Chemistry Commons^™

Yttrium And Hydrogen Superstructure And Correlation Of Lattice Expansion And Proton Conductivity In The Bazr0.9y0.1o2.95 Proton Conductor, A. Braun, A. Ovalle, V. Pomjakushin, A. Cervellino, S. Erat, Wayne C. Stolte, T. Graule

Chemistry and Biochemistry Faculty Research

Bragg reflections in Y-resonant x-ray diffractograms of BaZr_0.9Y_0.1O_2.95 (BZY10) reveal that Y is organized in a superstructure. Comparison with neutron diffraction superstructure reflections in protonated/deuterated BZY10 suggests that both superstructures are linked, and that protons move in the landscape imposed by the Y. The thermal lattice expansion decreases abruptly for protonated BZY10 at T≥648±20 K, coinciding with the onset of lateral proton diffusion and suggesting a correlation of structural changes and proton conductivity. The chemical shift in the Y L₁-shell x-ray absorption spectra reveals a reduction from Y³⁺ toward Y²⁺ upon …

Earth Field Magnetic Resonance Imaging And Paramagnetic Contrast Agents, Saideh Sadat Mortazavi

Open Access Theses & Dissertations

The goal of this research was to visualize the uptake of copper by plants to aid phyto-remediation research. The hypothesis was that regions of the plant with more copper will have an enhanced NMR signal using copper as a paramagnetic contrast agent.

As the name implies, Earth Field Magnetic Resonance Imaging (EFMRI) spectrometry uses a magnetic field 300,000 times weaker than a 600 MHz Nuclear Magnetic Resonance (NMR) spectrometer. Just like in conventional human MRI, this portable instrument is capable of recording one, two and three dimensional images though the sample size is much smaller.

The enhancement of signal was …

Salsola Kali (Tumbleweed): A Possible Biomonitoring Device For The Detection Of Airborne Heavy Metals, Tenoch Benitez

Open Access Theses & Dissertations

Vehicular congestion generates particulate matter and contaminants such as lead, cadmium, copper, chromium, nickel, and zinc which have been detected in the U.S.-Mexico border region. To overcome the inconvenience of expensive sampling techniques, scientists started to assess air quality by using bioindicator plants, a technique called biomonitoring. Biomonitoring is an inexpensive and environmentally friendly approach to determine inorganic contaminants at trace levels. The purpose of this project was to determine the effectiveness of tumbleweed (Salsola kali) plants, sprayed with chelating agents, as a passive monitoring device to determine the possible presence of heavy metals in the ambient air around international …

Towards More Reliable Extrapolation Algorithms With Applications To Organic Chemistry, Jaime Nava

Open Access Theses & Dissertations

One of the main objectives of science and engineering is to predict the results of different situations. For example, in Newton's mechanics, we want to predict the positions and velocities of different objects (e.g., planets) at future moments of time.

In this Thesis, as a case study, we take the problem of predicting the properties of new chemical substances. One of the main objectives of chemistry is to design new molecules (and, more generally, new chemical compounds) which are useful for various practical tasks. New substances have already resulted in new materials for buildings and for spaceships, new explosives and …

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 …

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^{- …}

Optimization Of The Microprecipitation Procedure For Nuclear Forensics Applications, Lyndsey Renee Kelly

UNLV Theses, Dissertations, Professional Papers, and Capstones

Microprecipitation has become one of the most widely used sample preparation techniques for alpha spectroscopy. Many factors during the precipitation process can affect the yield and energy resolution by adding unwanted mass to the sample. Current applications in nuclear forensics call for an optimization of energy resolution and yield in order to improve identification and quantify specific radionuclides. The purpose of this research is to determine the optimal parameters used for microprecipitation. The optimal solution temperature, precipitation time, carrier amount, and hydrofluoric acid amount are used to investigate the influence of varying the type of carrier, as well as, the …

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

Seton Hall University Dissertations and Theses (ETDs)

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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 …

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 …

Studies Of Surfactants Effect On Riboflavin Fluorescence And Its Determination In Commercial Food Products And Vitamin Tablets., William Emmanuel Ghann

Electronic Theses and Dissertations

A simple and economical fluorometer using blue LEDs excitation sources and simple PMT detection had been built, assembled, optimized, and employed for measurement of fluorescence from riboflavin (vitamin B₂). Surfactants have been known to enhance the intensity of fluorescence of fluorescent compounds. Fluorescence analysis of riboflavin in the presence of various anionic, cationic, and nonionic surfactants was also conducted to determine if they could improve analysis. However, the surfactants employed did not seem to have any meaningful enhancement; in fact, some actually diminished the fluorescence intensity of riboflavin. The procedure was linear for riboflavin from 0.01 to 2.5 …

Study On Methods Of Simultaneous Multi-Component Analysis., Jennifer Bernice Ashie

Electronic Theses and Dissertations

Many new instrumentation and different instrumental techniques have been developed to deal with increasing complexity of samples encountered. Many researchers also have coupled these instrumental techniques with chemometric algorithms to assist in the quantitative analysis of multi-component samples in the hope of alleviating the need of tedious separation and cleanup procedures. These newer chemometric procedures tend to be complex and difficult to understand and implement and are successful under different circumstances and conditions. In this study, we start from the very simple beginning and examine the factors that can present difficulties with obtaining the correct results and observe how the …

Fabrication And Optical Properties Of Noble Metal Nanostructures, Mark Kinnan

All Dissertations

Experimental and theoretical results are presented in Chapters 2, 3, and 4 on the effects of dielectric medium, particle size, and interparticle distance, respectively, on plasmon coupling in two-dimensional arrays of silver nanoparticles. The arrays were fabricated via the self-assembly of single crystal particles from c.a. 46 nm to 287 nm on PVP-modified glass substrates. Spin-coated poly(methylmethacrylate) layers were used to immobilize the particles and prevent their surface aggregation. Varying the thickness of the PMMA layer made it possible to change the average dielectric medium between the particles. UV-Visible spectra of different arrays were compared to the corresponding electron microscope …

Synthesis, Characterization, And Application Of Ag Nanostructures, Stephen Hudson

All Dissertations

Noble metal nanoparticles (NPs) have been used for many centuries; however their properties were not truly scrutinized until Michael Farady's investigations in the 1850's. Advances in the field of nanotechnology over the last three decades have enabled insights into the properties of materials as their dimensions are reduced to the nanoscale. The repercussions of these insights are seen in many modern applications.
In this dissertation, properties of novel nanostructures based on Ag NPs are presented and discussed. The exceptional optical properties of Ag NPs stem from the collective oscillations of the conduction electrons known as plasmon resonances. The excitation of …

Pulse-Laser Infrared Photothermal Spectrometry Of Condensed-Phase Aerosols Based On Photothermal Deflection Spectroscopy, Oluwatosin Olubunmi Dada

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The research reported in this dissertation is aimed at development of photothermal deflection detector that is consistent with constraints imposed by aerosols sampling and analysis. The main objectives of this project are: 1) the design and evaluation of initial apparatus prototypes and 2) a test of the prototype apparatus with surrogate substances using conventional mid-infrared gas lasers.

Experimental evaluation of reduced size photothermal apparatus is first performed with gaseous samples. Analysis of trichlorofluoromethane (CFC-11) and ethanol vapors is performed with both conventional large apparatus and the prototype small apparatus. Comparison studies in terms of photothermal signal from both apparatuses are …

Sources And Source Processes Of Organic Nitrogen Aerosols In The Atmosphere, Mark E. Erupe

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The research in this dissertation explored the sources and chemistry of organic nitrogen aerosols in the atmosphere. Two approaches were employed: field measurements and laboratory experiments. In order to characterize atmospheric aerosol, two ambient studies were conducted in Cache Valley in Northern Utah during strong winter inversions of 2004 and 2005. The economy of this region is heavily dependent on agriculture. There is also a fast growing urban population. Urban and agricultural emissions, aided by the valley geography and meteorology, led to high concentrations of fine particles that often exceeded the national ambient air quality standards. Aerosol composition was dominated …

Linear Dichroism In Resonant Inelastic X-Ray Scattering To Molecular Spin-Orbit States, Renaud Guillemin, Stephane Carniato, Wayne C. Stolte, Loic Journel, Richard Taieb, Dennis W. Lindle, Marc Simon

Chemistry and Biochemistry Faculty Research

Polarization-dependent resonant inelastic x-ray scattering (RIXS) is shown to be a new probe of molecular-field effects on the electronic structure of isolated molecules. A combined experimental and theoretical analysis explains the linear dichroism observed in Cl 2p RIXS following Cl 1s excitation in HCl and CF₃Cl as due to molecular-field effects, including singlet-triplet exchange, indicating polarized-RIXS provides a direct probe of spin-orbit-state populations applicable to any molecule.

Corrosion Inhibition Of Self-Assembled Films On Iron By Electrochemical Impedance Spectroscopy, Yuan-Yuan Feng, Shen-Hao Chen, Juan-Juan Zhou, Wen-Juan Guo

Journal of Electrochemistry

The self-assembled films of tetradecylamine were formed on iron surface, and the inhibition ability of which for iron corrosion in 0.5 mol/L H₂SO₄ solutions was studied by electrochemical impedance spectroscopy technique. Results indicated that longer immersion time would result in stronger inhibition ability of the films. The maximal inhibition efficiency(IE) of the tetradecylamine films was 68.7%. When the tetradecylamine films were modified by dodecylthiol, the mixed films became denser and more stable, thus the inhibition ability increased remarkably. The η of the mixed films increased to 78.2%.

Monitoring Metal Containing Particulates Distribution On A College Campus Using Dandelion (Taraxacum Officinale) Leaves As Receptors., Suresh Chandra Regmi

Electronic Theses and Dissertations

This study aims to determine the distribution of particulates carrying heavy metals at selected sites on a college campus using dandelion leaves as collectors. As a comparison, sites far away from the campus surrounding Bristol Motor Speedway Car Racing Stadium were also monitored. To reduce the probability of memory effects from the long-term atmospheric deposition or absorption of metals from soil a seasonal plant, dandelion, was used to monitor the metal contents. The metals monitored are cadmium, calcium, copper, chromium, iron, lead, and zinc. Fourteen sites were monitored and samples were collected once a week initially (growing time of the …

A Selectivity Study On The Use Of Caffeine And Theobromine Imprinted Polypyrrole Surface Electrodes, Anil Kiran Kumar Vinjamuri

Masters Theses & Specialist Projects

Molecularly imprinted polymers (MIPs) are proving to be very effective in development of synthetic recognition systems and are of great interest to those interested in the field of sensor technology. The use of MIPs is receiving considerable interest due to the ability to prepare recognition matrices that possess high substrate selectivity and specificity. Conducting polymers (CP) have proved to be an excellent tool for the preparation of nano-structured biologically selective systems. Polypyrrole (Ppy) is one such CP that is extensively used for the construction of bioanalytical sensors. Ppy has shown great promise primarily due to its biocompatibility and thermal stability …

Cyclic Voltammetry And In Situ Ftir Studies Of Cyanide Adsorption On Nanostructured Au Film Electrode In Alkaline Solutions, Chun-Hua Zhen, Chun-Jie Fan, Shi-Gang Sun

Journal of Electrochemistry

The adsorption of cyanide(CN^-) on electrodes of nanometer scale thin film of gold supported on glassy carbon(nm-Au/GC) in alkaline solutions were investigated using cyclic voltammetry and in situ FTIR spectroscopy.It has revealed that the electrodeposited nanostructured Au thin film exhibited AIREs(abnormal infrared effects) for CN^-adsorption,which manifested 3 nonlinear IR spectral features: inversion of the direction of CN^-band,enhancement of IR absorption of adsorbed CN-species(about 39.2 folds) and increase in the FWHM(full width at half maximum) of CN^-band.

Characterization Of Commercial Pectin Preparations By Spectroscopic And Chromatographic Techniques., Daniel Wayne Dixon

Electronic Theses and Dissertations

Pectin has a long history as a food additive. However, elucidation of its fine structural and property relationships remains elusive. Recent research has focused on pectin's ability to complex with divalent heavy metals to aid in characterizing it. Commercial pectins of unknown composition were obtained from local grocers. Purified pectin samples from orange peel, lemon peel, and apple pomace, each of low and high levels of methyl esterification and of unknown distribution pattern were also purchased. Instead of metal complexation, several highly absorbing dyes such as Ruthenium Red, Nile Blue, and Acridine Orange were used to complex with the pectins …

Preparation And Characterization Of Macroporous Electrodes For Electrochemical Bioassays, Ashwin Rao

All Dissertations

Applications such as point-of-care medical diagnosis and in-the-field biological warfare agent detection require portable bioassays which are less laborious yet cost effective. Conventional sandwich bioassays see limited use for such applications as it involves time consuming steps of reagent treatment and washings, and are restricted to use inside laboratories. We explore new platforms for sandwich bioassays required by such applications. The platform we have developed is based on electrochemical methods of detection. Flow-through three-dimensional electrodes suitable for use in electrochemical sandwich bioassays were fabricated. A composite of superporous agarose and reticulated vitreous carbon (SPA-RVC) material was used for the fabrication …

Preparation Of Halogenated Derivatives Of Thiazolo[5,4-D]Thiazole Via Direct Electrophilic Aromatic Substitution, Vladimir Benin, Alan T. Yeates, Douglas Dudis

Chemistry Faculty Publications

Chlorination and bromination reactions of thiazolo[5,4-d]thiazole led to the generation of its mono- and dihalogenated derivatives. These are the first instances of successful direct electrophilic aromatic substitution in the thiazolo[5,4-d]thiazole ring system. X-ray analysis demonstrates that both 2-bromothiazolo[5,4-d]-thiazole and 2,5-dibromothiazolo[5,4-d]thiazole are planar structures, with strongly manifested π-stacking in the solid state. Theoretical analysis of the pyridine-catalyzed halogenation (MP2/6-31+G(d) and B3LYP/6-31+G(d)calculations) reveals that introduction of one halogen actually leads to a slightly enhanced reactivity towards further halogenation. Several halogenation mechanisms have been investigated: 1) The direct C-halogenation with N-halopyridine as electrophile; …

Synthesis And Electrochemical Studies In Microstructured Media, Jamie Norton

All Dissertations

In-situ electrochemical methods involving both oxidative and reductive mediators were employed to modify the oxidation state (doping level) of PEDOT polymers in colloidal PEDOT-coated silica core-shell particles that were prepared as a dispersion encapsulated in a hydrogel matrix. The modifications of the redox states of the PEDOT coating induced a change in the absorbance characteristics. A mediated electron transfer system was employed to ferry charge from the electrodes of the cell to the isolated particles. The mediator diffuses between the electrode surface and the PEDOT-coated particles to accomplish (de)doping. The developed system was a fully self-contained and electrically driven device. …

Determination Of Endocannabinoid Receptor Antagonist Sr141716 (Rimonabant) In Plasma By Liquid Chromatograph Tandem Mass Spectrometry, Melissa Mcculloch, Xiang Zhou, Yan Xu, Steve Brunell, Linda Spear

Chemistry Faculty Publications

SR141716 (rimonabant) is an endocannabinoid receptor antagonist. Endocannabinoids are a class of chemicals that affect neurotransmission via G-protein coupled CB1 (brain) and CB2 (peripheral tissue) receptors. Numerous animal studies have shown that SR141716 binds with the CB1 receptor in the brain, resulting in several biological consequences including reduced alcohol intake and reward as well as reduced food consumption. In this work, an analytical method based on liquid chromatography and electrospray ionization tandem mass spectrometry (LC–ESI-MS/MS) has been developed and validated for the quantitative measurement of SR141716 in both human and rat plasma to support the investigation of this compound. A …

In Situ Measurement Of Chloride Concentration And Ph Distribution In The Crevice During The Crevice Corrosion Of Copper Electronic Board, Min Zhang, Xiang-Dong Zhuo, Chang-Jian Lin

Journal of Electrochemistry

Although the crevice corrosion of metals had been extensively studied in the past years,it remained lack of direct experimental information of the micro chemical environments and electrochemical conditions inside the corroding crevice.The distribution of chloride concentration and local pH in the occluded area are the most crucial factors in development of crevice corrosion.The array probes in one dimension of Ag/AgCl and IrO₂ array were developed in this work to in situ follow the distribution of chloride concentration and local pH in the occluded area during the crevice corrosion propagation.Based on a designed simulated crevice corrosion system in 0.5mol/L NaCl …

C–N Bond Rotation And E–Z Isomerism In Some N-Benzyl-N-Methylcarbamoyl Chlorides: A Dft Study, Michael Horwath, Vladimir Benin

Chemistry Faculty Publications

The current report presents the first theoretical study of the restricted CN bond rotation in carbamoyl chlorides. Several N-benzyl-N-methylcarbamoyl chlorides were investigated, with varying pattern of substitution in the aromatic ring. Optimizations and frequency calculations were conducted employing DFT at the B3LYP/6-31+G(d) level of theory. Each of the studied structures exhibits a pair of rotamers (s-Z and s-E), generated upon rotation around the C(O)N bond. The s-E isomer is the global minimum in every case, but the preference for it is usually less than 1 kcal/mol. Two possible transition state structures were identified …

Phosphorylation Of Claudin-5 And Occludin By Rho Kinase In Brain Endothelial Cells, Masaru Yamamoto, Servio H. Ramirez, Shinji Sato, Tomomi Kiyota, Ronald Cerny, Kozo Kaibuchi, Yuri Persidsky, Tsuneya Ikezu

Ronald Cerny Publications

Critical to the proper maintenance of blood-brainbarrier (BBB) integrity are the endothelial tight junctions (TJs). Posttranslational modifications of essential endothelial TJ proteins, occludin and claudin-5, contribute and possibly disrupt BBB integrity. Our previous work has shown that Rho kinase (RhoK) activation mediates occludin and claudin-5 phosphorylation resulting in diminished barrier tightness and enhanced monocyte migration across BBB in the setting of human immunodeficiency virus-1 encephalitis (HIVE). To determine whether RhoK can directly phosphorylate TJ proteins, we examined phosphorylation of cytoplasmic domains of recombinant claudin- 5 and occludin by RhoK. We found that RhoK predominately phosphorylated two sites on occludin (T382 …