Chemistry Commons^™

Cest And Paracest Mr Contrast Agents, Ileana Hancu, W. Thomas Dixon, Mark Woods, Elena Vinogradov, A. Dean Sherry, Robert E. Lenkinski

Chemistry Faculty Publications and Presentations

In this review we describe the status of development for a new class of magnetic resonance (MR) contrast agents, based on chemical exchange saturation transfer (CEST). The mathematics and physics relevant to the description of the CEST effect in MR are presented in an appendix published in the online version only. We discuss the issues arising when translating in vitro results obtained with CEST agents to using these MR agents in in vivo model studies and in humans. Examples are given on how these agents are imaged in vivo. We summarize the status of development of these CEST agents, and …

Associative Learning In Larval Dosophila Melanogaster: The Role Of Heredity In Learning Speed And Persistence Of Leaning Into Adulthood, Jasmin Hicklen, Domonique Jones, Michelle Vieyra

Journal of the South Carolina Academy of Science

No abstract provided.

The Effects Of The Sumter Wastewater Treatment Plant On The Survival And Reproduction Of Ceriodaphnia Dubia In Chronic Toxicity Tests, Erin Worley, Pearl R. Fernandes, S. Michele Harmon, Jeff Steinmetz

Journal of the South Carolina Academy of Science

No abstract provided.

Isomerization As A Key Path To Molecular Products In The Gas-Phase Decomposition Of Halons, Aimable Kalume, Lisa George, Scott Reid

Chemistry Faculty Research and Publications

The decomposition of halons remains controversial concerning the branching between radical and molecular products. The latter channel, where it has been found, is presumed to occur via a constrained symmetric multicenter transition state. Isomerization pathways in the gas-phase chemistry of halons have rarely been considered, despite the fact that the iso-halons, which feature a halogen−halogen bond, are widely recognized as important reactive intermediates in condensed phases. In this Letter, detailed calculations and modeling of the unimolecular decomposition of several important halons, including CF₂Cl₂, CF₂Br₂, and CHBr₃, reveal that isomerization is …

Immobilization Of Motile Bacterial Cells Via Dip-Pen Nanolithography, Dorjderem Nyamjav, Sergey Rozhok, Richard C. Holz

Chemistry Faculty Research and Publications

A strategy to bind bacterial cells to surfaces in a directed fashion via dip-pen nanolithography (DPN) is presented. Cellular attachment to pre-designed DPN generated microarrays was found to be dependent on the shape and size of the surface feature. While this observation is likely due in part to a dense, well formed mercaptohexadecanoic acid (MHA) monolayer generated via DPN, it may also simply be due to the physical shape of the surface structure. Motile Pseudomonas aeruginosa bacterial cells were observed to bind to DPN generated mercaptohexadecanoic acid/poly-L-lysine (MHA/PLL) line patterns, 'blocks' made up of eight lines with 100 nm spacings, …

Investigation Of The Sources And Sinks Of Atmospheric Methane, Christopher Lee Butenhoff

Dissertations and Theses

The work presented here represents a number of independent studies that investigated various components of the CH₄ budget, namely the sources and sinks. We used a chemical-tracer model and created unique long-term time series of atmospheric CH₄, carbon monoxide (CO), molecular hydrogen (H₂), and methylchloroform (CH₃CCl₃) measurements at marine background air to derive histories of atmospheric hydroxyl radical (OH) - the main chemical oxidant of CH₄, biomass burning - an important source of CH₄ in the tropics, and emissions of CH₄ from rice paddies - one of …

The Stereochemistry Of Selected Supramolecular Complexes Of Cucurbiturils And The Effect Of Homogeneous Equilibria And Electron Transfer Of The Guest, Arumugam Thangavel

Doctoral Dissertations

"From a practical perspective, host-guest complexes are vehicles for understanding and using supramolecular interactions for purposeful function in sensors, molecular machines and switches, while from a fundamental perspective they may lead to novel supramolecular protection schemes in basic organic reactions. This dissertation examines the interactions of cucurbiturils as barrel-shaped hosts, exhibiting a hydrophobic cavity, with substituted benzoylpyrydinium, phenypyrylium, and diazaanthraquinonediium cations as guests. In water, N-methyl-4-(p-substituted benzoyl)pyridinium cations exist in equilibrium with their hydrated forms (gem-diols), whose concentrations depend on the para substituent. In the presence of cucurbit7uril (CB[7]), the benzoyl group shows a preference for the CB[7] cavity, and …

Nanoporous High Surface Area Silicas With Chelating Groups For Heavy Metal Ion Adsorption From Aqueous Solution, Kothalawalage Nuwan Kothalawala

Masters Theses

No abstract provided.

Ditopic Dithiophosphonates And Their Related Rotaxanes, Robert Ray Baum Jr.

Masters Theses

No abstract provided.

Conversion Of Racemic Ibuprofen To (S)-Ibuprofen, David Chavez-Flores

Open Access Theses & Dissertations

Ibuprofen is a common Non-Steroidal Anti-Inflammatory Drug (NSAID) sold as a racemic or equal mixture of (R) and (S) mirror-image enantiomers. Without patent protection, ibuprofen is an orphan drug even though one enantiomer, (S)-ibuprofen, provides relief three times faster than its racemic mixture with fewer side effects. The goal of this research was to develop a facile, environmentally benign (no waste of ibuprofen or catalysts), and inexpensive process to convert a commercially available racemic mixture of ibuprofen to the therapeutically active (S)-ibuprofen.

After many attempts, the most successful conversion of racemic ibuprofen to (S)-ibuprofen was the in situ racemization and …

Experimental Determination Of The Weiss Temperature Of Mn12-Ac And Mn12-Ac-Meoh, Christos Lampropoulos, Shiqi Li, Lin Bo, Bo Wen, M P. Sarachik, P Subedi, A D. Kent, Y Yeshurun, A J. Millis, S Mukherjee, G Christou

Chemistry Faculty Research and Scholarship

We report measurements of the susceptibility in the temperature range from 3.5 to 6.0 K of a series of Mn₁₂-ac and Mn₁₂-ac-MeOH samples in the shape of rectangular prisms of length l_c and square cross section of side l_a. The susceptibility obeys a Curie-Weiss law, χ=C/(T−θ), where θ varies systematically with sample aspect ratio. Using published demagnetization factors, we obtain θ for an infinitely long sample corresponding to intrinsic ordering temperatures T_c≈0.85 K and ≈0.74 K for Mn₁₂-ac and Mn₁₂-ac-MeOH, respectively. The difference in T_c for …

Reduced Electronic Spaces For Modeling Donor/Acceptor Interactions, Robert J. Cave, Stephen T. Edwards '06, John A, Kouzelos '07, Marshall D. Newton

All HMC Faculty Publications and Research

Diabatic states for donor (D) and acceptor (A) interactions in electron transfer (ET) processes are formulated and evaluated, along with coupling elements (H_DA) and effective D/A separation distances (r_DA), for reduced electronic spaces of variable size, using the generalized Mulliken Hush model (GMH), applicable to an arbitrary state space and nuclear configuration, and encompassing Robin−Day class III and as well as class II situations. Once the electronic state space is selected (a set of n ≥ 2 adiabatic states approximated by an orbital space based on an effective 1-electron (1-e) Hamiltonian), the charge-localized GMH …

Approaches Towards The Synthesis Of Bradyoxetin, Vanildo Martins Lima Braga

Electronic Theses and Dissertations

Quorum sensing bacteria produce and release chemical signal molecules (like N-acyl homoserine lactones, AHL) that increase in concentration as a function of cell density. The responses cover a large spectrum of process such as the virulence in Staphylococcus aureus, competence for DNA-uptake in Bacillus subtilis and Streptococcus pneumoniae, sporulation in Bacillus subtilis, conjugal plasmid transfer in Enterococcus faecalis, and bacteriocin production in lactic acid bacteria. The collapse of (AHL) signaling system in bacteria represents an attractive therapeutic approach towards the development of new antibiotics. Recently, a new extracellular modulator was isolated from a symbiotic bacterium (Bradyrhizobium japonicum) that nodulates soybean. …

Molecular Mechanics Studies Of Enzyme Evolutionary Mechanisms, Manoj Singh

All Dissertations

In the current dissertation, closely related studies to quantify the mechanism underlying enzyme evolution have been discussed. The HIV-1 protease and beta-lactamase enzymes were used as model systems for these studies. These are well known enzymes that are associated with drug resistance and are associated with the pathogenic diseases, and therefore, developing molecular level understanding of drug resistance through these enzymes has fundamental as well as practical importance.
In chapter 2, the relationship between errors in modeled protein structures and associated binding affinity predictions to small molecules is established. The results of this study are applicable in addressing a wide …

Synthesis And Characterization Of A [Ru(Bpy)2(Ncs)2] Derivative For Use As A Dye-Sensitizer In Nanocrystalline Solar Cells, Joel Thomas Kirner

Honors Program Theses

After extensive review of the field of dye-sensitized solar cells, the molecule [Ru(4,4’- dicarboxy-2,2’-bipyridine)(4,4’-di-(2-(2-pyridyl)ethenyl)-2,2’-bipyridine)(NCS)2] has been designed as an original contribution to the field. This dye sensitizer was chosen by derivatizing upon the structure of the standard sensitizer, cis-diisothiocyanatobis(4,4’-dicarboxylic acid-2,2’- bipyridine)ruthenium(II) (N3), by extending the conjugation of one bipyridine ligand. This structural derivatization should enhance light harvesting by red-shifting the dye’s absorbance and increasing the dye’s molar absorptivity, which should result in a dye-sensitized solar cell with higher efficiency. The Density Functional Theory (DFT) molecular orbital calculations of the new dye complex indicate that the HOMO is highly localized …

Toward A General Approach For Rna-Templated Hierarchical Assembly Of Split-Proteins, Jennifer L. Furman, Ahmed H. Badran, Oluyomi Ajulo, Jason R. Porter, Cliff I. Stains, David J. Segal, Indraneel Ghosh

Cliff Stains Publications

The ability to conditionally turn on a signal or induce a function in the presence of a user-defined RNA target has potential applications in medicine and synthetic biology. Although sequence-specific pumilio repeat proteins can target a limited set of ss- RNA sequences, there are no general methods for targeting ssRNA with designed proteins. As a first step toward RNA recognition, we utilized the RNA binding domain of argonaute, implicated in RNA interference, for specifically targeting generic 2-nucleotide, 3′ overhangs of any dsRNA. We tested the reassembly of a split-luciferase enzyme guided by argonaute-mediated recognition of newly generated nucleotide overhangs when …

The Efficacy Of Chemistry Outreach Programs On Middle School Students, Erica M. Dumeyer

Mahurin Honors College Capstone Experience/Thesis Projects

The current project was designed to determine if science outreach programs affect the attitude of the students toward science and increase the science content knowledge of the students participating in the program. Students from middle schools surrounding the Bowling Green area participated in the project. The data set includes a total of 850 students from 7th and 8th grade. Students were given a pre-test (taken several days before the presentation) and a post-test (taken several days after the presentation). The tests contain both subjective, affective as well as objective, content questions. The individual student pre-/post-tests were index numbered to protect …

Charge Transfer And Nanostructure Formation During Electroless Etching Of Silicon, Kurt W. Kolasinski

Chemistry Faculty Publications

No abstract provided.

Contact Angle Of A Nano-Drop On A Heterogeneous Surface, John Ritchie

Theses and Dissertations

CONTACT ANGLE OF A NANO-DROP ON A HETEROGENEOUS SURFACE By John Andre Ritchie, Master of Science A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science at Virginia Commonwealth University Virginia Commonwealth University, 2010 Major Director: Dr. Alenka Luzar, Professor of Chemistry

We examine the relation between contact angle of a nanodrop of water and the location of surface-water interaction energy at the perimeter and beneath the drop. Young’s equations gives the relationship between surface tension, at the three phase solid liquid vapor interface, and contact angle on a homogeneous surface. Cassie and Baxter …

Microporous Organic Polymers: Synthesis And Post Synthetic Modifications, Phillip Andrew Kerneghan

Theses and Dissertations (Comprehensive)

Microporous solids are an important class of materials that have been studied extensively. Newer to this field are Microporous Organic Polymers (MOPs) which are networks constructed from smaller organic building blocks and exhibit large surface areas, small pore sizes and low densities. It is due to these characteristics that MOPs have attracted attention because of their potential use in applications such as catalysis, chemical separations and gas storage.

In this thesis is described the synthesis of two novel MOPs, the first of which being a network based on benzenediboronic acid and triptycene building blocks linked together by boronate esters. This …

Alternative Splicing And Polyadenylation Contribute To The Generation Of Herg1 C-Terminal Isoforms, Qiuming Gong, Matthew R. Stump, A. Russell Dunn, Vivianne Deng, Zhengfeng Zhou

Faculty Publications - Department of Biological & Molecular Science

The human ether-a-go-go-related gene 1 (hERG1) encodes the pore-forming subunit of the rapidly activating delayed rectifier potassium channel. Several hERG1 isoforms with different N- and C-terminal ends have been identified. The hERG1a, hERG1b, and hERG1-3.1 isoforms contain the full-length C terminus, whereas the hERG1_USOisoforms, hERG1a_USO and hERG1b_USO, lack most of the C-terminal domain and contain a unique C-terminal end. The mechanisms underlying the generation of hERG1_USOisoforms are not understood. We show that hERG1 isoforms with different C-terminal ends are generated by alternative splicing and polyadenylation of hERG1 pre-mRNA. We identified an …

Mutational Studies Uncover Non-Native Structure In The Dimeric Kinetic Intermediate Of The H2a–H2b Heterodimer, Matthew R. Stump, Lisa M. Gloss

Faculty Publications - Department of Biological & Molecular Science

The folding pathway of the histone H2A–H2B heterodimer minimally includes an on-pathway, dimeric, burst-phase intermediate, I2. The partially folded H2A and H2B monomers populated at equilibrium were characterized as potential monomeric kinetic intermediates. Folding kinetics were compared for initiation from isolated, folded monomers and the heterodimer unfolded in 4 M urea. The observed rates were virtually identical above 0.4Murea, exhibiting a log-linear relationship on the final denaturant concentration. Below ∼0.4 M urea (concentrations inaccessible from the 4-M urea unfolded state), a rollover in the rates was observed; this suggests that a component of the I2 ensemble contains non-native structure that …

S-Nitrosothiols: Formation, Decomposition, Reactivity And Possible Physiological Effects, Moshood Kayode Morakinyo

Dissertations and Theses

Three biologically-active aminothiols cysteamine (CA), DL-cysteine (CYSH) and DL-homocysteine, were studied in this thesis. These aminothiols react with nitrous acid (HNO₂), prepared in situ, to produce S-nitrosothiols (RSNOs): S-nitrosocyteamine (CANO), S-nitrosocysteine (CYSNO) and S-nitrosohomocysteine (HCYSNO). They also react with S-nitrosoglutathione (GSNO) and S-nitroso-N-acetylpenicillamine (SNAP) through a transnitrosation reaction to produce their corresponding RSNOs. A detailed kinetics and mechanistic study on the formation of these RSNOs and their subsequent decomposition to release nitric oxide (NO) were studied.

For all three aminothiols the stoichiometry of their reaction with nitrous acid is strictly 1:1 with the formation of one mole …

Ambient Pressure Organic Semiconductor Thin Film Growth By Ambient Axisymmetric Spray, Kevin A. (Kevin Anthony) Bufkin

WWU Graduate School Collection

Interest in using organic semiconductors in applications such as large area displays, photovoltaic devices, and radio frequency identification tags stems in part from their prospects for enabling significantly reduced manufacturing costs compared to traditional inorganic semiconductors. However many of the best performing prototype devices produced so far have involved expensive or time-consuming fabrication methods, such as the use of single crystals or thin films deposited under high vacuum conditions. This thesis examines a new approach for growing low molecular weight organic crystalline films at ambient conditions based on an organic vapor-liquid-solid growth (OVLS) mechanism using thermotropic nematic liquid crystal (LC) …

Investigating Fabrication Methods For Micro Single-Chamber Solid Oxide Fuel Cells, Man Yang

Dissertations

A Solid Oxide Fuel Cell (SOFC) is a green energy technology that offers a cleaner and efficient alternative to fossil fuels. The efficiency and utility of SOFCs can be enhanced by fabricating miniaturized component structures within the fuel cell footprint. This research focuses on the microfabrication of parallel-connected inter-digitized design of micro single chamber SOFC (μ-SC-SOFCs). In this dissertation, candidate micro/nano fabrication techniques to precisely fabricate micro patterns on planar substrates have been studied. These include EBL, soft lithography, photolithography, and direct-writing. After analyzing preliminary results, two combinational approaches were further investigated. The first method involves the combination of the …

Structural Characterization Of Cytoskeleton Regulating Protein Villin And Its C-Terminal Modular Domains, Danielle A. Pfaff

WWU Graduate School Collection

Villin is a modular protein that regulates F-actin bundles in the microvilli of absorptive epithelial cells in the intestine. At low (10-100 nM) calcium levels, Villin is an F-actin bundling agent supporting the specialized brush border membrane of the absorptive epithelium. At intermediate micromolar calcium levels, Villin nucleates and caps the barbed ends of F-actin and in high (> 100 μM) calcium Villin is an F-actin severing agent (Bretsher & Weber, 1980; Glenney et al., 1980, 1981; Mooseker et al. 1980). The amino acid sequence of Villin has seven modular domains. The first six Villin domains (D1-D6) form a "core" …

Transition States In Ei Reactions, Charles A. Kingsbury

Chemistry Department: Faculty Publications

The pyrolysis of amine oxides, sulfoxides, selenoxides, and esters to form alkenes is believed to be a concerted reaction with a cyclic transition state. Phosphine oxides, sulfones, and nitro compounds are unreactive. This study seeks to identify reasons for the lack of reactivity of the latter. Transition states were located for all substrates progressing from RHF/3-21G* to the MP2/6-31+G(d,p) level (in certain cases). For sulfones and nitro compounds, two possible reasons for lack of reactivity were considered: (1) Atoms approaching one another in the transition state may be considered to participate in a local n_O→σ*_{CH …}

Synthesis And Applications Of Ring Opening Metathesis Polymerization Based Functional Block Copolymers, Sanchita Biswas

Electronic Theses and Dissertations

Ring opening metathesis polymerization (ROMP) is established as one of the efficient controlled living polymerization methods which have various applications in polymer science and technology fields. The research presented in this dissertation addresses several applications of multifunctional well-defined norbornene-based block copolymers synthesized by ROMP using ruthenium-based Grubbs catalysts. These novel block copolymers were applied to stabilize maghemite nanoparticles, creating the superparamagnetic polymeric nanocomposites. The Jaggregation properties of the porphyrin dyes were improved via self-assembly with a customized norbornene polymer. Novel multimodal copolymer probes were synthesized for two-photon fluorescence integrin-targeted bioimaging. In Chapter 1 a brief overview of ROMP along with …

Physicochemical And Thermochemical Properties Of Sulfonated Poly(Etheretherketone) Electrolyte Membranes, Stephen Rhoden

Electronic Theses and Dissertations

Fuel cells have long been seen as an alternative to combustion powered and diesel powered engines and turbines. Production of energy via a fuel cell conversion method can generate up to 60% efficiency in comparison to 30% using a combustion powered engine, with low co-production of harmful side-products. The polymer electrolyte membrane (PEM) adapted for the fuel cell application is one of the main components that determines the overall efficiency. This research project was focused towards novel PEMs, such as sulfonated poly(etheretherketone) or SPEEK, which are cost-efficient and robust with high proton conductivities under hydrated conditions. The degree of sulfonation …

Statistical Analysis Of Visible Absorption Spectra And Mass Spectra Obtained From Dyed Textile Fibers, Katie Margaret White

Electronic Theses and Dissertations

The National Academy of Sciences recently published a report which calls for improvements to the field of forensic science. Their report criticized many forensic disciplines for failure to establish rigorously-tested methods of comparison, and encouraged more research in these areas to establish limitations and assess error rates. This study applies chemometric and statistical methods to current and developing analytical techniques in fiber analysis. In addition to analysis of commercially available dyed textile fibers, two pairs of dyes are selected based for custom fabric dyeing on the similarities of their absorbance spectra and dye molecular structures. Visible absorption spectra for all …