Chemistry Commons^™

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 …

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 …

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 …

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 …

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%.

Small Heat Shock Protein Activity Is Regulated By Variable Oligomeric Substructure, J. L. Benesch, M. Ayoub, C. V. Robinson, J. A. Aquilina

Faculty of Science - Papers (Archive)

The alpha-crystallins are members of the small heat shock protein (sHSP) family of molecular chaperones which have evolved to minimize intracellular protein aggregation, however they are also implicated in a number of protein deposition diseases. In this study we have employed novel mass spectrometry techniques to investigate the changes in quaternary structure associated with this switch from chaperone to adjuvant of aggregation. We have replicated the oligomeric rearrangements observed for in vivo disease-related modifications, without altering the protein sequence, by refolding the alpha-crystallins in vitro. This refolding results in a loss of dimeric substructure concomitant with an augmentation of substrate …

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 …

Advancing Data Analysis For Spectroscopic Imaging By Combining Wavelet Compression With Chemometrics, Robert Daryl Luttrell

Doctoral Dissertations

Spectroscopic imaging is a vital tool for studying heterogeneous samples such as bacteria and tissue. Its ability to acquire spatially resolved information allows for identification and classification of the various constituents within a sample. Spectroscopic imagers quickly acquire thousands to tens of thousands of spectra per measurement. These data are often arranged in the form of a 3-dimensional (3D) data cube which contains two spatial dimensions and one spectral dimension. This large amount of data is beneficial for gaining a thorough understanding about the distributions of chemical information. If too little information is measured, important chemical behavior may be overlooked. …

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 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. …

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 …

Expanding The Range Of Halogenated 1′-Methyl-1,2′-Bipyrroles (Mbps) Using Gc/Ecni-Ms And Gc × Gc/Tof-Ms, Kristin Pangallo, Robert K. Nelson, Emma L. Teuten, Emma L. Teuten, Byron E. Pedler, Christopher M. Reddy

Kristin Pangallo

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 solution,the …

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 …

Hypothetical Thermodynamic Properties. Subcooled Vaporization Enthalpies And Vapor Pressures Of Polyaromatic Hydrocarbons, William Hanshaw, Marjorie Nutt, James S. Chickos

James Chickos

No abstract provided.

Enthalpies Of Vaporization And Vapor Pressures Of Some Deuterated Hydrocarbons. Liquid−Vapor Pressure Isotope Effects, Hui Zhao, Patamaporn Unhannanant, William Hanshaw, James S. Chickos

James Chickos

No abstract provided.

2008 Newsletter, Morton Sternheim

STEM Education Institute Newsletters

NANOTECHNOLOGY 2008 INSTITUTE P. 2

IPY STEM CONNECTIONS P. 4

TEACHING PHYSICS TO TEACHERS

THE ARSENIC PROJECT P.10

STEM BRIDGE FOR

NOYCE SCHOLARS UPDATE

CONFERENCE ON ALTERNATIVE CERTIFICATION: LESSONS LEARNED

Phosphorylation Of Muc1 By Met Modulates Interaction With P53 And Mmp1 Expression, Pankaj K. Singh, Michelle E. Behrens, John P. Eggers, Ronald Cerny, Jennifer M. Bailey, Kandavel Shanmugam, Sandra J. Gendler, Eric P. Bennett, Michael A. Hollingsworth

Ronald Cerny Publications

MUC1, a transmembrane mucin, is a key modulator of several signaling pathways that affect oncogenesis, motility, and cell morphology. The interaction of MUC1 cytoplasmic tail (MUC1CT) with signal transducers and its nuclear translocation and subsequent biological responses are believed to be regulated by phosphorylation status, but the precise mechanisms by which this occurs remain poorly defined. We detected a novel association between the Met receptor tyrosine kinase and the MUC1CT. Met catalyzed phosphorylation of tyrosine at YHPM in the MUC1CT. Stimulation of S2-013.MUC1F pancreatic cancer cells with hepatocyte growth factor facilitated nuclear localization of MUC1CT, as determined by real time …

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 …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Matrix, Spencer M. Steinberg, Gary Cerefice, David W. Emerson

Separations Campaign (TRP)

Observations related to the oxidation of iodide to iodine (I₂) or hypoiodic acid (HIO) by MnO₂ were continued. The formation of triiodide presumable involves the adsorption of iodide onto the MnO₂ surface (perhaps displacing a surface hydroxyl group). The iodide should be subsequently oxidized and released back into solution as IOH or I₂, which rapidly forms I₃ ^-. The kinetic data has been modeled as a first order process. First order rate constants have been obtained for the formation of iodine in the presence of MnO₂. The increase in iodide …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective was to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in RTIL solutions, and use this data to effectively separate species with very similar chemical properties.

In consultation with a DOE collaborator, electrochemical methods and materials were evaluated and used to exploit the thermodynamic differences between similar chemical species enhancing the ability to selectively target and sequester individual species from mixtures. This project, in its third year, successfully completed phases 1, 2. Phase 3 was partially completed. The project expanded to include phase 4.

The following were specific goals for 2007-2008:

• To …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski

Separations Campaign (TRP)

The research objective is to experimentally evaluate the fundamental speciation of Pu and U in the TBP-dodecane-nitric acid- AHA system and the effect of pertechnetate, specifically:

• To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration, actinide ion concentration, temperature, and time.

• To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and …

Evaluation Of Fundamental Radionuclide Extraction Data For Urex, Kenneth Czerwinski

Separations Campaign (TRP)

The speciation of technetium and actinides in advanced solvent extraction systems is the basis for their manipulation in separations. The ability to understand and predict radionuclide speciation is paramount to successful modeling of proposed separation systems. This project will examine the speciation of radionuclides in different stages of the uranium extraction (UREX) separation scheme, providing data useful to modeling. The areas to be examined include the speciation of uranium and plutonium with tributylphosphate and the kinetics and thermodynamics of lanthanides and actinides in the TALSPEAK (Trivalent actinide lanthanide separation by phosphorous reagent extraction from aqueous complexes) system. The complexation constants …