Chemistry Commons^™

Design Synthesis And Evaluation Of Diterpenones As Potent Chemopreventive Agents For Aflatoxin B1 Induced Carcinogenesis In Human Liver Cells, Miguel Angel Zuniga

Theses and Dissertations

DESIGN, SYNTHESIS, AND EVALUATION OF DITERPENONES AS POTENT CHEMOPREVENTIVE AGENTS FOR AFB1 INDUCED CARCINOGENISIS IN HUMAN LIVER CELLS By Miguel A. Zuniga, Ph.D. A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at Virginia Commonwealth University. Major Director: Qibing Zhou, Ph.D Assistant Professor Department of Chemistry Terpene quinone methides (TPQMs) have been isolated from a variety of plants and show broad activities against bacteria, fungi, and cancerous cell lines. The biological activity has been attributed to the reactive electrophilic QM moiety, this structural feature has long been recognized as an intermediate in organic …

Structures And Reactivities Of Ionized And Metal Cation-Containing Acetylene Clusters, Paul O. Momoh

Theses and Dissertations

In this dissertation, the ion mobility technique is used to determine the structures of small acetylene cluster ions, (C2H2)1-3+, mass-selected from the largest ever reported ionized acetylene clusters. The technique is also used to characterize the reaction of acetylene clusters with water in an effort to elucidate thermochemistry and kinetics of some interesting ion-molecule reactions suspected to occur in interstellar clouds and other interplanetary bodies.A combination of ion mobility measurements, collision induced dissociation (CID), and theoretical calculations are used to provide the most conclusive evidence for the frequently hypothesized trimerization of ionized acetylene to form the benzene ion. The results …

Initial Studies On A Novel Target-Promoted Dna Alkylation System, Ting Xu

Theses and Dissertations

A novel target-promoted DNA alkylation system was designed, which consists of a DNA intercalating/alkylating quinone methide (QM) precursor, a removable amine linker, and a sequence-specific delivery. The QM in this system was regenerated by eliminating the amino linker promoted by the hydrophobic interaction between the target DNA and the intercalating QM precursor. Three alkylation model systems (methoxyl polycyclic system, intramolecular hydrogen bonding system and biaryl system) were proposed and synthesized. The potential DNA QM alkylation was investigated by deoxyadenosine (dA) and deoxyguanosine (dG) alkylation with the biaryl system. Only one deoxynucleoside adduct was observed when dA or dG reacted with …

Study Of Covalent And Non-Covalent Interactions In Ternary Systems Involving: Metal/Dna-Rna/Protein, Where Metal = Platinum(Ii), Palladium(Ii), Anzellotti I. Atilio

Theses and Dissertations

Ternary systems comprising DNA/RNA, proteins and one (or more) metal ion are generating increased interest due to its biological relevance. The knowledge gained from the study of these systems could provide important clues regarding the precise mechanism for transcription factors, repair proteins and metal complexes with anti-tumoral/anti-viral activities.The interactions occurring among the components of these ternary systems can be broadly grouped into covalent and non-covalent. The first kind of interactions can lead to the irreversible transformation of the components in the system, while the second is thought to be reversible leading to transient states and fluxionality. Both kinds of interaction …

Mechanisms Of Accumulation And Biological Consequences Of Polynuclear Platinum Compounds, Peyman Kabolizadeh

Theses and Dissertations

The novel trinuclear complex, BBR3464 has undergone Phase II clinical trials and been shown to have greater cytotoxicity and cellular uptake than clinical anticancer platinum drugs such as cisplatin, oxaliplatin and carboplatin. The clinical efficacy of cisplatin, oxaliplatin and carboplatin is limited due to acquired resistance and dose limiting side effects. The three major pharmacological factors contributing to the intrinsic cytotoxicity of, and cellular resistance to, platinum drugs are (i) cellular uptake and efflux of platinum; (ii) the frequency and nature of Pt-DNA adducts; and (iii) deactivating metabolic reactions with sulfur-containing nucleophiles. Since decreased cellular uptake of platinum drugs is …

Theoretical Investigation Of The Structure And Vibrational Frequencies Of Water And Methanol Complexes, John Michael Craig

Theses and Dissertations

Water and methanol are common solvents used in liquid chromatographic (LC) separations. It is highly desirable to model .the interactions of these solvents in order to better understand the nature of analyte solvation and its effect on retention. Therefore, structure and frequencies of complexes of these solvent molecules have been studied from a theoretical perspective as a first step in this direction. Specifically, cluster structures have been optimized at the RHF and MP2 levels in various flexible basis sets and with the counterpoise correction for basis set superposition error, and trends in the structure and binding energies of several clusters …

Reversible Paramagnetism To Ferromagnetism In Transition Metal-Doped Tio2 Nanocrystals Prepared By Microwave Irradiation, Garry Glaspell, Asit B. Panda, M. S. El-Shall

Chemistry Publications

TiO2nanoparticlesdoped with 1%, 5%, and 10% M (M=Co, Fe, and Ni) were prepared by microwave irradiation and characterized using x-ray diffraction, transmission electron microscopy, and magnetometry. The as-prepared samples are found to be paramagnetic at room temperature, with the magnetic susceptibility following the Curie-Weiss law in the investigated range of 2–300K. However, transformation from paramagnetism to room-temperature ferromagnetism (RTFM) was observed by hydrogenating the samples at 400°C. Reheating in air converted the samples back to paramagnetic while rehydrogenating the samples again induced ferromagnetism. It is argued that the reversible RTFM observed is due to interaction between the dopant metal ions …

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 …

Cation Occupancy Determination In Manganese Zinc Ferrites Using Fourier Transform Infrared Spectroscopy, M. D. Shultz, E. E. Carpenter, S. A. Morrison, S. Calvin

Chemistry Publications

The magnetic and electric properties of ferrites are influenced by the cation distribution within the crystalline spinel lattice. Methods such as extended x-ray-absorption fine structure(EXAFS) have been used to determine cation occupancies within the crystalline structure of materials such as manganesezincferrite (MZFO); however, it is not practical to be used for daily analysis. Fourier transform infrared (FTIR)spectroscopy is another technique which has the potential to determine cation occupancy while offering speed and convenience. In the literature it has been demonstrated that in ferrite systems FTIR data can be correlated to cation percentages when comparing tetrahedral (Td) and octahedral (Oh) sites. …

Optical Susceptibilities Of Supported Indium Tin Oxide Thin Films, Jonathan L. Humphrey, Darius Kuciauskas

Chemistry Publications

The third-order nonlinear optical susceptibility of indium tin oxide (ITO) thin films on glass substrates, χ(3)ITO, was determined in the near-IR spectral region using degenerate four wave mixing (DFWM)spectroscopy with 100fs laser pulses. A DFWM method for measuring thin films on thick substrates was refined for the characterization of films less than 100nm thick and applied to ∼25nm thick ITO films. It was found that χ(3)ITO is purely electronic at 900–1300nm (11000–7700cm−1) and has a value of (2.16±0.18)×10−18m2V−2. Theχ(3)ITO value reaches (3.36±0.28)×10−18m2V−2 at 1500nm (6700cm−1) due to two-photon absorption by free carriers (electrons). Ultrafast electron relaxation was also observed. The …

Magnetic And Mossbauer Spectroscopy Studies Of Nanocrystalline Iron Oxide Aerogels, E. E. Carpenter, J. W. Long, D. R. Rolison, M. S. Logan, K. Pettigrew, R. M. Stroud, L. Theil Kuhn, B. Rosendahl Hasen, S. Mørup

Chemistry Publications

A sol-gel synthesis was used to produce iron oxide aerogels. These nanocrystalline aerogels have a pore-solid structure similar to silica aerogels but are composed entirely of iron oxides. Mössbauer experiments and x-ray diffraction showed that the as-prepared aerogel is an amorphous or poorly crystalline iron oxide, which crystallized as a partially oxidized magnetite during heating in argon. After further heat treatment in air, the nanocrystallites are fully converted to maghemite. The particles are superparamagnetic at high temperatures, but the magnetic properties are strongly influenced by magnetic interactions between the particles at lower temperatures.

Quantitative Model For The Prediction Of Hydrodynamic Size Of Nonionic Reverse Micelles, Melissa A. Michaels

Theses and Dissertations

The sizes of nonionic reverse micelles were investigated as a function of the molecular structure of the surfactant, the type of oil, the total concentration of surfactant [NP], the ratio of NP4 to total surfactant (r), the water to surfactant molar ratio (ω), temperature, salt concentration, and polar phase. The basis of our investigation was nonylphenol polyethoxylates - NP4 and NP7. Micelle sizes were determined using dynamic light scattering (DLS). A central composite experimental design was used to quantitatively model reverse micelle size as a function of ω, [NP], and r. The model has demonstrated the capability of predicting the …

Enhancing The Third-Order Nonlinear Optical Properties Of Porphyrins And Molecular Wires, Jonathan L. Humphrey

Theses and Dissertations

The third-order nonlinear optical (NLO) properties of indium tin oxide (ITO) thin films, Fe3+, Mn3+, Co2+ 5,10,15,20-tetrakis-4hydroxytetraphenyl)porphyrin (TPP) films, and a series of ethynyl-linked azobenzene oligomers were investigated using degenerate four wave mixing (DFWM) with 100 fs laser pulses. To measure the NLO of ITO thin films, A DFWM method for measuring thin films on thick substrates was refined for the characterization of films less than 100 nm thick and applied to ITO films ~25 nm thick. It was found that the third-order nonlinear susceptibility of ITO, χ(3)ITO, is purely electronic at 900 - 1300 nm (11000 - 7700 cm-1) …

Chemometric Analysis Of Multivariate Liquid Chromatography Data: Applications In Pharmacokinetics, Metabolomics, And Toxicology, Sarah Elizabeth Graham Porter

Theses and Dissertations

In the first part of this work, LC-MS data were used to calculate the in-vitro intrinsic clearances (CLint) for the metabolism of p-methoxyrnethamphetamine (PMMA) and fluoxetine by the CYP2D6 enzyme using a steady-state (SS) approach and a new general enzyme (GE) screening method. For PMMA, the SS experiment resulted in a CLint of 2.7 ± 0.2 µL pmol 2D6-1min-1 and the GE experiment resulted in a CLint of 3.0 ± 0.6 µL pmol 2D6-1min-1. For fluoxetine, the SS experiment resulted in a CLint of 0.33 ± 0.17 µL pmol 2D6-1min-1 and the GE experiment resulted in a CLint of 0.188 …

Photochemical Applications To The Study Of Complexity Phospholipid Bilayer Environments, Christopher John Wohl Jr.

Theses and Dissertations

The physical and biophysical properties of a biological membrane model, phosphatidylcholine bilayers, were investigated using novel spiropyran/merocyanine molecular probes. The femtosecond to second dynamics of this system's photochemistry enabled bilayer viscosity and free volume to be studied over a broad time scale. Spiropyrans/merocyanines with different polarity were synthesized by changing the substitution of the indole moiety enabling determination of the trans-membrane properties of the bilayer. In addition, transient grating spectroscopy was used to study thermal energy transfer in phospholipid bilayers on a picosecond time scale.Femtosecond transient absorption spectroscopy was used to study the photo-induced spiropyran ring-opening and isomerization reactions that …

A Prelude To A Third Dimension Of The Periodic Table: Superatoms Of Aluminum Iodide Clusters, Naiche Owen Jones

Theses and Dissertations

Calculations have been carried out to investigate the stability and electronic structure of aluminum iodide clusters using first principles gradient-corrected density functional theory. Analysis of A113Ix-, A114Ix-, and A17I- clusters reveals that their stability is governed by the geometrically unperturbed A113-, A1142+, and A17+ units, respectively, that are demonstrated to constitute the compact cores of the clusters upon significant iodine content. The compact, icosahedral A113, icosahedral-like A1 14, and capped square bi-pyramid A17 superatom structures of the stable aluminum cores have an analogous electronic configuration to that of halogen, alkaline-earth, and alkaline atoms, respectively. Novel chemistry is demonstrated in superatoms, …

Synthesis Of Novel Antimycobacterials And A Fluorescent Sensor For Simple Carbohydrates, Brian Thomas Walker

Theses and Dissertations

Cell surface carbohydrates play an important role in a wide variety of biological processes such as inflammation, tumor metastasis, and viral and bacterial infection. The goal of our research has been two-fold. The first objective was the synthesis of antimycobacterial compounds. A mannose containing tetrasaccharide from the mannan core of lipoarabinomannan (LAM) of Mycobacterium tuberculosis has been synthesized using α-D-methylmannopyranoside as starting material and Koeings-Knorr reactions to couple saccharides. The synthesis was completed in nine steps and in 14% total yield. This compound should be useful in competitive inhibition studies with macrophages or as an immunological marker. We have successfully …

Thermodynamics Of Folding And Association Of Lattice-Model Proteins, Troy Cellmer, Dusan Bratko, John M. Prausnitz, Harvey Blanch

Chemistry Publications

Closely related to the “protein folding problem” is the issue of protein misfolding and aggregation. Proteinaggregation has been associated with the pathologies of nearly 20 human diseases and presents serious difficulties during the manufacture of pharmaceutical proteins. Computational studies of multiprotein systems have recently emerged as a powerful complement to experimental efforts aimed at understanding the mechanisms of proteinaggregation. We describe the thermodynamics of systems containing two lattice-model 64-mers. A parallel tempering algorithm abates problems associated with glassy systems and the weighted histogram analysis method improves statistical quality. The presence of a second chain has a substantial effect on single-chain …

Kinetics Of Ion-Induced Nucleation In A Vapor-Gas Mixture, Sergey P. Fisenko, David B. Kane, M. Samy El-Shall

Chemistry Publications

A general solution for the steady-state ion-induced nucleation kinetics has been derived, considering the differences between ion-induced nucleation and homogeneous nucleation. This solution includes a new effect for nucleation kinetics, the interaction of charged clusters with vapor molecules. Analytical expressions for the ion-induced nucleation rate have been obtained for the limiting cases of high and low thermodynamic barriers. The physical explanation of the so-called sign effect is proposed based on multipole expansion of an electric field of the cluster ion. This theory gives good agreement with experiments and is used to elucidate experimentally observed phenomena.

Gas Phase Studies Of Molecular Clusters Containing Metal Cations, And The Ion Mobility Of Styrene Oligomers, Edreese Housni Alsharaeh

Theses and Dissertations

This study is divided into three parts. Part I deals with the mechanism of the self-initiated polymerization (or thermal polymerization) of styrene in the gas phase. In this work, we present the first direct evidence for the thermally self-initiated polymerization of styrene in the gas phase. Our approach is based on on-line analysis of the gas phase Oligomers by mass-selected ion mobility. The mobility measurements provide structural information on the ionized oligomers based on their collision cross-sections (Ω) which depend on the geometric shapes of the ions. Theoretical calculations of possible structural candidates of the Oligomers ions are then used …

Experimental Studies On Nucleation, Nanoparticle's Formation And Polymerization From The Vapor Phase, Victor Maher Abdelsayed

Theses and Dissertations

This research is divided into three major parts. In part I, the critical supersaturations required for the homogeneous nucleation of 2,2,2-trifluorothanol (TFE) vapor have been measured over a temperature range (266-296 K) using an upward thermal diffusion cloud chamber (DCC). The measured supersaturations are in agreement with the predictions of both the classical and the scaled theory of nucleation. Moreover, the condensation of supersaturated TFE vapor on laser-vaporized magnesium nanoparticles has been studied under different experimental conditions, such as the supersaturation, the pressure and the electric field. In part II, the laser vaporization controlled condensation (LVCC) technique was used to …

Resonance Two Photon Ionization Study Of Binary Clusters Of Styrene With Polar Molecules, Hatem Ahmed Mahmoud

Theses and Dissertations

One-color resonance two-photo ionization (R2PI) spectra of mixed clusters of styrene molecule (S) with polar molecules [water (W), methanol (M), ethanol (E), and trifuoroethanol (T)] were measured through the S1←S0 transition of the styrene molecule. The spectra reveal a rapid increase in complexity with the number of polar molecules in the cluster, associated with van der Waal modes and isomeric forms. The spectral shifts of the cluster origins from the S1-S0 transition of the bare styrene molecule reflect the nature of the intermolecular interactions within the binary clusters. The obtained R2PI spectra xv were compared with the spectra of the …

Experimental And Theoretical Study Of Benzene (Acetonitrile)(N) Clusters, N=1-4, M. Samy El-Shall, George M. Daly, Douglas Wright

Chemistry Publications

Well-resolved spectra of benzene–acetonitrile binary clustersBAn, with n=1–4 have been obtained by the (one-color) resonant two-photonionization technique using the benzene’s B2u←A1g 000 and 610 resonances. The spectra reveal a rapid increase in complexity with the number of acetonitrile molecules in the cluster, associated with van der Waal modes and isomeric forms. While only single cluster origins are found for the benzene–acetonitrile (BA) and the BA2clusters, two and four distinct isomers are identified for the BA3 and BA4clusters, respectively. The origins of the BA and BA2clusters are blueshifted with respect to the free benzene molecule by 38 cm⁻¹ and 26 …

Fluoroalcohols As Nucleating Agents In Supersaturated Vapors: Efficient Clustering With Water In The Vapor Phase, V. Abdalsayed, Y. Ibrahim, M. Rusyniak, M. Rabeony, M. S. El-Shall

Chemistry Publications

Fluoroalcohols in small concentrations in the vapor phase display striking enhancing effects on homogeneous nucleation of supersaturated aliphatic alcohols, and on the formation of water clusters by supersonic expansion. The enhanced nucleationeffects are attributed to the surfactant properties of fluoroalcohols, which lower the surface tension of the growing droplets, and therefore lower the barrier to nucleation.

The Effect Of Carrier Gas Pressure On Vapor Phase Nucleation Experiments Using A Thermal Diffusion Cloud Chamber, D. Kane, S. P. Fisenko, M. Rusyniak, M. S. El-Shall

Chemistry Publications

Recent measurements of critical supersaturations for the vapor phase homogeneous nucleation of several substances using a diffusion cloud chamber technique exhibit a dependence on the pressure of the carrier gas used in the experiments. A model of droplet growth and motion in a diffusion cloud chamber, combined with the density and temperature profiles of the chamber is presented to explain the pressure dependent results. The model demonstrates that at higher carrier gas pressures the growth of the droplets is retarded and the optical scattering signal from the particles is reduced. It is concluded that the observed effect may not result …

Neural Networks In The Analysis Of Water-Soluble Sulfonylurea Herbicides Using An Lc/Ms, Joseph Michael Pompano

Theses and Dissertations

In this research, a hidden node pruning algorithm was developed for an artificial neural network (ANN) that automatically determined a more efficient size of the hidden layer, caused the ANN to resize itself, and then continued to train using a standard back-propagation algorithm. The hidden-node pruning algorithm was based on determining the number of significant eigenvalues present in the matrix of values produced by the hidden layer, starting with an excessive number of hidden nodes.

Eight sulfonylurea herbicides were used as the target analytes in this study. The ability of an ANN to simplify the sample preparation needed for analysis …

Directed Panspermia. 3. Strategies And Motivations For Seeding Star-Forming Clouds, Michael Noah Mautner

Chemistry Publications

Microbial swarms aimed at star-forming regions of interstellar clouds can seed stellar associations of 10 - 100 young planetary systems. Swarms of millimeter size, milligram packets can be launched by 35 cm solar sails at 5E-4 c, to penetrate interstellar clouds. Selective capture in high-density planetary accretion zones of densities > 1E-17 kg m-3 is achieved by viscous drag. Strategies are evaluated to seed dense cloud cores, or individual protostellar condensations, accretion disks or young planets therein. Targeting the Ophiuchus cloud is described as a model system. The biological content, dispersed in 30 μm, 1E-10 kg capsules of 1E6 freeze-dried microorganisms …

Termolecular Proton Transfer Reactions Assisted By Ionic Hydrogen Bond Formation: Reactions Of Aromatic Cations With Polar Molecules, George M. Daly, Michael Mautner, Y. B. Pithawalla, M. Samy El-Shall

Chemistry Publications

We present a new method that applies resonant‐two‐photon ionization to generate reactant ions selectively in the source of a high‐pressure mass spectrometer (R2PI‐HPMS) for kinetic and equilibrium studies. Applications to reactions that would be obscured otherwise in a complex system are illustrated in mixtures of benzene with polar solvent molecules (S). We observe a novel type of proton transferreactions from C₆H₆ ^+• to two S molecules where S=CH₃CN, CH₃OH, C₂H₅OH and CH₃COOC₂H₅, and from C₆H₅CH₃ ^+• to two …

Space-Based Genetic Cryoconservation Of Endangered Species, Michael Noah Mautner

Chemistry Publications

Genetic materials of endangered species must be maintained, for cryoconservation, permanently near liquid nitrogen temperatures below 77 K. Due to the instability of human institutions, permanent safety is best provided at storage sites that maintain passively the needed low temperatures, and provide barriers to access. The required conditions are available in permanently shaded polar lunar craters with equilibrium temperatures of 8 to 40 K, on the moons of Saturn, and unshielded storage satellites. A genetic depository can be incorporated readily into planned lunar programmes.

A Monte Carlo Study Of Methanol Clusters (Ch3oh)N, N=5-256, D. Wright, M. S. El-Shall

Chemistry Publications

The thermodynamic and structural properties of methanol clusters (CH₃OH) _N , N=5–15, 20, 30, 60, 128, 256 and the bulk liquid have been investigated using Monte Carlo simulation. Calculated properties as a function of size include electrostatic and dispersive contributions to the configurational energy, configurational heat capacities,fractal dimension, density profiles, order parameters characterizing dipole and bond vector orientation, and the Lindemann index. The clusterheat capacities as a function of N possess an interior maximum near N=128 and converge to the bulk value from above. Monocyclic, semiplanar structures are found to persist at liquidlike temperatures up to …