Physical Sciences and Mathematics Commons^™

High Resolution X-Ray Diffraction Analysis Of Cb1 Receptor Antagonists As A Means To Explore Binding Affinity, Steven P. Fournet

University of New Orleans Theses and Dissertations

Abstract

Charge density studies have been conducted on ten CB₁ cannabinoid receptor antagonists via high resolution x-ray crystallography. Bond critical point values and various other properties derived from these studies including the electrostatic potential were analyzed in correlation to the affinity of each compound with the CB₁ receptor. Correlation/anti-correlation was found between several properties and K_i. The data was also interpreted by principal component analysis with three principal components accounting for 85% of the data variation. Data mining was limit due to the low sample count and the requirements set for the inclusion of correlated/anti-correlated variables …

High Yield Solvothermal Synthesis Of Hexaniobate Based Nanocomposites Via The Capture Of Preformed Nanoparticles In Scrolled Nanosheets, Shivaprasad Reddy Adireddy

University of New Orleans Theses and Dissertations

The ability to encapsulate linear nanoparticle (NP) chains in scrolled nanosheets is an important advance in the formation of nanocomposites.These nanopeapods (NPPs) exhibit interesting properties that may not be achieved by individual entities. Consequently, to fully exploit the potential of NPPs, the fabrication of NPPs must focus on producing composites with unique combinations of morphologically uniform nanomaterials. Various methods can produce NPPs, but expanding these methods to a wide variety of material combinations can be difficult. Recent work in our group has resulted in the in situ formation of peapod-like structures based on chains of cobalt NPs. Building on this …

Synthesis Of Novel Azetidines, Amber Thaxton

University of New Orleans Theses and Dissertations

Azetidine is a four-membered nitrogen-containing heterocyclic ring that has recently received a great deal of attention as a molecular scaffold for the design and preparation of biologically active compounds. Structure-activity studies employing functionalized azetidines have led to the development of variety of drug molecules and clinical candidates encompassing a broad spectrum of biological activities.

Herein, the synthesis a novel series of 3-aryl-3-arylmethoxyazetidines is described. Selected 3-aryl-3-arylmethoxyazetidines were evaluated for their binding affinity to multiple monoaminergic transporters for the potential treatment of methamphetamine addiction. It was discovered that this scaffold exhibits high binding affinity (nM) for both the serotonin and dopamine …

Synthesis, Structural Variations And Trends In The Properties Of Unique Dinuclear And Polynuclear Complexes Of Bis(Pyrazolyl)Methane Ligands In Solid State And Solution, Andrea Eva Pascui

Theses and Dissertations

The semi-rigid ligands, p-[CH(pz)₂]₂C₆H₄, L_p, m-[CH(pz)₂]₂C₆H₂, L_m, and m-[CH(3,5-Me₂pz)₂]₂C₆H₄, L_m* (pz = pyrazolyl ring), link two bis(pyrazolyl)methane units into a single molecule by a rigid phenylene spacer and are used to study the structural variations and magnetic interactions in self-assembled first row, divalent transition metal complexes in polymeric, dinuclear and dinuclear metallacyclic settings. The formation of these architectures highly depend on the geometry of these ligands: anti, the …

Glycosyl Thiocarbamates As New Building Blocks For Chemical Glycosylation, Sneha Chandrashekhar Ranade

Dissertations

Having multiple functions in biological systems e.g. fertilization, blood group determination, cell growth; carbohydrates have remained attractive subjects for the study. They are also involved in various life threatening biological processes, such as viral and bacterial infections, tumor development, etc. Understanding of these involvements/interactions of carbohydrates in such critical processes is essential for the development of carbohydrate based vaccines and therapeutics. Although carbohydrates are present abundantly in nature, their isolation is cumbersome and low yielding, which is why, the synthesis of carbohydrate units has been of interest to many scientists. Efforts have been made to make these synthetic methods more …

Characterization Of Complexes Of 2,2-Cis [Rh2(N{C6h5}Coch3)4] With Nitriles., Megan Ketron

Undergraduate Honors Theses

Complexes of 2,2-cis [Rh2(N{C6H5}COCH3)4] bound to benzonitrile, ortho-tolunitrile, and meta-tolunitrile were synthesized and characterized using X-ray crystallography, IR spectroscopy, and proton NMR. The crystal structures of 2,2-cis [Rh2(N{C6H5}COCH3)4]•2NCC6H5, 2,2-cis [Rh2(N{C6H5}COCH3)4]•2NC{2-CH3}C6H4, and 2,2-cis [Rh2(N{C6H5}COCH3)4]•2NC{3-CH3}C6H4 were solved using a Rigaku Mercury375R/M CCD XtaLab Mini Diffractometer. The 2,2-cis [Rh2(N{C6H5}COCH3)4]•2NCC6H5 complex had unit cell dimensions of a=10.2115(7) Å, b=9.9667(7) Å, c=21.367(2) Å, and β=100.971(7)° with a P21/n space group. The 2,2-cis [Rh2(N{C6H5}COCH3)4]•2NC{2-CH3}C6H4 complex had unit cell dimensions of a=10.3625(8) Å, b=10.0489(7) Å, c=21.611(2) Å, and β=100.868(7)° with a P21/n space group. The 2,2-cis [Rh2(N{C6H5}COCH3)4]•2NC{3-CH3}C6H4 complex had unit cell dimensions of a=10.849(3) Å, b=11.530(3) Å, …

Mechanistic Studies Of Bimolecular Electron Transfer Self-Exchange Rates Of Ruthenium Ammine Pyridyl Complexes Measured By Nmr Line Broadening Techniques, Yishun Qin

Master's Theses

The electron transfer (ET) self-exchange rates on a series of complexes of (NH₃)₅Ru^II/III L^2+/3+ in D₂O (where L is a substituted pyridyl ligand) were investigated by dynamic NMR measurements. Significant rate enhancement was observed for the cases of L = 3-phenylpyridine and 4-phenylpridine due to possible π-π stacking between Phpy ligands. These observations matche well with recent stopped-flow work by Mehmood on a similar set of related pseudo-self exchange reactions. Kinetics of the (NH₃)₅Ru^II/III (3-trifluoromethylpyridine)^2+/3+ self-exchange reactions with addition of various simple/complex salts and hexacyano salts …

Multinuclear Solid-State Nuclear Magnetic Resonance Spectroscopy Of Microporous Materials, Jun Xu

Electronic Thesis and Dissertation Repository

Microporous materials have attracted tremendous attention since 18^th century due to their industrial importance. It is essential to understand the relationships between the properties of microporous materials and their structures. However, the structures of many microporous materials are determined from the more limited powder X-ray diffraction (XRD) data due to the lack of suitable single-crystals for XRD. In such cases, an unambiguous structure solution of microporous materials requires additional information from other techniques such as solid-state NMR (SSNMR) spectroscopy. This thesis is focused on the study of two types of microporous materials, metal–organic frameworks (MOFs) and titanosilicates, by multinuclear …

Real Time Monitoring Of Surface Chemical Events By Streaming Potentials In Microfluidic Channels, Kenji Nokura

Theses and Dissertations

Zeta potential is one of the tools to measure the surface charge of materials, and Alvarez et al. have developed a microchannel device to measure zeta potentials in real time for label-free sensing using immobilized receptors on microchannel surfaces. However, the challenge has been the charge interference of surface modifiers on analyte detection. Therefore, it was necessary to find the best strategy to regenerate minimal surface charge after modifying the channel with polymer films that would anchor the affinity groups for the analyte. It was demonstrated that adsorption of positively and negatively charged analytes were monitored via real time zeta …

Synthesis, Characterization, And Application Of High Surface Area, Mesoporous, Stabilized Anatase Tio2 Catalyst Supports, Rebecca Elizabeth Olsen

Theses and Dissertations

Nanomaterials have attracted substantial attention in the area of catalysis due to the unique properties they exhibit such as high surface areas, intricate pore networks and unique morphologies. TiO2 has attracted attention as a catalyst since the discovery of its high photocatalytic activity by Fuishima and Honda in 1972. Given its high thermal stability, low cost, low environmental impact, and versatility, TiO2 is a widely used commercial catalyst and catalyst support. TiO2 is used in many applications such as photocatalysis is also an excellent support material for noble metals in a number of oxidative synthesis and pollution-control reactions. Though TiO2 …

Progress Toward Synthesis Of Molecular Beacons Incorporating Dabcyl Analog Quenchers, Christie M. Ettles

Electronic Thesis and Dissertation Repository

Progress toward the synthesis of molecular beacons containing analogs of the universal quencher 4-(4'-dimethylaminophenylazo)benzoic acid (DABCYL) has been made. A synthetic methodology has been developed for the differential labeling of a PNA molecular beacon with quencher and fluorophore moieties. A DABCYL analog diarylazo compound and three small fluorescent molecules have been derivatized with terminal alkyne groups for incorporation into azide-decorated PNA oligomers by on-resin “click” chemistry. An optimized on-resin procedure was used to determine the viability of the fluorophores and quencher for incorporation into PNA.

The synthesis of a pyrrolocytidine phosphoramidite containing a diarylazo DABCYL analog moiety was undertaken with …

Nonlinear Spectroscopic Investigation Of Adsorption To C-18 Model Stationary Phase, Anthony D. Peterson

Theses and Dissertations

Reversed-phase liquid chromatography (RPLC) is a commonly used separation technique in chemistry. Nevertheless, the mechanistic interactions at the molecular level among the eluent, analyte, and the stationary phase are not fully understood. Because of this limited understanding, optimization of the separation must be done experimentally. Learning more about molecular interactions should aid in improving separations. We are currently using second-harmonic generation (SHG) spectroscopy to investigate how analytes adsorb to the surface. SHG is a spectroscopic technique that produces signal only at places of non-isotropic symmetry; this typically occurs at surfaces. SHG can be used to produce surface isotherms of test …

Synthesis, Characterization, And Functionalization Of Magnetic Iron Nanoparticles For Enhanced Biological Applications, Christopher Warren

Theses and Dissertations

The transition metal ferrites of composition MFe2O4 where M is Fe, Co, or Ni are well established materials for various biological applications due to their interesting magnetic properties. Their elemental and stochiometric composition can be easily manipulated which allows further tuning of their ferrimagnetic properties. By changing the identity of M and by changing the crystallite size of the ferrites, nanocrystals with diverse magnetic properties can be systematically produced. Furthermore, ferrites are more stable in diverse chemical environments, as compared to metallic nanoparticles, which make ferrites particularly useful for a broad range of biomedical applications, especially in the field of …

When All Seems Lost: A Discussion On The Implications Of Using Medicine For Scientific Advances, Rebecca Monterusso

Honors Theses

When All is Lost is a creative non-fiction piece following the lives of two fictional characters living during World War" and the Holocaust. It is meant to discuss the moral quandary when human experimentation is used for the purpose of scientific advancement. The two main characters lives' are depicted in a series of modified scenes that describe what happens to them throughout the war. Leo Weinstock is a Jewish man who is chosen for the high-altitude experiments at Dachau after he is imprisoned during Kristallnacht. Erich, on the other hand, is a young, successful Luftwaffe pilot defending his country. Both …

Electrochemical And Surface Compositional Studies On Uranium Dioxide, Mayuri Razdan

Electronic Thesis and Dissertation Repository

This thesis describes electrochemical and surface compositional studies performed on a number of simulated nuclear fuel (SIMFUEL) materials under conditions relevant to permanent disposal of spent nuclear fuel in a geologic repository. This is important since a number of critical issues have been identified in the event of waste container failure. The research performed was mainly focused in three areas: (i) the influence of low pH on the surface chemistry of UO₂, since acidity could develop within corrosion product deposits and flaws in the fuel; (ii) the combined influence of dissolved H₂ and H₂O_{2 …}

The Design And Synthesis Of Magnetic Nanocomposites, Daniel Hudgins

Theses and Dissertations

Magnetism lies at the core of modern technology and can be found in industries such as oil refining, automotive, telecommunications, personal electronics, and power generation that are integral to our day to day lives. This permeation into everyday life has been enhanced in the past several decades with improvements in material design based upon the principles of nanotechnology leading to smaller, faster, and more efficient devices. The presented research will discuss the synthesis and processing of multiple magnetic nanoparticle structures designed for the enhancement of various, application specific, properties. In the first experiments a tunable core/shell structure was developed with …

Zinc Environment In Proteins: The Flexible And Reactive Core Of Hiv-1 Ncp7 And The Inhibitory Site Of Caspase-3, A. Gerard Daniel

Theses and Dissertations

Zinc is an essential cofactor of several proteins. The roles of zinc in these proteins are classified as catalytic, structural or regulatory. Zinc present in structural sites is considered to be a chemically inert, static structural element. On the contrary, previous studies on a C2H2 type zinc finger model compound and the C3H type HIV-1 NCp7 C-terminal zinc knuckle have shown that zinc at these sites can undergo coordination sphere expansion under the influence of a Pt based electrophile. The pentacoordination observed around zinc in these experiments raises an important question: are the structural zinc motifs found in the proteins …

Formation And Analysis Of Zinc Oxide Nanoparticles And Zinc Oxide Hexagonal Prisms And Optical Analysis Of Cadmium Selenide Nanoparticles, Jared M. Hancock

Theses and Dissertations

In this dissertation, methods to synthesize ZnO are reported. First, zinc oxide nanoparticles were synthesized with small amounts of transition metal ions to create materials called dilute magnetic semiconductors (DMS). We employed a low temperature sol-gel method that produces ZnO nanoparticles of reproducible size and incorporates cobalt, nickel, and manganese ions into the nanoparticles. Conditions were controlled such that a range of amounts of Co, Ni, and Mn were incorporated. The incorporation was tracked by color changes in the white ZnO powder to blue for Co, green for Ni and yellow for Mn. XRD measurements showed the nanoparticles were on …

An Insight Into Asymmetric Synthesis And Bioorganic Applications Of Novel Cα- Methyl-Lysine, - Proline, - Nipocotic Acid Analogues, Souvik Banerjee

Dissertations

Prochiral malonic diesters consisting of a quaternary carbon center have been successfully converted into a different set of tBoc-Fmoc-α2,2-methyllysine-OH analogues through chiral malonic half-ester intermediates achieved via enzymatic (Pig Liver Esterase, PLE) hydrolysis. The selection of chiral half-ester intermediates, which vary from 1 to 6 methylene units in the side chain, are achieved in high optical purity (92% - 97% ee) and in good yields (65% - 72%). The PLE hydrolysis of malonic diesters with a variety of side chain lengths observed to obey the Jones’s PLE model as evidenced from the stereochemical configurations of the resulting chiral half-esters. The …

Theoretical Tailoring Of Perforated Thin Silver Films For Surface Plasmon Resonance Affinity, Renan Gongora

HIM 1990-2015

Metallic films, in conjunction with biochemical-targeted probes, are expected to provide early diagnosis, targeted therapy and non-invasive monitoring for epidemiology applications [1-4]. The resonance wavelength peaks, both plasmonic and Wood-Rayleigh Anomalies (WRAs), in the scattering spectra are affected by the metallic architecture. As of today, much research has been devoted to extinction efficiency in the plasmonic region. However, Wood Rayleigh Anomalies (WRAs) typically occur at wavelengths associated with the periodic distance of the structures. A significant number of papers have already focused on the plasmonic region of the visible spectrum, but a less explored area of research was presented here; …

Syntheses And Reactions Of Early Transition Metal Amidinate Compounds, Adam Christopher Lamb

Doctoral Dissertations

Homoleptic Groups 4 and 5 metal amide compounds have been used as precursors in CVD/ALD processes to make microelectronic metal oxide thin films. These compounds are often very air sensitive. Ancillary ligands such as amidinates have been used to reduce their air sensitivity and to make their handling easier. Reactions of amidinates with dioxygen and water have thus been used to make metal oxide thin films. Studies of these reactions are important in order to make better precursors and purer thin films. This dissertation focuses on the following areas: (a) Syntheses of zirconium and Group 5 amidinate amides; (b) Studies …

Design And Synthesis Of Novel Sultams As Non-Nucleoside Inhibitors Of Hiv Reverse Transcriptase, Brian Chadwick Lecroix

Doctoral Dissertations

The compound 2-methyl-3-phenyl-2,3-dihydro-1,2-benzisothiazole 1,1-dioxide (NSC 108406) was identified as an HIV-1 reverse transcriptase inhibitor by the National Cancer Institute. Using this lead, the Baker group has developed a series of analogues with various groups at the 3-position that show a spectrum of biological activities. In the end, the substituents used could not compare to the biological activity of the inhibitor efavirenz (Sustiva^® [trademark]), and so it was decided to synthesize sultams with alkylethynyl substituents at the 3-position of the sultams in an attempt to mimic the activity of efavirenz.

Previous research analyzed the proposed novel sultams in the modeling …

Synthesis And Characterization Of Fullerene-Based Hydrogen Storage Materials, Patrick Alan Ward

Doctoral Dissertations

Storing hydrogen safely and efficiently is an area of great interest for the utilization of hydrogen as an energy carrier in transportation applications. The feasibility of using fullerenes in hydrogen storage materials was investigated. Alkali decorated fullerenes Li_xC₆₀ [LixC60] and Na_xC₆₀ [NaxC60] were found to enhance the hydrogen chemisorption and physisorption properties of fullerenes. Although the overall hydrogen physisorption uptake in these materials is low due to the crystalline nature of the material, the isosteric heats of adsorption of fullerenes were increased by lithium doping. C₆₀ [C60] is also capable of acting as …

Magneto-Optical Properties Of Complex Oxides, Peng Chen

Doctoral Dissertations

Complex oxides give rise to rich physics and exotic cross-coupled electronic and magnetic properties. This is because of the competing interaction between charge, structure, and magnetism in the materials. In this dissertation I present a spectroscopic investigation of several model complex oxides under external stimuli of magnetic field and temperature. The compounds of interest include BiFeO₃ [bismuth ferrite] nanoparticles and tetragonal film, Bi_1-xNd_xFeO₃ [neodymium doped bismuth ferrite], α-Fe₂O₃ [hematite], Ni₃V₂O₈ [nickel vanadate], and RIn_1-xMn_xO₃ [manganese doped rare earth indium oxide]. …

Design And Synthesis Of Flexible And Functional Polybenzoxazine Thin Films, Austin David Baranek

Dissertations

Polybenzoxazines offer the unique ability to incorporate a variety of properties and functionality into a single polymer network through simple synthetic techniques. However, within benzoxazine materials exist certain drawbacks of which brittleness is the primary issue when exploring thin film applications. This brittleness leads to poor mechanical stability and would reduce the lifetime of any device sought after. It is, however, through the simplistic nature of the benzoxazine monomer synthesis that the mechanical stability could be addressed chemically, avoiding the complications of using rubber toughening agents or plasticizers. The monomer synthesis offers tailorability of both the phenol and amine to …

Synthesis And Characterization Of A New Cyano-Substituted Tris(Pyrazolyl)Borate And Its Thallium(I) Complex, Bozumeh Som

Electronic Theses and Dissertations

A new cyanoscorpionate - tris(4-cyano-3,5-diphenylpyrazolyl)borate (Tp^Ph2,4CN) has been synthesized and characterized. The thallium complex of this ligand TlTp^Ph2,4CN has also been prepared and characterized by FT-IR, ¹H NMR, and single-crystal X-ray-diffraction. The complex TlTp^Ph2,4CN crystalized in the monoclinic space group C2/c with unit cell a = 14.6697(10) Å, b = 13.9493(10) Å, c = 19.3347(12) Å, and b= 91.761(2)°. Structural comparison of TlTp^Ph2,4CN with analogous complexes demonstrated the effects of both steric and electron-withdrawing substituents on coordination geometry and the electronic properties of the metal ion. There were short contacts between the cyano groups …

Synthesis And Characterization Of 2,2-Cis-[Rh2(Nphcoch3)4]•Ncc6h4r Where R = H, 2-Ch3, 3-Ch3, 4-Ch3 And [Rh2(O2cch3)(Nphcocf3)3], Fredricka F. Quarshie

Electronic Theses and Dissertations

Five novel compounds were synthesized and characterized. Crystal structures were determined using Rigaku Mercury 375/MCCD(XtaLAB mini) diffractometer with graphite monochromated MoKα radiation. The crystal structures of [Rh₂(NPhCOCH₃)₄•xNCC₆H₄R where x = 1 or 2 and R=H, 2-CH₃,3-CH₃ and 4-CH₃ were solved to an R₁ value of less than 5 (R₁= Σ||F_o| - |F_c|| / Σ |F_o|). In each of the nitrile complexes, the rhodium is five or six coordinate and possesses pseudo D_4h symmetry. The complexes were …

Assessing Different Zeolitic Adsorbents For Their Potential Use In Kr And Xe Separation, Breetha Alagappan

UNLV Theses, Dissertations, Professional Papers, and Capstones

Separation of Kr from Xe is an important problem in spent nuclear fuel fission gas management. The energy intensive and expensive cryogenic distillation method is currently used to separate these gases. In this thesis, we have carried out the research into appropriate sorbents for the separation of Kr and Xe using pressure swing adsorption. We have examined zeolites using gas adsorption studies as they have the potential to be more cost effective than other sorbents. Zeolites are microporous aluminosilicates and have ordered pore structures. The pores in zeolites have extra-framework cations are substantially free to move. The mobility of cations …

Characterization Techniques And Electrolyte Separator Performance Investigation For All Vanadium Redox Flow Battery, Zhijiang Tang

Doctoral Dissertations

The all-vanadium redox flow battery (VRFB) is an excellent prospect for large scale energy storage in an electricity grid level application. High battery performance has lately been achieved by using a novel cell configuration with advanced materials. However, more work is still required to better understand the reaction kinetics and transport behaviors in the battery to guide battery system optimization and new battery material development. The first part of my work is the characterization of the battery systems with flow-through or flow-by cell configurations. The configuration difference between two cell structures exhibit significantly different polarization behavior. The battery output can …

Evaluation Of Vdr-Coactivator Inhibitors Using Biochemical And Cell-Based Assays, Athena Marie Baranowski

Theses and Dissertations

ABSTRACT

EVALUATION OF VDR–COACTIVATOR INHIBITORS USING BIOCHEMICAL AND CELL–BASED ASSAYS

by

Athena Baranowski

The University of Wisconsin–Milwaukee, 2013

Under the Supervision of Dr. Alexander Arnold

The vitamin D receptor (VDR) is a ligand–dependent transcription factor, which belongs to the nuclear receptor superfamily. VDR–mediated gene regulation is governed by coregulators (coactivators and corepressors). VDR coregulator binding inhibitors (CBIs), which were discovered using high throughput screening (HTS), were evaluated using cell–based assays and biochemical assays to determine their ability to inhibit the interaction between VDR and steroid receptor coactivator–2 (SRC–2). Determining their ability to inhibit the VDR–SRC–2 interaction can lead to the …