Chemistry Commons^™

Spectroelectrochemical Studies Of Metalloporphyrins In Room Temperature Ionic Liquid, Yong Soo Hoo

Master's Theses (2009 -)

The oxidation/reduction reactions of porphyrins and metalloporphyrins play an important role in medicinal, industrial and biochemical reactions. Metalloporphyrins are particularly useful as potential catalysts for a variety of processes including catalytic oxidations. The unique properties of metalloporphyrins make them good candidates as electrocatalysts for fuel cells. Metalloporphyrins also play some important roles in biological functions.

By incorporating spectroscopic experiments such as UV-visible or infra-red spectroscopy along with electrochemical experiments such as cyclic voltammetry, one is able to determine the structural changes of the molecule when oxidation or reduction reaction is carried out.

Perfluoroalkyl Phosphonic And Phosphinic Acid Electrolytes For Proton Exchange Membrane Fuel Cells, Mahesha Herath

All Dissertations

Perfluorinated sulfonic acid polymers have been considered as the state-of-art membrane materials for proton exchange membrane fuel cells. A major technical issue with these polymers is that they do not function well at temperatures above 80 °C and at low humidities. Therefore, research has been focused on developing PEM materials that can operate independent of hydration requirements. The operation of fuel cells at high temperature (e.g. 120 oC) increases fuel cell system efficiency due to faster electrode kinetics and better CO tolerance. This dissertation will describe a study of proton-transport rates and mechanisms under anhydrous and aqueous conditions using a …

Rapid Multi-Class Multi-Residue Method For The Confirmation Of Chloramphenicol And Eleven Nitroimidazoles In Milk And Honey By Liquid Chromatography Tandem Mass Spectrometry, Mark Cronly, Patrice Behan, Barry Foley, Liam Regan, Sheila Martin, Michael Doyle, Edward Malone

Articles

A confirmatory method has been developed to allow for the analysis of eleven nitroimidazoles and also chloramphenicol in milk and honey samples. These compounds are classified as A6 compounds in annex IV of council regulation 2377/90 and therefore prohibited for the use in animal husbandry. Milk samples are extracted by acetonitrile with addition of NaCl, while honey samples are first dissolved in water before a similar extraction. Honey extracts undergo a hexane wash to remove impurities. Both milk and honey extracts are evaporated to dryness and reconstituted in initial mobile phase. These are then injected onto an LC-MS/MS system and …

Measurement And Wavelet Analysis Of The Electrochemical Noise Of Rebar Steel In Simulated Concrete Pore Solution, Rong-Gang Hu, Chen-Qing Ye, Shi-Gang Dong, Chang-Jian Lin

Journal of Electrochemistry

Electrochemical noise (ECN) measurement can provide information about both corrosion rate and corrosion type while inflicting no perturbation on the studied system. The ECN data of steel rebar in SPS with different amount of Cl-were collected and treated by discrete wavelet transformation to evaluate the contribution from transients in different frequency in the overall signals. Energy distribution plot (EDP) indicated in SPS with 0.0001 mol/L NaCl, the transients with time constant between 16 ～ 32 s were found to be predominant over other processes; while in SPS with higher Cl-concentration, the trend toward active corrosion became the main process. It …

Fabrication Of Electrochemically Activated Glassy Carbon/Bismuth Film Electrodes For Sensitive Analysis Of Pb(2+) And Cd(2+), Kang Shi, Wen-Jing Wang, Kun Hu

Journal of Electrochemistry

The application of electrochemically activated glassy carbon (GC) in the in-situ preparing of bismuth film electrodes (BiFEs) to analyze Pb^{2 +} and Cd^{2 +} was investigated. The glassy carbon electrodes were electrochemically activated by either potentiostic or cyclic polarization in 1 mol·L^-1 NaOH solution. Experimental results show that employment of HCl solution as the analytical solution not only can reproducibly renew the electrochemically activated GC electrode surface with an electrochemical clear procedure, but also can greatly enhance the sensitivity of BiFes method for analysis of Pb^{2 +} and Cd^{2 +}. The test range thus …

Blocking Method In Enzyme-Amplified Amperometric Dna Biosensor, Miao He, Wei Chen, Xiong-Wei Xu, Ai-Lin Liu, Xin-Hua Lin

Journal of Electrochemistry

Non-specific absorption of enzyme and nucleotide is a main source leading to the background staining in enzyme-amplified amperometric detection of DNA. To eliminate the background staining in this system, the blocking procedure by mercapto-hexanol (MCH) and bovine serum albumin (BSA) was studied systematically. The results show that the anti-fouling effect of BSA is better than that of MCH. A simple and efficient blocking strategy employing BSA as the sole blocking reagent was established and applied in the detection of PMLRARα fusion gene in acute promyelocytic leukemia. It can effectively eliminate the background staining,shorten the pre-processing time,and achieve strong signal amplification.

A Preliminary Study In Probing Rapid Method Of Isotope 87sr/86sr Analysis By Electrospray Ionization -Quadrupole Ion Trap - Mass Spectrometry, Sheng Song

Student Theses and Dissertations

The isotope ratio 87Sr/86Sr, typically reported in geologic investigations, is obtained by direct electrospray ionization of aqueous sample containing Sr(II), Rb(I) and 18c6. At relatively high concentrations, we observed favorable formation of Sr2+(18c6)₂ and Rb+(18c6) over Sr2+(18c6) complexes. Physical separation of Sr2+(18c6)₂ and Rb+(18c6) as well as separation of Sr2+(18c6)₂ is observed by simply injecting the sample solution to ESI source using simple PEEK tubing in neutral pH. These phenomena are caused by the difference in mobility of the complexes and masked by the gas phase association reactions. ESI-QITMS successfully obtained the expected isotope distribution of Sr(II) …

Chemical Characterization Of Botanical Products: Comprehensive Speciation By Liquid Chromatography Particle Beam Mass Spectrometry, Joaudimir Castro Georgi

All Dissertations

The dietary supplement industry has expanded and many of these supplements have become an important aspect of people's everyday lives. In 1994, the U.S. Dietary Supplement Health and Education Act (DSHEA) classified numerous nutraceutical/botanical products as dietary supplements because of their beneficial medicinal properties and provided the necessary regulation to the supplement producers. Since then, the interest of the scientific community towards dietary supplements has grown intensively and numerous studies have been carried out in order to understand the chemical behavior of the active molecules in the human body. The development towards analytical methods for the quantification of the active …

Analysis Of Ammonia And Volatile Organic Amine Emissions In A Confined Poultry Facility, Hanh Hong Thi Dinh

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The National Air Emission Monitoring Study (NAEMS) project was funded by the Agricultural Air Research Council (AARC) to evaluate agricultural emissions nationwide. Utah State University (USU) is conducting a parallel study on agricultural emissions at a Cache Valley poultry facility. As part of this parallel study, samples of animal feed, eggs and animal waste were collected weekly from three manure barns (designated: manure barn, barn 4 - manure belt and barn 5 - high rise) from May 2008 to November 2009.

These samples were analyzed to determine ammonia content, total Kjeldahl nitrogen content and ammonia emission. The yearly average calculated …

Chromatographic Studies Of Drug-Protein Binding In Diabetes, Kathryn (Krina) S. Joseph

Department of Chemistry: Dissertations, Theses, and Student Research

Drug-protein binding can have a dramatic impact on the distribution and metabolism of a drug. This manuscript describes the use of high-performance affinity chromatography to examine the binding of various compounds to human serum albumin (HSA) in normal and diabetic disease states. The first study examined the use of four coumarin compounds as possible alternatives to warfarin as a probe for Sudlow site I on HSA. High-performance affinity chromatography and immobilized HSA columns were used to compare and evaluate the binding properties of these probe candidates. It was found from this group that 4-hydroxycoumarin was the best alternative to warfarin …

Preparation And Characterization Of Extraction Chromatography Resins Using N-Donor Extractants For Trivalent Actinide And Lanthanide Separations, Christopher L. Klug

UNLV Theses, Dissertations, Professional Papers, and Capstones

Actinide and lanthanide elements exist in the geosphere and biosphere due to both natural abundances and anthropogenic activities. The investigation of the presence and transport of actinides through the environment is of great scientific interest. In order to prepare environmental samples for precise measurements, the individual actinides must be separated from the chemically similar lanthanides, and from neighboring actinides. Existing extraction chromatography resins are either poorly suited for this separation, have bleeding problems, are not reusable, or fail the CHON principle. In an effort to resolve these issues, malonamides and N-donor extractants from the BTP and BTBP classes of solvent …

Comparison Of Rna Quality From Stressed And Unstressed Recombinant Escherichia Coli, Mary Alice Salazar

All Theses

High quality, intact RNA is required for DNA microarray studies, cloning, and reverse transcriptase polymerase chain reaction (rt-PCR) analysis. There are several analytical methods used to assess the RNA quality. The RNA Integrity Number (RIN) from the Agilent Bioanalyzer is one quality control assay used to evaluate RNA. For recombinant Escherichia coli cultured under stressful conditions the RNA profiles obtained using the Agilent Bioanalyzer indicate RNA degradation; however, RNA obtained and purified in parallel from unstressed recombinant cultures indicate acceptable RNA values without significant degradation. We proposed that for stressed E. coli the RIN value is not necessarily indicative of …

Field And Smog Chamber Studies Of Agricultural Emissions And Reaction Products, Derek J. Price

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Agricultural emissions are an important contributor to atmospheric aerosol. These emissions include nitrogen containing organic compounds, primarily as amines, which have not been well investigated to date. Although there have been several studies that have looked at the emission of gas phase amines, there are only a few studies that have focused on ambient amine-based aerosol. There have also only been a handful of smog chamber studies that have investigated amine aerosol chemistry. Kinetic studies have looked at the reactions of amines with OH and ozone. However, amine reactions with nitrate radical (NO₃) are not well understood. Several …

A Synthetic Biological Engineering Approach To Secretion- Based Recovery Of Polyhydroxyalkanoates And Other Cellular Products, Elisabeth Linton

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The costs associated with cellular product recovery commonly account for as much as 80% of the total production expense. As a specific example, significant recovery costs limit commercial use of polyhydroxyalkanoates (PHA), which comprise a class of microbially-accumulated polyesters. PHAs are biodegradable compounds that are of interest as a sustainable alternative to petrochemically-derived plastics. Secretion-based recovery of PHAs was studied to decrease PHA production costs. Type I and II secretory pathways are commonly used for the translocation of recombinant proteins out of the cytoplasm of E. coli. Proteins were targeted for translocation using four signal peptides (HlyA, TorA, GeneIII, …

Pulsed-Laser Excited Photothermal Study Of Glasses And Nanoliter Cylindrical Sample Cell Based On Thermal Lens Spectroscopy, Prakash Raj Joshi

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The research in this dissertation presents Pulsed-Laser Excited photothermal studies of optical glasses and cylindrical sample cell.

First, a study of a photothermal lens experiment and the finite element analysis modeling for commercial colored glass filters is done. The ideal situation of a semiinfinite cylinder approximate model used to describe the photothermal lens experiment requires the boundary condition that there is no transfer of heat from the glass to surrounding when the glass is excited with a laser. The finite element analysis modeling for photothermal signal with coupling heat with surrounding shows the thermal heat transfer between the glass surface …

Characterization Of Glycation Sites On Human Serum Albumin Using Mass Spectrometry, Omar S. Barnaby

Department of Chemistry: Dissertations, Theses, and Student Research

The modification of proteins by reducing sugars is a process that occurs naturally in the body. This process, which is known as glycation, has been linked to many of the chronic complications encountered during diabetes. Glycation has also been linked to changes in the binding of human serum albumin (HSA) to several drugs and small solutes in the body. While these effects are known, there is little information that  explains why these changes in binding occur. The goal of this project was to obtain qualitative and quantitative information about glycation that occurs on HSA. The first section of this dissertation …

Molecular Characterization Of The Soluble Fraction Of Atmospheric Particulate Matter Obtained By Chemical Oxidation With Nitric Acid, Amanda Susan Priest

Chemistry & Biochemistry Theses & Dissertations

The availability of information regarding the composition of ambient atmospheric particulate matter and the transformations that these compounds may undergo upon atmospheric transit is surprisingly absent. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry is used in this study to rapidly evaluate the composition of the water-soluble organic fraction of standard and collected atmospheric particulate matter samples, and the changes that these mixtures undergo upon oxidation with nitric acid. The standard samples include representative particulate matter collected over the course of a year in Washington, D.C. and particulate matter from the exhaust of a diesel-powered engine. The collected sample …

An Electrochemical Cell For The Efficient Turn Around Of Wafer Working Electrodes, Nicholas Wozniak, Alyssa Frey, Lucas Osterbur, Timothy Boman, Jennifer R. Hampton

Faculty Publications

We present a new design for an electrochemical cell for use with wafer working electrodes. The key feature of the design is the use of half turn thumb screws to form a liquid-tight seal between an o-ring and the sample surface. The assembly or disassembly of the cell requires a half turn of each thumb screw, which facilitates the quick turn around of wafer samples. The electrochemical performance of the cell is demonstrated by cyclic voltammetry and double step chronoamperometry measurements of the ferricyanide/ferrocyanide couple.

The Analysis Of Cyanide And Its Breakdown Products In Biological Samples, Brian A. Logue, Diane M. Hinkens, Steven I. Baskin, Gary A. Rockwood

Chemistry and Biochemistry Faculty Publications

Cyanide is a toxic chemical that may be introduced into living organisms as a result of natural processes and/or anthropogenic uses (legal or illicit). Exposure to cyanide can be verified by analysis of cyanide or one of its breakdown products from biological samples. This verification may be important for medical, law-enforcement, military, forensic, research, or veterinary purposes. This review will discuss current bioanalytical techniques used for the verification of cyanide exposure, identify common problems associated with the analysis of cyanide and its biological breakdown products, and briefly address the metabolism and toxicokinetics of cyanide and its breakdown products in biological …

A Bland–Altman Comparison Of The Lead Care® System And Inductively Coupled Plasma Mass Spectrometry For Detecting Low-Level Lead In Child Whole Blood Samples, Christina Sobin, Tanner Schaub, Natali Parisi, Eva De La Riva

Selected Works Temporary Series

Chronic childhood lead exposure, yielding blood lead levels consistently below 10 μg/dL, remains a major public health concern. Low neurotoxic effect thresholds have not yet been established. Progress requires accurate, efficient, and cost-effective methods for testing large numbers of children. The LeadCare® System (LCS) may provide one ready option. The comparability of this system to the “gold standard” method of inductively coupled plasma mass spectrometry (ICP-MS) for the purpose of detecting blood lead levels below 10 μg/dL has not yet been examined. Paired blood samples from 177 children ages 5.2–12.8 years were tested with LCS and ICP-MS. Triplicate repeat tests …

Transition States In Ei Reactions, Charles A. Kingsbury

Department of Chemistry: Faculty Publications

The pyrolysis of amine oxides, sulfoxides, selenoxides, and esters to form alkenes is believed to be a concerted reaction with a cyclic transition state. Phosphine oxides, sulfones, and nitro compounds are unreactive. This study seeks to identify reasons for the lack of reactivity of the latter. Transition states were located for all substrates progressing from RHF/3-21G* to the MP2/6-31+G(d,p) level (in certain cases). For sulfones and nitro compounds, two possible reasons for lack of reactivity were considered: (1) Atoms approaching one another in the transition state may be considered to participate in a local n_O→σ*_{CH …}

Two-Dimensional To Three-Dimensional Structural Transition Of Gold Cluster Au 10 During Soft Landing On Tio 2 Surface And Its Effect On Co Oxidation, Hui Li, Yong Pei, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

We investigate the possible structural transition of a planar Au₁₀ cluster during its soft landing on a TiO₂ (110) surface with or with no oxygen defects. The collision between the gold cluster and the oxide surface is simulated using the Car–Parrinello quantum molecular dynamics method. Both high-speed and low-speed conditions typically implemented in soft-landing experiments are simulated. It is found that under a high-speed condition, the gold cluster Au₁₀ can undergo a sequence of structural transitions after colliding with a defect-free TiO₂ (110) surface. When the TiO₂ (110) surface possesses oxygen vacancies, however, chemical bonds …

Process For Preparation Of Conducting Polymers, Reuben D. Rieke

Department of Chemistry: Faculty Publications

Methods of preparing conducting polymers and the conductive polymers prepared therefrom are provided. The method includes a) combining a monomer-metal complex together with a manganese (II) halide to provide a monomer-manga nese complex, and b) combining the monomer-manganese complex together with a metal catalyst to provide the conductive polymer. Electronic devices can be made using the polymers prepared as described herein.

Icosahedral B12-Containing Core–Shell Structures Of B80, Hui Li, Nan Shao, Bo Shang, Lan-Feng Yuan, Jinlong Yang, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Low-lying icosahedral (I_h) B₁₂-containing structures of B₈₀ are explored, and a number of core–shell isomers are found to have lower energy than the previous predicted B₈₀ fullerene. The structural transformation of boron clusters from tubular structure to core–shell structure may occur at a critical size less than B₈₀.

Graphene-Like Bilayer Hexagonal Silicon Polymorph, Jaeil Bai, Hideki Tanaka, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

We present molecular dynamics simulation evidence for a freezing transition from liquid silicon to quasi-twodimensional (quasi-2D) bilayer silicon in a slit nanopore. This new quasi-2D polymorph of silicon exhibits a bilayer hexagonal structure in which the covalent coordination number of every silicon atom is four. Quantum molecular dynamics simulations show that the stand-alone bilayer silicon (without the confinement) is still stable at 400 K. Electronic band-structure calculations suggest that the bilayer hexagonal silicon is a quasi-2D semimetal, similar to a graphene monolayer, but with an indirect zero band gap.

Physical And Biochemical Assessment Of Mexican Palo Verde Response To Chromium Toxicity, Yong Zhao

Open Access Theses & Dissertations

In the United States, about 1/3 of the 1400 superfund sites have been reported to be chromium contaminated, making chromium the second most common metal found in superfund chemical contamination sites. Chromium removal from soil has commonly been carried out via chemical, physical, and thermal processes. However, these methods are expensive and/or invasive to local ecosystems. In contrast to these techniques, phytoremediation (the use of plants to remove toxic substances from areas containing contamination at low or medium levels) appears to be a cost-effective and environmentally friendly process for chromium removal. However, most reports on chromium phytoremediation suggest that this …

Geochemical Investigation Of An Offshore Sewage Sludge Deposit, Barcelona, Catalonia, Spain, Michael A. Kruge, Albert Permanyer, Jordi Serra, Danlin Yu

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

For 20 years ending in the 1990’s the city of Barcelona discharged the products from a large primary sewage treatment plant directly into the Mediterranean Sea via underwater conduits. About ca. 3 million m³ of relict sewage sludge, rich in organic matter and heavy metals, has spread over an elongated area offshore, due to successive ruptures of the conduits. The use of the discharge pipes ceased, but he sludge deposit remains in place for the time being.

To understand the history and present state of the sludge deposit in advance of future remediation, a program of geophysical mapping, sampling, …

Toxicodynamics And Biotransformation Of Azaspiracids Incorporating Liquid Chromatography-Tandem-Mass Spectrometry (Lc-Ms/Ms) Techniques., Daniel O'Driscoll

Theses

Azaspiracids (AZAs) are a family of lipophilic polyether marine biotoxins, that have caused a number of human intoxication incidents in Europe since 1995, which was the first incident reported following the consumption by consumers of intoxicated shellfish {Mytilus edulis). This class of phycotoxins has been responsible for extended closures of shellfisheries in various locations around Europe, where levels of AZAl-3 are regulated in shellfish. Since their discovery in 1995, AZAs have become the focus of extensive research, resulting in the discovery of numerous analogues. Only AZAl and AZA2 have been found in phytoplankton and all the other analogues are believed …

Application Of Liquid Chromatography - Tandem Mass Spectrometry For The Determination Of Veterinary Drug Residues In Food Of Animal Origin, Brian Kinsella

Theses

The QuEChERS (quick, easy, cheap, effective, rugged and safe) sample preparation approach was evaluated for the extraction of anthelmintic residues from bovine milk and tissues. Liquid chromatography coupled to tandem mass spectrom.etry (LC- MS/MS) was used for detection and quantification of residues, which included the benzimidazoles (BZs), macrocyclic lactones (MLS) and the generally overlooked flukicides.

Initial work focused on the optimisation of a QuEChERS method to effectively extract anthelmintic residues from milk and liver. The method involves the extraction of residues with acetonitrile (MeCN) in the presence of salts (MgS04 and NaCl) to induce phase separation. After shaking and centrifugation, …

Determination Of Lead, Cadmium, Zinc And Nickel Inedible Oil Products By Stripping Voltammetry., Ng Khan Loon

Student Works (2010-2019)

Edible oil products had become an everyday food that been consumed by most of the people either for dressing or for cooking purpose. Metal has become a common contamination to the food product, which it found the way into the edible oil through environment and processing contamination such as crushing, distillation, and hydrogenation. In this Study, the main focuses of metal analysis are only confined to 4 common metals which are the Cadmium, Lead, Zinc and Nickel. These elements are selected in this study due to reason that Cadmium and Lead are commonly known for their contamination from environment and …