cationic groups that mimic proximate side chains. A DNA duplex was modified with one or two centrally located deoxyuracils substituted at the 5-position with either a flexible 3-aminopropyl group or a rigid 3-aminopropyn-1-yl group. End-to-end helical distances and duplex flexibility were obtained from measurements of the time-resolved Fö̈rster resonance energy transfer between 5’- and 3’-linked dye pairs. …

A Bidomain Nonribosomal Peptide Synthetase Encoded By Fum14 Catalyzes The Formation Of Tricarballylic Esters In The Biosynthesis Of Fumonisins, Kathia Zaleta-Rivera, Chunping Xu, Fengan Yu, Robert A. E. Butchko, Robert H. Proctor, Maria E. Hidalgo-Lara, Ashraf S. Raza, Patrick Dussault, Liangcheng Du

Patrick Dussault Publications

Fumonisins are a group of polyketide-derived mycotoxins produced by Fusarium Verticillioides, a filamentous fungus infecting corn and contaminating food and feeds. Fumonisins contain two tricarballylic esters that are critical for toxicity. Here, we present genetic and biochemical data for the esterification mechanism. FUM14 in F. Verticillioides has been deleted by homologous recombination, and the resultant mutant lost the ability to produce fumonisins. Two new metabolites, HFB₃ and HFB₄, which are biosynthetic precursors of fumonisins lacking the tricarballylic esters, were detected in the mutant. The results suggest that FUM14 is required for the esterification of fumonisins. FUM14 …

Characterization, Functionalization And Applications Of Alkyl Monolayers On Silicon Surfaces, Guilin Jiang

Theses and Dissertations

Investigations were performed on the stability, mechanism of formation and an application of alkyl monolayers chemomechanically prepared on silicon surfaces. A new method of surface modification, laser-activation modification of surfaces (LAMS), and multivariate analyses of time-of-flight secondary ion mass spectrometry (ToF-SIMS) images of LAMS spots were also reported. X-ray photoelectron spectroscopy (XPS) and other data show that alkyl monolayers prepared by scribing silicon under 1-iodoalkanes and 1-alkenes were stable over extended periods of time to air, water, a boiling acid and Al Ka X-rays. The stability is attributed to direct Si-C bonding in the monolayers. The observation that the oxygen …

1,3-Indane-Based Chromogenic Calixpyrroles With Push-Pull Chromophores: Synthesis And Anion Sensing, Ryuhei Nishiyabu, Pavel Anzenbacher Jr.

Chemistry Faculty Publications

Knoevenagel condensation of 2-formyl-octamethylcalix[4]pyrrole with selected 1,3-indanedione derivatives yields calix[4]pyrrole anion sensors with push-pull chromophores displaying strong intramolecular charge transfer. The push-pull feature results in augmented signal output as well as in dramatic changes in anion selectivity exemplified by a 50-fold increase in acetate vs chloride selectivity compared to the parent calix[4]pyrrole.

Femtosecond Nuclear Motion Of Hcl Probed By Resonant X-Ray Raman Scattering In The Cl 1s Region, Marc Simon, Loic Journel, Stephane Carniato, Richard Taieb, I. Minkov, Faris Gel'mukhanov, P. Salek, H. Agren, Renaud Guillemin, Wayne C. Stolte, A. C. Hudson, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Femtosecond dynamics are observed by resonant x-ray Raman scattering (RXS) after excitation along the dissociative Cl 1s→6ơ* resonance of gas-phase HCl. The short core-hole lifetime results in a complete breakdown of the common nondispersive behavior of soft-x-ray transitions between parallel potentials. We evidence a general phenomenon of RXS in the hard-x-ray region: a complete quenching of vibrational broadening. This opens up a unique opportunity for superhigh resolution x-ray spectroscopy beyond vibrational and lifetime limitations.

Enzyme Dynamics Along The Reaction Coordinate: Critical Role Of A Conserved Residue, Evgenii L. Kovrigin, J. Patrick Loria

Chemistry Faculty Research and Publications

Conformational flexibility of the enzyme architecture is essential for biological function. These structural transitions often encompass significant portions of the enzyme molecule. Here, we present a detailed study of functionally relevant RNase A dynamics in the wild type and a D121A mutant form by NMR spin-relaxation techniques. In the wild-type enzyme, the dynamic properties are largely conserved in the apo, enzyme−substrate, and enzyme−product complexes. In comparison, mutation of aspartic acid 121 to alanine disrupts the timing of active-site dynamics, the product-release step, and global conformational changes, indicating that D121 plays a significant role in coordinating the dynamic events in RNase …

Ligand-Based Design Of Dopamine Reuptake Inhibitors : Fuzzy Relational Clustering And 2-D And 3-D Qsar Modleing, Milind Misra

Dissertations

As the three-dimensional structure of the dopamine transporter (DAT) remains undiscovered, any attempt to model the binding of drug-like ligands to this protein must necessarily include strategies that use ligand information. For flexible ligands that bind to the DAT, the identification of the binding conformation becomes an important but challenging task. In the first part of this work, the selection of a few representative structures as putative binding conformations from a large collection of conformations of a flexible GBR 12909 analogue was demonstrated by cluster analysis. Novel structurebased features that can be easily generalized to other molecules were developed and …

Study Of Organic Reactions In Pyridinium-Based Ionic Liquids, Ying Xiao

Dissertations

Recently, ionic liquids have attracted a lot of attention as novel materials for organic transformations. This is due to their unique properties, which make them suitable substitutes for organic solvents. Most of the available literature is focused on the application of imidazolium-based ionic liquids for organic reactions, while very limited information is available on the application of pyridinium-based ionic liquids.

In this study, two different ionic liquids, 1 -ethyl-pyridinium tetrafluoroborate ([EtPy]⁺[BF₄]^-) and 1 -ethyl-pyridinium trifluoroacetate ([EtPy]⁺[CF₃COO]^-) have been investigated. Compared to previous reports, the synthetic technique for preparation …

Domain Architecture Of Protein-Disulfide Isomerase Facilitates Its Dual Role As An Oxidase And An Isomerase In Ero1p-Mediated Disulfide Formation, Mohini Kulp, Eva Maria Frickel, Lars Ellgaard, Jonathan S. Weissman

Chemistry: Faculty Publications

Native disulfide bond formation in eukaryotes is dependent on protein-disulfide isomerase (PDI) and its homologs, which contain varying combinations of catalytically active and inactive thioredoxin domains. However, the specific contribution of PDI to the formation of new disulfides versus reduction/rearrangement of non-native disulfides is poorly understood. We analyzed the role of individual PDI domains in disulfide bond formation in a reaction driven by their natural oxidant, Ero1p. We found that Ero1p oxidizes the isolated PDI catalytic thioredoxin domains, A and A′ at the same rate. In contrast, we found that in the context of full-length PDI, there is an asymmetry …

Global Characterization Of Porcine Intrauterine Proteins During Early Pregnancy, Jean-Patrick R. Kayser, Jong G. Kim, Ronald Cerny, Jeffrey L. Vallet

Ronald Cerny Publications

Total protein secreted in the intrauterine lumen increases between day 10 and 13 post-estrus in both cyclic and pregnant gilts. The objective of this experiment was to identify those intrauterine proteins whose secretion changes during this time period. Sixteen mature gilts were either mated (day 0) or remained cyclic and were slaughtered at either day 10 or day 13 (n = 4 per status by day). At slaughter, each uterine horn was flushed with 20 ml Minimal Essential Medium. Flushings were dialyzed extensively against distilled water. A 0.5 ml aliquot of each was lyophilized, subjected to two-dimensional PAGE, and protein …

Orientational Correlations In Liquid Acetone And Dimethyl Sulfoxide: A Comparative Study, Sylvia E. Mclain, Alan K. Soper, Alenka Luzar

Chemistry Publications

The structure of acetone and dimethyl sulfoxide in the liquid state is investigated using a combination of neutron diffractionmeasurements and empirical potential structure refinement (EPSR) modeling. By extracting the orientational correlations from the EPSR model, the alignment of dipoles in both fluids is identified. At short distances the dipoles or neighboring molecules are found to be in antiparallel configurations, but further out the molecules tend to be aligned predominately as head to tail in the manner of dipolar ordering. The distribution of these orientations in space around a central molecule is strongly influenced by the underlying symmetry of the central …

Optimization Of Long Range Electron Transfer For Solar Energy, Randall H. Goldsmith

Link Foundation Energy Fellowship Reports

Organic photovoltaics have the potential to become an accessible form of alternative energy production because of their ease of manufacture via traditional printing techniques and consequent low cost.1 However, the simplicity of device manufacture belies the complex cascade of processes that allow light to be efficiently converted into electrical power.2 Electron transfer (ET) events constitute the most critical steps. ET is known to be governed by a complex function of many system-specific variables including distance, orientation, and energetics of the donor and acceptor species.3

Spectroscopic And Thermodynamic Analysis Of Co Rebinding And Photodissociation From Fe (Ii) Lpo, Dustin Michael Lockney

Theses, Dissertations and Capstones

Lactoperoxidase (LPO) is a heme peroxidase found in tears, milk, saliva, and cervical fluids that has bactericidal activity. The bactericidal nature of LPO is due to its ability to oxidize halides and pseudohalides in the presence of H2O2. Full understanding of the catalytic cycle of LPO requires detailed characterization of the mechanism of ligand binding to the enzyme active site. This includes a dynamic and energetic description of conformational changes associated with heme-ligand interactions. Photoacoustic calorimetry is applied to determine the kinetics and magnitude of reaction volume and enthalpy changes for CO dissociation from CO-LPO. Time-resolved absorption spectroscopy was used …

Scanning Probe Microscopy And Oxidation Of Silicon At Breakdown Voltages, Thabo Gcwabaza

Theses, Dissertations and Capstones

The growing importance of Scanning Probe Microscopy (SPM) as a tool for nanofabrication is opening many avenues in lithography nano-science. One type of Scanning Probe Lithography involves electrochemistry at the tip/substrate interface. Atomic Force Microscopy (AFM) with conductive tips and substrates was used in our study to both pattern and image those patterns on silicon substrates. Our long-term objective is to design and fabricate micron-scale patterns of nanometer sized spots on silicon chips that can serve as attachment sites for DNA based nano-arrays. In order to fabricate such substrates a study of the underlying electrochemistry was required. A most promising …

Design And Implementation Strategies For Peer-Led Team Learning In Organic Chemistry, Stephen K. Manu

Capstone Research Projects

Peer-Led Team Learning (PLTL), which initially began as an effort to improve undergraduate chemistry education, has shown the potential to improve learning among college students in all disciplines. The model applies the desired qualities of teamwork to learning. This project is aimed at designing and setting up a PLTL Workshop at Southern Adventist University (SAU). Nine students currently taking organic chemistry at SAU volunteered to participate in the project. In order to determine the effectiveness of the project, test scores were collected and analyzed for any apparent trends, and an end-of-semester survey was conducted. The results indicate that the program …

Purified Water: A Closer Look At Bottled Waters And Their Claims, Henry Piñango

Capstone Research Projects

The claims made by three bottled water manufacturers were checked through a series of tests. CHA ™ (by Abundant Life CHA ™ Water Company in Chattanooga, TN), Penta ® (by Bio-hydration Research Lab, Inc.), and Mountain Fresh superoxygenated water (Collegedale, TN) were the subject of this study. Three tests were done on these samples: pH level, dissolved oxygen, and osmosis rate test. The pH level test confirmed the claim that CHA ™ water is alkaline (pH = 9.6); the other samples tested had pH levels ranging from 6.5 to 7.6. The dissolved oxygen test compared the oxygen concentration of several …

Structure And Vibrational Spectra Of Mononitrated Benzo [A] Pyrenes., Kefa Karimu Onchoke, Christopher M. Hadad, Prabir K. Dutta

Faculty Publications

The molecules benzo[a]pyrene (BaP) and 1-, 3-, and 6-nitrobenzo[a]pyrene (1-NBaP, 3-NBaP, 6-NBaP) are currently of significant interest due to their presence in respirable combustion exhaust particulates and their mutagenic and carcinogenic properties. Structure−function correlations as well as spectroscopic signatures for trace analysis are necessary for these benzo[a]pyrene derivatives. In this paper, detailed infrared and Raman spectroscopic data of BaP and its three mononitrated isomers are provided for the first time. By utilizing density functional theory (DFT, B3LYP method with 6-311+G** basis set), the molecular geometries and the vibrational spectra are calculated. Good agreement is …

Exchange Coupling And Contribution Of Induced Orbital Angular Momentum Of Low-Spin Fe^3+ Ions To Magnetic Anisotropy In Cyanide-Bridged Fe2m2 Molecular Magnets: Spin-Polarized Density-Functional Calculations, Stephen Holmes, Kyungwha Park

Chemistry & Biochemistry Faculty Works

Electronic structure and intramolecular exchange constants are calculated for three cyanide-bridged molecular magnets, [Tp⋆FeIII(CN)3MII(DMF)4]2(OTf)2∙2DMF (MII=Mn,Co,Ni) (abbreviated as Fe2Mn2, Fe2Co2, and Fe2Ni2) that have been recently synthesized, within a generalized-gradient approximation in spin-polarized density-functional theory (DFT). Here Tp⋆=[C3(CH3)2HN2]3BH, OTf=O3SCF3, and DMF=HCON(CH3)2. Due to strong ligand fields present in the [Tp⋆FeIII(CN)3]− units, the Fe3+ ions exhibit a low ground-state spin of S=1/2. Our calculations show that the metal ions in the Fe2Mn2 molecule interact antiferromagnetically via cyanide ligands, while those in the Fe2Co2 and Fe2Ni2 molecule interact ferromagnetically. The calculations also suggest that the smallest gaps between the highest occupied molecular orbital …

Development Of Dirhodium Sugar-Substituted Carboxylate And Acetamide Complexes And Evaluation Of Their Potential As Lectin Inhibitors, Bethany Masten

Undergraduate Review

No abstract provided.

Nmr Investigations Of Natural Organic Matter In Forest Ecosystems, Chris E. Johnson

Civil and Environmental Engineering - All Scholarship

No abstract provided.

1,1´-Diethyl-2,2´,3,3´,4,4´,5,5´-Octamethylferrocenium Tetracyanoethylenide, [Fe(C5etme4)2]+[Tcne]–, A Charge-Transfer Salt Magnetic Solid With A Novel Structural Motif, T. David Harris, Michael Castellani, Arnold L. Rheingold, William M. Reiff, Gordon T. Yee

Chemistry Faculty Research

1,1′-Diethyl-2,2′,3,3′,4,4′,5,5′-octamethylferrocene has been utilized as a one-electron donor in the synthesis of a tetracyanoethylene charge-transfer salt, [Fe(C₅EtMe₄)₂]⁺[TCNE]⁻. Structural characterization shows that it adopts an arrangement of anions and cations completely different from the usual π stacking seen in analogous decamethylferrocenium compounds. The TCNE radical sits along side of the ferrocene, nearly perpendicular to the planes of the C₅ rings. The nearly square geometry of the TCNE anion creates disorder over two orientations. [Fe(C₅EtMe₄)₂]⁺[TCNE]⁻ is a simple paramagnet exhibiting neither long-range …