Chemistry Commons^™

Lithiation Reactions Of 3-(4-Chlorophenyl)Sydnone And 3-(4-Methylphenyl)Sydnone, Nigel Ngonidzashe Chitiyo

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Ortho-iodophenyl sydnones are key intermediates in Sonogashira coupling reactions and the resulting ortho alkynyl sydnones are useful precursors to functionalized sydnonquinolines. In this work, three synthetic routes leading to the synthesis of these versatile intermediates were explored.

Lithiation reactions of 3-(4-chlorophenyl) sydnone and 3-(4-methylphenyl) sydnone followed by trapping with iodine electrophiles yielded the expected disubstituted species 3-(4-chloro-2-iodophenyl)-4-iodosydnone and 3-(4-methyl-2-iodophenyl)-4-iodosydnone in yields ranging from 14% to 75%. Subsequent reduction with sodium sulfite removed the iodine at the C-4 position in both species yielding the ortho iodophenyl sydnones in 80% and 85% yield, respectively.

A surprising result was the discovery that careful …

Conducting Polymer Matrix Poly(2,2'-Bithiophene) Mercuric Metal Ion Incorporation, Rachel Michele Kingdom

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The synthesis of poly(2,2'bithiophene) was carried out utilizing the Epsilon 2000 cyclic voltammeter. In order to incorporate the mercuric ion into the polymer matrix, the polymer was grown on an Iridium Oxide conductive glass, immersed into a solution of 0.005M HgSO4 for 15 minutes. The mercuric ion became covalently bonded to the sulfur from the polymer. The comparison of the bare platinum electrode in a solution of 0.005M pyrocatechol to the modified poly(2,2'-bithiophene) polymer was ran at a scan rate of 100mVs-1. This gave a direct comparison of oxidation/reduction peak potentials. As seen, the modified poly(2,2'-bithiophene) polymer with the mercuric …

Tailoring The Degree Of Branching In Hyperbranched Poly (Arylene Ether Sulfone)S And Poly(Arylene Ether Ketone)S Prepared Via An A2 + Bb'b" Approach, Shravanthi Raghavapuram

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The synthesis and characterization of hyperbranched poly(arylene ether)s with tailored degrees of branching has been explored via an A₂+B₃ approach. The reactivity of the individual electrophilic sites towards nucleophilic aromatic substitution, NAS, of the BB'B" monomers 4, 3', 5'-trifluorophenyl sulfone, 1 and 4, 3', 5'-trifluoro benzophenone, 2 were studied. The concentration, temperature and solvent conditions had an effect on the degree of branching, DB, in 1 and 2 and were probed via ¹³C and ¹⁹F NMR spectroscopy as well as a series of model reactions employing p-cresol 16, which acts as the nucleophile. Soluble, …

Dipole-Induced, Thermally Stable Lamellar Structure By Polar Aromatic Silane, Jinyue Jiang, Ocelio V. Lima, Yong Pei, Xiao Cheng Zeng, Li Tan, Eric Forsythe

Xiao Cheng Zeng Publications

Lamellar structures, consisting of alternating inorganic layers separated by organic moieties, have attracted much attention over a wide range of applications, such as polymer-clay composites, rheology control, and optoelectronic devices. Organosilanes are ideal candidates for such efforts due to their ability to self-assemble and the intrinsic hybrid configuration of organic/inorganic moieties. Yet, the main emphasis has been focused on alkylsilane, where an alkyl group is linked with a silane terminal, i.e., R-SiX₃ (R is alkane and X can be halogen or alkoxy). Construction of stacked monolayers of alkylsilane through chemisorption is possible. The demonstrated pathway usually takes place after …

Materials Design Of Half-Metallic Graphene And Graphene Nanoribbons, Menghao Wu, Xiaojun Wu, Yi Gao, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Through patterned chemical modification, we show that both graphene sheets and zigzag-edged graphene nanoribbons (ZGNRs) can be converted to half-metals as long as the unmodified carbon strip (or width of ZGNRs) is sufficiently wide. Periodically functionalized graphene can mimic electronic behavior of edge-modified ZGNRs as the edge-modified zigzag carbon chains effectively divide a graphene sheet into a series of identical ZGNRs.

First-Principles Study Of Methane Dehydrogenation On A Bimetallic Cu/N(111) Surface, Wei An, Xiao Cheng Zeng, C. Heath Turner

Xiao Cheng Zeng Publications

We present density-functional theory calculations of the dehydrogenation of methane and CH_x (x = 1 – 3) on a Cu/Ni(111) surface, where Cu atoms are substituted on the Ni surface at a coverage of 1/4 monolayer.

On The Phase Diagram Of Water With Density Functional Theory Potentials: The Melting Temperature Of Ice /H With The Perdew–Burke–Ernzerhof And Becke–Lee–Yang–Parr Functionals, Soohaeng Yoo, Xiao Cheng Zeng, Sotiris C. Xantheas

Xiao Cheng Zeng Publications

The melting temperature (T_m) of ice I_h was determined from constant enthalpy and pressure (NPH) Born–Oppenheimer molecular dynamics simulations to be 417±3 K for the Perdew–Burke– Ernzerhof and 411±4 K for the Becke–Lee–Yang–Parr density functionals using a coexisting ice (I_h)-liquid phase at constant pressures of P=2500 and 10 000 bar and a density p=1 g/cm³, respectively.

Noncovalent Interactions In The Asymmetric Synthesis Of Rigid, Conjugated Helical Structures, Makoto Miyasaka, Maren Pink, Suchada Rajca, Andrzej Rajca

Andrzej Rajca Publications

Helical supramolecular architecture, such as helical foldamers, supramolecular helicates and aggregates, helical molecules, macromolecules, and oligomers, is a fascinating topic of interest in chemistry and materials science. Although such supramolecular structures may provide advantages in the design of stimuli-responsive and functional materials, the weak nature of the noncovalent forces, as well as the dependency of the dynamic process on their local environments, may hinder their possible applications because of their limited structural stability and processibility. Stabilization of these supramolecular structures could be achieved by modification of the molecular backbone with specific functional groups that permit intramolecular cross-linking, in which covalent …

Androgen-Stimulated Udp-Glucose Dehydrogenase Expression Limits Prostate Androgen Availability Without Impacting Hyaluronan Levels, Qin Wei, Robert Galbenus, Ashraf Raza, Ronald Cerny, Melanie A. Simpson

Ronald Cerny Publications

UDP-glucose dehydrogenase (UGDH) oxidizes UDP-glucose to UDP-glucuronate, an essential precursor for production of hyaluronan (HA), proteoglycans, and xenobiotic glucuronides. High levels of HA turnover in prostate cancer are correlated with aggressive progression. UGDH expression is high in the normal prostate even though HA accumulation is virtually undetectable. Thus, its normal role in the prostate may be to provide precursors for glucuronosyltransferase enzymes, which inactivate and solubilize androgens by glucuronidation. In this report, we quantified androgen dependence of UGDH, glucuronosyltransferase, and HA synthase expression. Androgen dependent and independent human prostate cancer cell lines were used to test the effects of UGDH …

Continuous And Smooth Potential Energy Surface For Conductorlike Screening Solvation Model Using Fixed Points With Variable Areas, Peifeng Su, Hui Li

Department of Chemistry: Faculty Publications

Rigorously continuous and smooth potential energy surfaces, as well as exact analytic gradients, are obtained for a conductorlike screening solvation model (CPCM, a variant of the general COSMO) with Hartree–Fock (RHF, ROHF, UHF, and MCSCF) and density functional theory (R-DFT, RO-DFT, and U-DFT) methods using a new tessellation scheme, fixed points with variable areas (FIXPVA). In FIXPVA, spheres centered at atoms are used to define the molecular cavity and surface. The surface of each sphere is divided into 60, 240, or 960 tesserae, which have positions fixed relative to the sphere center and areas scaled by switching functions of their …

Smooth Potential Energy Surface For Cavitation, Dispersion, And Repulsion Free Energies In Polarizable Continuum Model, Yali Wang, Hui Li

Department of Chemistry: Faculty Publications

The fixed points with variable areas [FIXPVA (Ref. 1)] tessellation scheme is used to obtain smooth potential energy surfaces for the cavitation G_cav, dispersion G_dis, and repulsion G_rep free energies in the polarizable continuum model (PCM). It is shown that FIXPVA can reproduce the standard GEPOL (Ref. 4) results to within 1 kcal/mol.

A New Peroxide Fragmentation: Efficient Chemical Generation Of 1O2 In Organic Media, Patrick Dussault, Prasanta Ghorai

Department of Chemistry: Faculty Publications

Monoactivated derivatives of 1,1-dihydroperoxides undergo an unprecedented base-promoted fragmentation to efficiently generate singlet oxygen (¹O₂) in anhydrous organic solvents.

A Multi-Step Nmr Screen For The Identification And Evaluation Of Chemical Leads For Drug Discovery, Kelly A. Mercier, Matthew D. Shortridge, Robert Powers

Department of Chemistry: Faculty Publications

A multi-step NMR based screening assay is described for identifying and evaluating chemical leads for their ability to bind a target protein. The multi-step NMR assay provides structure-related information while being an integral part of a structure based drug discovery and design program. The fundamental principle of the multi-step NMR assay is to combine distinct 1D and 2D NMR techniques, in such a manner, that the inherent strengths and weakness associated with each technique is complementary to each other in the screen. By taking advantage of the combined strengths of 1D and 2D NMR experiments, it is possible to minimize …

Anhydrous Fluoride Salts And Reagents And Methods For Their Production, Stephen G. Dimagno, Haoran Sun

Department of Chemistry: Faculty Publications

Anhydrous organic fluoride salts and reagents prepared by a method comprising the nucleophilic Substitution of a fluorinated aromatic or fluorinated unsaturated organic compound with a salt having the formula: [Q_nM]^x+A_x^- in an inert polar, aprotic solvent; wherein M is an atom capable of supporting a formal positive charge, the n groups Q are independently varied organic moieties, n is an integer such that the [Q_nM] carries at least one formal positive charge, x is an integer defining the number of formal positive charge(s), +, carried by the [Q_nM], A^{- …}

Energy Gradients In Combined Fragment Molecular Orbital And Polarizable Continuum Model (Fmo/Pcm) Calculation, Hui Li, Dmitri G. Federov, Takeshi Nagata, Kazuo Kitaura, Jan H. Jensen, Mark S. Gordon

Hui Li Publications

The analytic energy gradients for the combined fragment molecular orbital and polarizable continuum model (FMO/PCM) method are derived and implemented. Applications of FMO/PCM geometry optimization to polyalanine show that the structures obtained with the FMO/PCM method are very close to those obtained with the corresponding full ab initio PCM methods. FMO/PCM (RHF/6-31G* level) is used to optimize the solution structure of the 304-atom Trp-cage miniprotein and the result is in agreement with NMR experiments. The key factors determining the relative stability of the a-helix, b-turn and the extended form in solution are elucidated for polyalanine.

Optimising The Synthesis And Red–Green–Blue Emission Of A Simple Organic Dye, Martha Sibrian-Vazquez, Robert M. Strongin

Chemistry Faculty Publications and Presentations

Synthetic dyes have been widely used in supramolecular chemistry not only to probe fundamental chemical interactions but also as components of functional materials. Most current efforts in this regard are directed at designing new host systems for the dyes. Herein we report on the study of a versatile new organic fluorophore. We describe a synthesis which affords improved yields in a convenient one pot procedure. Moreover, a simple method for predicting and controlling the dye’s responses to external stimuli affords a potentially practical method for achieving red–green–blue and concomitant white light generation.

Effect Of The Regiochemistry Of Butyl Amide Substituents On The Solution-State Structures Of Lanthanide(Iii) Dota-Tetraamide Complexes, Tomoyasu Mani, Gyula Tircsó, Piyu Zhao, A. Dean Sherry, Mark Woods

Chemistry Faculty Publications and Presentations

The coordination geometry adopted by the lanthanide complexes of DOTA-tetraamides is a critical factor in determining their water exchange kinetics. Controlling the water exchange kinetics of DOTA-tetraamide complexes, and by extension their coordination geometry, is of particular interest because of the potential application of this class of complex as PARACEST MRI contrast agents. To facilitate the maximum CEST effect at the lowest pre-saturation powers much slower exchange kinetics are required than are commonly observed with these types of chelates. Complexes that adopt the more slowly exchanging square antiprismatic coordination geometry are therefore preferred; however, the factors that govern which coordination …

Generation Of Novel Pikromycin Antibiotic Products Through Mutasynthesis, Shuchi Gupta, Venkatraman Lakshmanan, Beom Seok Kim, Robert Fecik, Kevin A. Reynolds

Chemistry Faculty Publications and Presentations

Mutasynthesis in pikromycin PKS: The amenability of pikromycin polyketide synthase to mutational biosynthesis has been demonstrated. A natural triketide and its analogues, activated as N-acetyl-cysteamine thioesters, were synthesized and fed to a pikAI-deleted strain; this led to the production of new antibiotics. A vinyl analogue was found to have better antibacterial activity than pikromycin.

The Effect Of Adsorbent Geometry And Surface Chemistry On Hplc Retention, Zhaoxia Liu

Seton Hall University Dissertations and Theses (ETDs)

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Determination Of Partition And Activity Coefficients Using Headspace- Gas Chromatography, Gregory Paul Bullock

Seton Hall University Dissertations and Theses (ETDs)

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Room Temperature Fluorescence Spectroscopy As A Tool For The Forensic Trace Analysis Of Textile Fibers, Matthew Rex

Electronic Theses and Dissertations

Trace textile fiber evidence is found at numerous crime scenes and plays an important role in linking a suspect to the respective scene. Several methods currently exist for the analysis of trace fiber evidence. Microscopy provides information regarding the fibers material, color and weave. For more detailed chemical analysis chromatographic methods are employed and for discrimination between dyes, liquid chromatography coupled with mass spectrometry (LC-MS) is currently the method providing the most discrimination. These methods have primarily focused on the dyes used to color the fibers and have not investigated other components that can potentially discriminate among fibers. This dissertation …

Investigations Of S-Glutathionylation Of Brain Proteins In The Progression Of Alzheimer's Disease And Of A Potential Glutatione Mimetic As A Treatment Of Alzheimer's Disease, Shelley Faye Newman

University of Kentucky Doctoral Dissertations

Alzheimer’s disease (AD) is a neurodegenerative disorder characterized by neurofibrillary tangles, senile plaques and loss of synapses. Many studies support the notion that oxidative stress plays an important role in AD pathogenesis. Previous studies from our laboratory employed redox proteomics to identify oxidatively modified proteins in the AD inferior parietal lobule (IPL). The proteins were consistent with AD pathology and have been central to further investigations of the disease. The present study was focused on the identification of specific targets of protein S-glutathionylation in AD, early AD (EAD), and mild cognative impairment (MCI) using a redox proteomics approach. In AD …

A Versatile Synthesis Of Electroactive Stilbenoprismands For Effective Binding Of Metal Cations, Sergey V. Lindeman, Rajendra Rathore, Paromita Debroy

Chemistry Faculty Research and Publications

A versatile synthesis of a new class of polyaromatic receptors (stilbenoprismands) containing a Δ-shaped cavity similar to that of the π-prismand together with an intimately coupled electroactive stilbenoid moiety was accomplished via an efficient intramolecular McMurry coupling reaction. The presence of the Δ-shaped cavity in stilbenoprismands allows an efficient binding of a single silver cation as probed by ¹H NMR spectroscopy. Electron-rich stilbenoprismands undergo a ready oxidation to their highly robust cation−radical and dicationic salts. X-ray structure determination of a representative dicationic stilbenoprismand showed that the charges were largely localized on the tetraarylethylene moiety, which results in a twisting …

Desert Varnish As An Indicator Of Modern-Day Air Pollution In Southern Nevada, Piotr Nowinski

UNLV Theses, Dissertations, Professional Papers, and Capstones

Rock varnish, often called desert varnish, is a slow-growing, manganese-rich coating that accumulates on exposed rock surfaces. The mechanism of varnish formation is not fully understood, however, most authors agree that varnishes derive their components from the atmosphere. The main goal of this study was to demonstrate the potential use of desert varnish as a passive environmental monitor of present and past atmospheric pollution. Analysis of varnishes is a new field that can potentially provide records of pre-anthropogenic levels of atmospheric metals and other environmental pollutants. To evaluate the potential of desert varnish as an environmental monitoring tool, the following …

Substituent Effect On The Electronic And Assembling Properties Of Asymmetric Phenazine Derivatives, Bin Cao

UNLV Theses, Dissertations, Professional Papers, and Capstones

Currently, one-dimensional (1-D) nanostructures have drawn much interest because of their potential applications for nanoscale optoelectronic devices. Self-assembly (SA) based on π-conjugated systems through various intermolecular interactions has been widely used to produce 1-D nanostructure. Morphology of the assembled structures can be modified by incorporating substituents, which provide additional secondary interactions. Meanwhile, those substituents also influence the electronic properties of the molecules. Previous studies have made little effort to systematically study subsistent effects on both electronic and SA properties.

The primary objective of this research is to generate controllable 1-D structures through SA, and to provide a fundamental understanding of …

Controlled Functionalization Of Crystalline Polyolefins And Their Application In Soluble Polymer Support, Jihoon Shin

UNLV Theses, Dissertations, Professional Papers, and Capstones

Functionalization of polyolefins has been recognized as a useful methodology for the generation of new materials with a wide range of applications. Recently, crystalline or semi-crystalline polyolefins have drawn increasing attention in both industrial and academic fields as one of the most interesting engineering plastics, due to their remarkable physical and mechanical properties. This dissertation describes: (1) novel methods for the direct postfunctionalization of crystalline polyolefins to introduce functionality, (2) characterizations for the functionalized polymers to analyze their structures, molecular-weight properties, thermal properties, and hydrophilicity, and (3) an application of the modified crystalline polystyrene as a soluble polymer support for …

Evaluation Of Extraction Chromatography Resins For Rapid Actinide Analysis, Julie Marisa Gostic

UNLV Theses, Dissertations, Professional Papers, and Capstones

In this work, physical and chemical parameters associated with extraction chromatography separation procedures were investigated for rapid actinide analysis. A vacuum box system was designed in-house and was characterized in terms of flow rate reproducibility, matrix effects on flow rate for sequential elution, and actinide separation efficiency using different types of resin (TEVA, DGA and TRU). Results indicated that the columnar kinetics of the resins were sufficiently rapid to run high purity samples through the unit over a wide range of flow rates for all resin types. Single matrix interferences at a metal ion ratio of 1:10 6 relative to …

Spectroscopic Investigation Of Palladium-Copper Bimetallic Systems For Pem Fuel Cell Catalysts, Timo Hofmann

UNLV Theses, Dissertations, Professional Papers, and Capstones

One of the main barriers to commercialization of polymer electrolyte membrane fuel cells systems is cost, which is largely due to the need of platinum (Pt)-containing catalysts. In this thesis we investigate bimetallic systems consisting of a base metal (copper) and a noble metal (palladium) that, as an alloy on the nanoscale, mimic the electronic properties that make Pt desirable as a catalyst.

We present a detailed investigation of the electronic structure of carbon-supported Pd/Cu nanoparticle catalysts, model bilayer thin film systems, alloys, and various metal reference samples. We have investigated the valence band structure of the catalysts using a …

Analytical Method Development For Determination Of Volatile Organic Compounds In Calcareous Desert Soil, Mary F. Turner

UNLV Theses, Dissertations, Professional Papers, and Capstones

Soil sample preservation for volatile organic compound analysis generally requires short sample holding times or preservation of the sample's chemical constituents with sodium bisulfate (NaHSO 4 ). Calcareous soils cannot be preserved using NaHSO4 because effervescence will promote the loss of analytes, and short holding times before analysis are not practical for remote sampling locations. An experimental approach was developed for determination of volatile organic compounds (VOCs) in soil that utilizes solid sorbents for sample preservation and solid-phase microextraction (SPME) sample preparation technique coupled with gas chromatography/mass spectrometry (GC/MS) for analysis. Solid sorbents are used to sequester readily extractable (vapor …

Cloning, Overexpression, Purification And Characterization Of Gcp Ii Homologous Metalloprotein From Caulobacter Crescentus, Dilani Nilushika Gigiriwala Gamage

Masters Theses

A novel zinc metalloprotease gene isolated from Caulobacter crescentus (CCM) was cloned and overexpressed in Escherichia coli. A protease database search using MEROPS predicted this protein is a homolog of Glutamate Carboxypeptidase II (GCP II), a zinc metalloprotease found in humans and many other organisms. GCP II is considered as a suitable target for treating stroke, neurological disorders and a biomarker for prostate cancer. Chromatographic purification of CCM produced pure protein in milligram quantities. Molecular weight detern1ination using MALDI-TOF showed 51,582 Da and the extinction coefficient was found to be 33,007 M"1cm·1. Metal analysis and substrate profiling showed neither sufficient …