Chemistry Commons^™

Magnetic Order In Quasi-Two-Dimensional Molecular Magnets Investigated With Muon-Spin Relaxation, A J. Steele, T Lancaster, S J. Blundell, P J. Baker, F L. Pratt, C Baines, M M. Conner, H I. Southerland, Jamie L. Manson, J A. Schlueter

Chemistry and Biochemistry Faculty Publications

We present the results of a muon-spin relaxation (mu+SR) investigation into magnetic ordering in several families of layered quasi-two-dimensional molecular antiferromagnets based on transition-metal ions such as S = 1/2 Cu2+ bridged with organic ligands such as pyrazine. In many of these materials magnetic ordering is difficult to detect with conventional magnetic probes. In contrast, mu+SR allows us to identify ordering temperatures and study the critical behavior close to T-N. Combining this with measurements of in-plane magnetic exchange J and predictions from quantum Monte Carlo simulations we may assess the degree of isolation of the 2D layers through estimates of …

Synthesis Of Cyclen Based Receptors And Their Use In Separations Biotechnology., Vivek Kaushik

Theses and Dissertations

A number of purification techniques such as adsorption, centrifugation, chromatography, extraction, distillation, filtration, precipitation etc. to name a few, are commonly used for the purification. However, due to a constant need of purification of even more complex crude mixtures, be it reaction mixtures, various proteins and DNA from cell extracts or medicinal compounds and fragrances from plant extracts, scientists needed to consistently develop new and improved techniques of purification. One such great advancement in the field of chromatography was the development of affinity chromatography. It revolutionized the field of bioseparations technology, and the dream of single stage purification of complex …

Mechanistic Studies On Xanthine Oxidoreductase Enzymes, Abebe Berhane

Chemistry and Chemical Biology ETDs

In humans, the xanthine oxidoreductase enzymes are known to catalyze the final two steps of purine metabolism by converting hypoxanthine successively to xanthine and uric acid. Xanthine oxidoreductase also metabolizes a wide variety of drugs in vivo, and activates a number of antiviral prodrugs of clinical importance. Therefore, understanding the reaction mechanism of this enzyme is of prime importance in furthering our understanding of enzyme-drug interactions. In order to provide a greater understanding on the reaction mechanism, theoretical and enzymatic spectroscopic experimental approaches have been utilized. The theoretical approaches were used to elucidate the electronic structure and geometry of the …

Quenching Of The Fluorescence Of Tris (2 2-Bipyridine) Ruthenium(Ii) [Ru(Bipy)3]2+ By A Dimeric Copper(Ii) Complex., Kevin E. Cummins

Electronic Theses and Dissertations

The quenching of the [Ru(bipy)₃]²⁺ by Cu₂L²⁺ was studied and the data were plotted with the Stern-Volmer equation. The plot showed a break and was divided into 2 regions, <0.5 and >0.5 Cu₂L²⁺: [Ru(bipy)₃]²⁺ molar ratio. Quenching above the 0.5 Cu₂L²⁺: [Ru(bipy)₃]²⁺ molar ratio was slower (330 x 10^-6 M^-1s^-1) than the quenching rate reaction below 0.5 ratio (387 x 10^-6 M^-1s^-1).

With Cu₂L²⁺ being a dimeric complex the …

Electrochemical Studies Of The Interaction Between Dna And A Compound Having Anticancer Properties., Antibe Pouliwe

Electronic Theses and Dissertations

Electrochemical method has been used to study the interaction between DNA and the compound N-(3',6'-dihydroxy-3-oxospiro[isobenzofuran-1(3H),9'-[9H]xanthen]-5-yl)-N'-(2-imidazoyl)urea having anticancer properties. A DNA modified nanometer-sized gold electrode was prepared by surface modification of a bare gold electrode using cysteamine. These electrodes have been characterized using electrochemical techniques and were used to study the interaction between DNA and the compound. Our results showed an increase in the adsorption peak current and a negative shift of E_1/2 in the oxidation of ferrocyanide on cysteamine and DNA modified electrodes. For the interaction between the DNA and the compound having anticancer properties, a decrease in peak …

Select Ruthenium Complexes As Potential Candidates For Thiol Ligation, Adam Blake Reinhart

Student Theses and Dissertations

Hydrodesulfurization is an industrial process used to remove sulfur impurities from fossil fuel feedstocks in order to prevent air pollution and acid deposition. The sulfur impurities are passed over a transition-metal sulfide catalyst producing pure hydrocarbons and usable sulfur byproduct. The current process occurs under high temperature and pressure. Molecular models of the catalyst/substrate interaction have been synthesized in order to study the electron density about the sulfur atom and thus give insight to the HDS activity of the complexes. CpRu(dppe)Cl and Ru(9S3)(dmso)Cl2 were studied for their ability to coordinate thiols. A new preparative method using microwave-assisted synthesis was found …

The Nucleotide Exchange Factor Ric-8a Is A Chaperone For The Conformationally Dynamic Nucleotide-Free State Of G Alpha I1, Celestine J. Thomas, Klara Briknarova, Jonathan K. Hilmer, Navid Movahed, Brian Bothner, John P. Sumida, Gregory G. Tall, Stephen R. Sprang

Chemistry and Biochemistry Faculty Publications

Heterotrimeric G protein alpha subunits are activated upon exchange of GDP for GTP at the nucleotide binding site of G alpha, catalyzed by guanine nucleotide exchange factors (GEFs). In addition to transmembrane G protein-coupled receptors (GPCRs), which act on G protein heterotrimers, members of the family cytosolic proteins typified by mammalian Ric-8A are GEFs for Gi/q/12/13-class G alpha subunits. Ric-8A binds to G alpha.GDP, resulting in the release of GDP. The Ric-8A complex with nucleotide-free G alpha i1 is stable, but dissociates upon binding of GTP to G alpha i1. To gain insight into the mechanism of Ric-8A-catalyzed GDP release …

Aryl Acetate Phase Transfer Catalysis: Method And Computation Studies, Meisha A. Binkley

Theses and Dissertations

Brief explanation and history of cinchona based Phase Transfer Catalysis (PTC). Studied aryl acetates in PTC, encompassing napthoyl, 6-methoxy napthoyl, phenyl and protected 4-hydroxy phenyl acetates. Investigated means of controlling the selectivity of the PTC reaction by changing the electrophile size, the ether side group size or by addition of inorganic salts. Found that either small or aromatic electophiles increased enantioselectivity more than aliphatic electrophiles, and that increasing the size of ether protecting group also increased selectivity. Positive effects of salt addition included either decreasing reaction time or increasing enantiomeric excess. Applied findings towards the synthesis of S-equol. Computational experiments …

Neutron Diffraction Of Nabd4: Phase Transition, Rietveld Structure Refinements, And Equation Of State, Guillermo Esparza, Esparza, Patricia Kalita, Andrew Cornelius

Undergraduate Research Opportunities Program (UROP)

NaBH4 is a hydride with possible applications as a hydrogen storage material for future renewable energy technologies. It’s dehydrogenation properties are enhanced with the mixture of particular catalysts through ball-milling techniques during which local pressures may exceed several GPa’s. It is for this reason that understanding the behavior of pressure induced phase changes of its crystalline unit cell is an area of interest.

Cell Migration Dynamics After Alteration Of Cell-Cell Contacts In Fibrosarcoma And Glioblastoma Cell Lines, Hassan S. Rizvi, Ronald K. Gary

Undergraduate Research Opportunities Program (UROP)

Cell migration is a vital component of metastasis. In this study, our intent was to study cell migration by alteration of the Wnt/GSK-3 Pathway. Since BeSO4 is a known GSK-3 kinase inhibitor, we hypothesized that this agent would cause cell migration to decrease as a result of β-catenin stabilization. Two human cell lines, HT-1080 (fibrosarcoma) and A172 (glioblastoma), were used to observe migration levels in the presence and absence of BeSO4. Our results show that cell migration is diminished for cells that were pre-treated with BeSO4, in comparison to the untreated (control) cells.

Undergraduate Research Opportunities Program 2011, Nicholle Booker, University Of Nevada, Las Vegas

Undergraduate Research Opportunities Program (UROP)

Undergraduate Research Opportunities Program

On August 9, 2011 the UNLV College of Sciences will celebrate the accomplishments of undergraduate students participating in the Summer 2011 Undergraduate Research Opportunities Program (UROP) and the Research Experience For Undergraduates (REU) Program.

The public is invited to attend, beginning at 10:00 a.m.

Please join us to view student research posters. Student research topics include: biomedicine and human health, Nevada's fragile environment and ecosystems, climate change, stem cell research, microbiology, astrophysics, and many others.

Over 25 UNLV undergraduates and a cohort of 25 undergraduates selected from colleges and universities across the nation will mark the …

The Formation And Stability Of Radical-Molecule And Radical-Radical Complexes And Their Importance In Atmospheric Processes, Jared M. Clark

Theses and Dissertations

This research explores the role that radical-molecule complexes play in the chemistry of Earth's atmosphere. The formation of such complexes can have direct and pronounced effects on the reaction and product outcome of atmospheric chemical reactions. Some attention is also given to the formation of radial-radical pre-reactive complexes in the HO + ClO system. Peroxy radicals (RO2) can form stable complexes with polar compounds such as H2O, NH3, and CH3OH. For the simplest RO2 radical, HO2, complex formation (e.g., HO2-H2O, HO2-NH3, and HO2-722;CH3OH) gives rise to a significant increase in the HO2 self-reaction rate constant. Although this phenomenon has been …

Group 11 Metal Compounds With Tripodal Bis(Imidazole) Thioether Ligands. Applications As Catalysts In The Oxidation Of Alkenes And As Antimicrobial Agents, Fangwei Liu, Reema Anis, Eunmi Hwang, Rafael Ovalle, Armando Varela-Ramírez, Renato J. Aguilera, María Contel

Publications and Research

New group 11 metal complexes have been prepared using the previously described tripodal bis(imidazole) thioether ligand (N-methyl-4,5-diphenyl-2- imidazolyl)2C(OMe)C(CH3)2S(tert-Bu) ({BITOMe,StBu}, 2). The pincer ligand offers a N2S donor atom set that can be used to coordinate the group 11 metals in different oxidation states [AuI , AuIII, AgI , CuI and CuII]. Thus the new compounds [Au{BITOMe,StBu}Cl][AuCl4]2 (3), [Au{BITOMe,StBu}Cl] (4), [Ag{BITOMe,StBu}X] (X = OSO2CF3 - 5, PF6 - 6) and [Cu{BITOMe,StBu}Cl2] (7) have been synthesized from reaction of 2 with the appropriate metal precursors, and characterized in solution. While attempting characterization in the solid state of 3, single crystals of the …

Ferritin Diversity: Mechanistic Studies, Disease Implications, And Materials Chemistry, Robert Joseph Hilton

Theses and Dissertations

The study of ferritin includes a rich history of discoveries and scientific progress. Initially, the composition of ferritin was determined. Soon, it was shown that ferritin is a spherical, hollow protein. Eventually, over several decades of research, the structure and some function of this interesting protein was elucidated. However, the ferritin field was not completely satisfied. Today, for example, researchers are interested in refining the details of ferritin function, in discovering the role of ferritin in a variety of diseases, and in using ferritin for materials chemistry applications. The work presented in this dissertation highlights the progress that we have …

Water In Protein Cavities: Free Energy, Entropy, Enthalpy, And Its Influences On Protein Structure And Flexibility, Hongtao Yu

LSU New Orleans Theses and Dissertations

Complexes of the antibiotics novobiocin and clorobiocin with DNA gyrase are illustrative of the importance of bound water to binding thermodynamics. Mutants resistantto novobiocin as well as those with a decreased affinity for novobiocin over clorobiocinboth involve a less favorable entropy of binding, which more than compensates for amore favorable enthalpy, and additional water molecules at the proteinligandinterface.Free energy, enthalpy, and entropy for these water molecules were calculated by thermodynamicintegration computer simulations. The calculations show that addition of thewater molecules is entropically unfavorable, with values that are comparable to the measuredentropy differences. The free energies and entropies correlate with the …

Towards The Synthesis Of Magnesidin, Subramanya Pingali

LSU New Orleans Theses and Dissertations

Magnesidin is a magnesium chelate of the 3-hexanoyl and 3-octanoyl tetramic acid derivatives isolated from Psuedomonas magensiorubra. Its activity against grampositive bacteria was found to be a specific target for Gingivitis, a dental plaque.Although the synthesis of magnesidin has been reported earlier, it was not reproducible. The highly polar nature and it’s ability to exhibit tautomerization makes their chemical behavior complex and difficult to predict its structure. A variety of reactions and an in depth understanding of the chemical structure is necessary to attain the synthesis of these compounds. This dissertation focuses on addressing the attempts towards the synthesis …

Synthesis And Characterization Of Nanostructures In Porous Anodic Aluminum Oxide Templates, Jin-Hee Lim

LSU New Orleans Theses and Dissertations

In this study, template-based methods are used for the fabrication of various nanostructures such as nandots, nanorods, nanowires, nanotubes, and core-shell structures. Porous alumina membranes were employed as templates and metal nanostructures were synthesized in the templates by electrodeposition. By using lithography techniques, controlled patterned nanostructures were also fabricated on alumina templates. The magnetic properties of the various metal nanostructures were investigated. The pore size, interpore distance, and pore geometry highly affect magnetic properties of nanostructures grown in the templates. Hexagonally ordered porous alumina templates can be fabricated by two-step anodization. The pore diameters and interpore distances were readily controlled …

Synthesis Of Chiral Intermediates By Deritivization Of Monosaccharides, Sanjeeva Dodlapati

LSU New Orleans Theses and Dissertations

Conformationally constrained bicyclic amino acids are invaluable in the synthesis of natural products and peptidomimetics. Aeruginosins contain novel bicyclic amino acid, 2--‐carboxy--‐6--‐hydroxyl octahydrindole (Choi) as the core structure. Aeruginosins are tetra peptide serine protease inhibitors isolated from marine sponges and cyanobacterial water blooms. Rigid bicyclic amino acid(Choi)is an essential core structure, which strongly influences biological activity of aeruginosin family members. Aeruginosins showed promising inhibitory activity against thrombin, trypsin, and factor VIIa. Thrombin and factor VIIa play a major role in blood clotting cascade; excessive coagulation leads to thrombosis and other cardiovascular diseases. Several research groups have reported a number of …

Topochemical Manipulation Of Layered Perovskites, Elisha A. Josepha

LSU New Orleans Theses and Dissertations

Topochemical strategies, techniques that allow one to effectively manipulate the structures of nonmolecular solids once a crystal lattice is established, are effective in the low temperature (< 500 °C) modification of solid state structures, allowing the preparation of nonmolecular compounds not accessible by standard synthetic routes. Some of the techniques, ion exchange, intercalation/deintercalation, have proven to be excellent synthetic methods for preserving specific frameworks. The combination of these techniques can allow one to create a multistep approach that can be used to design new compounds with interesting properties.

As an expansion to the field of topotactic reactions, a multistep approach was developed towards the synthesis of the new compounds (A xM0.5Cly)LaNb2O7 (where A = Rb, Cs; M = Fe, Ni; x ≈ 1.5;y ≈ 1) at temperatures below 400oC. The first reaction step involved the ion exchange of the host materials (ALaNb2O7, A = Rb, Cs) to form the products M0.5LaNb2O7 (where M = Fe, Ni), a structure open to further …

Characterization Of The Desorption Electrospray Ionization Mechanism Using Microscopic Imaging Of The Sample Surface, Michael Craig Wood

Theses and Dissertations

Desorption electrospray ionization (DESI) is an ambient ionization technique for mass spectrometry. This solvent based desorption ion source has wide applicability in surface analysis with minimal sample preparation. Interest in improving detection limits, broadening applications, and increasing the spatial resolution for chemical imaging has led to studies of the DESI mechanism. An inverted microscope has been used to image interactions between the DESI spray and test analytes on a glass surface. Microscopic images recorded with millisecond time resolution have provided important insights into the processes governing analyte transport and desorption. These insights are the basis of a rivulet-based model for …

The Characterization Of Avian Polyomavirus, Satellite Tobacco Mosaic Virus, And Bacteriophage Cw02 By Means Of Cryogenic Electron Microscopy, Peter S. Shen

Theses and Dissertations

Viruses are the most abundant biological entity in the biosphere and are known to infect hosts from all domains of life. The aim of my work is to identify conserved and non-conserved features among the capsid structures of related and divergent icosahedral viruses via cryogenic electron microscopy, sequence analysis, molecular modeling, and other techniques. Bird polyomaviruses often cause severe disease in their hosts whereas mammalian polyomaviruses generally do not. Avian polyomavirus is a type of bird polyomavirus with an unusually broad host range compared to the restricted tropism of other polyomaviruses. Although most polyomaviruses have a conserved, rigid capsid protein …

Synthesis Of (±)-Cyclophostin, (±)-Cyclipostin P, Their Phosphonate Analogs And New Chemistry Of Vinyl Phosphonates, Raj Kumar Malla

Dissertations

This work is divided into 2 parts: a) total synthesis of (±)-cyclophostin, (±)-cyclipostin P and their monocyclic analogs b) development of a metathesis based methodology for transformation of vinyl phosphonates. Cyclophostin (1) and cyclipostins (2) are bioactive natural bicyclic organophosphates. Cyclophostin is a powerful inhibitor of acetyl cholinesterase (AChE), whereas members of the cyclipostins are potent inhibitors of hormone sensitive lipase (HSL). Cyclophostin (1) and cyclipostin (2) have the same structural core unit, but different phosphate ester substituents. While cyclophostin is a methyl ester, the members of the cyclipostins are phosphate esters of different alkyl groups of various length and …

Vapor Liquid Solid Growths Of Germanium And Gallium Antimonide Nanowires, Ralph Alvarez, Esmeralda Arreola, Michael Oye, Meyya Meyyappan

STAR Program Research Presentations

Determining the optimal growth parameters for germanium (Ge) and gallium antimonide (GaSb) nanowires is the focus of this research. Given the fact that nano materials behave differently from their bulk counterparts we are researching some variables that influence nanowire diameter and length such as temperature, ramp rate, gas flow rate, and catalyst particle size. Based on the nano material size which is typically a few 10s of nanometers wide, these nano materials can be engineered to take advantage of their optical properties. Specifically the infrared (IR) response of Ge and GaSb nanowires are directly controllable based on their geometry. Fine …

Effects Of Ambient Gases On Icf Target Capsules, Bryan Chambers, Steve Letts, Michael Stadermann

STAR Program Research Presentations

We researched how the chemical and physical properties of a plasma polymer fuel capsule change as they are exposed to ambient gases. The fuel capsules contain the deuterium fuel inside them, they serve as the outer shell for the fuel and act as a ablator for the process. If they are reactive or diffusive with the atmosphere this can change their mass and effect the outcome of the fusion shots performed at the National Ignition Facility where High Powered Lasers are incident upon a gold hohlraum containing a capsule. We discovered that nitrogen and water vapor diffuse into the material …

Characterization Of Uranium Species In Sediments Under Iron And Sulfate Reducing Conditions Using Synchrotron-Based Techniques, Don Q. Pham, John Bargar

STAR Program Research Presentations

Uranium is one of the most common and problematic contaminants at legacy Department of Energy sites. Groundwater contamination is particularly problematic because it occurs at depth, is present in large volumes, and cannot be easily accessed for clean-up. One method of remediation being investigated is the bioreduction of soluble U(VI) to insoluble U(IV) complexes through the in-situ stimulation of metal-reducing bacteria. Understanding the structure of these uranium complexes can help us determine their fate and stability in groundwater and map out the biological process of uranium reduction by metal-reducing bacteria. In this study, we used the synchrotron-based techniques, X-ray absorption …

Exploring Methods For Earthquake Prediction: The Effects Of Water On The Flow Of Stress-Activated Electric Currents In Igneous Rocks, Aaron M. Jahoda, Friedemann T. Freund

STAR Program Research Presentations

Much of the devastation and damage of earthquakes can be attributed to the fact that they occur suddenly and without much warning, which limits the ability of people to evacuate and/or properly prepare. One method, however, that might be used to predict seismic events is the generation of electric currents in rocks when stresses are applied. It is observed in this research that the application of direct force onto samples of igneous rock causes the rocks to generate a measurable current, which is attributed to positive-hole charges moving within the oxygen sub-lattice. Because large and changing forces are acted upon …

Spectroscopic Properties Of Lanthanide (Iii) Compounds In Aqueous And Ionic Media, Orissa A. Burghard, Sayandev Chatterjee, Zheming Wang, Samuel A. Bryan

STAR Program Research Presentations

Lanthanide containing materials are receiving increasing attention due to their wide range of potential applications including bioanalytical imaging, dye-sensitized solar cells, nano-biotechnology and catalysis. The unique spectroscopic properties (intense and sharp emission bands with high color purity and high quantum efficiency) of lanthanides make them strong candidates for use as bio-markers or selective detectors. The attractiveness of lanthanides as future imaging agents as well as recent interest in their potential use in biological media has increased the need to understand the behavior of lanthanides in the presence of other ions or in ionic media.

The complexity of the biological media …

Effect Of Au Content On Microstructural Evolution Of Snagcu Solder Joints That Undergo Isothermal Aging And Reliability Testing, Patrick J. Hyland

Master's Theses

Electronics, especially, printed circuit boards (PCBs) are a widespread technology. Metal coatings or “surface finishes” are often added to PCB board pads and component leads during manufacturing to improve their performance. Electroplated nickel/gold over copper is a popular surface finish for printed circuit boards and component leads. The presence of gold in solder joints, however, is known to have detrimental effects referred to as gold embrittlement. It is generally understood that tin-lead solder joints with less than 3 weight percent (wt%) of gold will not experience reliability issues. The acceptable level of gold in lead-free solder joints, however, is less …

Synthesis And Structure Of A Substituted Pyridazine, Kiranmai Byrichetti

Masters Theses & Specialist Projects

Pyridazines are heterocyclic compounds with an N-N bond in their ring structure. Heterocyclic aromatic compounds are of great interest as a result of their novel properties and commercial applications. Our current research is focused on the potential role of pyridazines in next generation electronic devices that utilize organics as the semiconducting material. The synthesis of 5, 6-fused ring pyridazines beginning from fulvenes (Scheme 1) is described herein. These fused heterocycles will serve as synthetic models and building blocks for potential organic or organometallic conducting polymers.

Our goal was to modify the route of Snyder et al. previously reported for the …

Regiospecific Synthesis Of Ortho Substituted Phenols, Ravindra Kotha Balasainath

Masters Theses & Specialist Projects

Phenol is highly reactive toward electrophilic aromatic substitution. By this general approach, many groups can be appended to the ring, via halogenation, acylation, sulfonation, and other processes. Phenol contains the hydroxyl group (–OH), which is a strongly activating ortho/para directing group in aromatic electrophilic substitution (AES). AES gives a mixture of ortho-and para isomers, which must be separated.

The strong directing ability of phenol can also result in multiple substitutions on the aromatic ring which could be a major concern in the regiospecific synthesis of phenols. AES and Directed ortho--Metalation (DoM) are the only ways to directly substitute …