Analytical Chemistry Commons^™

Gc×Gc-Ms And Parallel 2dlc-Ms Based Untargeted Metabolomics., Md Aminul Islam Prodhan

Electronic Theses and Dissertations

Untargeted metabolomics aims to analyze as many metabolites as possible in a biological system. Due to the vast complexity of the metabolome, bioanalytical platforms have been developed for untargeted metabolomics. While comprehensive two-dimensional gas chromatography mass spectrometry (GC×GC-MS) has been used in different scientific fields, its use in untargeted metabolomics is limited due to several challenges, such as complicated data analysis and limited accuracy of metabolite identification. Two-dimensional liquid chromatography mass spectrometry (2DLC-MS) has also been employed in untargeted metabolomics, but with limited metabolite coverage. This dissertation describes the efforts in developing new data analysis algorithms to improve the accuracy …

Structure Elucidation Of A Pyrrolobenzodiazepine Alkaloid And A Biologically Active Polyketide Produced By Rhodococcus Sp. Mtm3w5.2 Via Two-Dimensional Nmr Spectroscopy, Garrett Johnson

Electronic Theses and Dissertations

As the battle against ever-increasing drug resistence bacteria rages on, novel and sometimes more complex natural products can be used to combat this. In this study, two-dimensional NMR techniques were utilized to collect a complete spectral data set for two natural products. The first structure, a synthesized Pyrrolobenzodiazepine alkaloid natural product was confirmed through these methods. The second, a strain of Rhodococcus, MTM3W5.2, produces a novel antibacterial molecule in broth cultures and the active compound was fractionated using a Sephedex LH-20 column. Chromatographic purification yielded a pure sample at 58.90 minutes, RT.58. HRMS data deduced an exact mass of …

An Electrochemical Instrument For The Analysis Of Heavy Metals In Water Via Anodic Stripping Coulometry For Applications In Remote Sensing., Kelsey Lynn Kaht

Electronic Theses and Dissertations

From the high levels of arsenic in groundwater in Bangladesh to the lead contamination of drinking water in Flint, Michigan, there are incidents across the globe that highlight the need for a reliable instrument capable of monitoring heavy metals remotely and continuously in a variety of geographical locations. Typical instrumentation for water analysis, such as ICP and AAS, must be housed in a central lab and relies on an operator traveling to the collection site, obtaining a sample, and transporting it back to the lab. This analysis provides a snapshot of the water quality that is limited to the specific …

Stability And Reactivity Analysis Of Single Metal And Bimetallic Nanostructures By Anodic Stripping Voltammetry., Dhruba Kumar Pattadar

Electronic Theses and Dissertations

This dissertation has two main themes. The first involves studies aimed at developing anodic stripping voltammetry (ASV) as an analytical tool to characterize metal nanoparticles (NPs), with a focus on the size and aggregate structure of single metal NPs and the composition and atomic arrangement of bimetallic NPs. The second main theme involves studies that use ASV and electrochemical surface area-to-volume (SA/V) measurements to study the unique reactivity and transformations of single metal and bimetallic NPs. The transformations involve size and composition changes in response to ozone and electrochemical potential. Reactions involve size dependent galvanic exchange and electrocatalytic activity. The …

Microbial Diversity Of The Symbiotic Colony Of Bacteria And Yeast (Scoby) And Its Impact On The Organoleptic Properties Of Kombucha, Danielle L. St-Pierre

Electronic Theses and Dissertations

Kombucha is an effervescent fermented tea beverage that is gaining popularity for its probiotic nature and purported health benefits. The market for kombucha is expected to reach $1.8 billion by the year 2020. The composition of microbes that compose the symbiotic colony of bacteria and yeast (SCOBY) is highly variable with some species commonly found from the Gluconobacter, Acetobacter, Zygosaccharomyces, Saccharomyces, and Schizosaccharomyces genera.

It was hypothesized that different SCOBYs, obtained from different sources would vary in microbial diversity and produce different biochemical and flavor profiles in the resulting beverage over several generations. Kombucha is a fermented …

Synthesis And Characterization Of Heteronuclear Inorganic Complexes For The Photodegradation Of Persistant Organic Pollutants, Matthew A. Moyet

Electronic Theses and Dissertations

The focus of this thesis is to investigate the structural modification and characterization potential of common photocatalysts that have various uses for environmental remediation purposes. Pollution involving organic chemicals is one of the most common scenarios found in communities throughout the country. Efforts to rid contaminated drinking water supplies of these chemicals include physical and chemical filters, which have limited ability and efficacy. This lack of efficient filtration services has led to an increased demand for more effective treatment methods. Chemical species that react in the presence of light are known as photocatalysts and have been used in previous studies …

Electrodeposition Of Hydrogen Molybdenum Bronze Films And Electrochemical Reduction Of Carbon Dioxide At Low Over Potentials, Sami Alharbi

Electronic Theses and Dissertations

Hydrogen molybdenum oxide, known has molybdenum bronze, is a material of interest due to catalyzing electron transfer reactions. Specifically, molybdenum bronze is an electrocatalyst toward carbon dioxide reduction. Electrochemical deposition from a peroxymolybdic acid solution is a method for preparing molybdenum bronze films. This work demonstrates reproducible electrodeposition on indium tin oxide substrates and conductive carbon paper. Film thickness depends on concentration, time and pH. After characterization by film thickness, resistance, XRD and XPS, the as deposited films served as the working electrode for electrochemical reduction of carbon dioxide in 0.1 M NaHCO₃. Ion chromatography determined formate resulting …

Modification Of Chemical Vapor-Deposited Carbon Electrodes With Electrocatalytic Metal Nanoparticles Through A Soft Nitriding Technique, Enoch Amoah

Electronic Theses and Dissertations

Metal nanoparticles have been widely used for many catalytic and electrocatalytic applications due to their larger surface area-to-volume ratios and higher densities of active sites compared to bulk materials. This has resulted in much interest in understanding the electrocatalytic behavior of metal nanoparticles with respect to their structure. However, most research on this topic has employed collections of nanoparticles. Due to difficulties in controlling and characterizing particle loading and interparticle distance in nanoparticle ensembles, single nanoparticles studies have recently become a topic of great interest. In this study, a soft nitriding technique was applied to chemical vapor-deposited carbon ultramicroelectrodes (UMEs) …

Peroxide Sensing Using Nitrogen-Doped And Platinum Nanoparticle-Modified Screen-Printed Carbon Electrodes, Chidiebere Ogbu

Electronic Theses and Dissertations

Nitrogen-doped carbon materials have garnered much interest due to their abilities to behave as electrocatalysts for reactions important in energy production (oxygen reduction) and biosensing (hydrogen peroxide reduction). Here, we demonstrate fabrication methods and determine electrocatalytic properties of nitrogen-doped screen-printed carbon (N-SPCE) electrodes. Nitrogen doping of graphite was achieved through a simple soft-nitriding technique which was then used in lab-formulated screen-printing inks to prepare N-SPCEs. N-SPCEs displayed good electrocatalytic activity, reproducibility and long term stability towards the electrochemical reduction of hydrogen peroxide. N-SPCEs exhibited a wide linear range (20 µM to 5.3 mM), reasonable limit of detection of 2.5 µM, …

Immobilization Of Electrocatalytically Active Gold Nanoparticles On Nitrogen-Doped Carbon Fiber Electrodes, Daniel Mawudoku

Electronic Theses and Dissertations

Studies of single, isolated nanoparticles provide better understanding of the structure-function relationship of nanoparticles since they avoid complications like interparticle distance and nanoparticle loading that are typically associated with collections of nanoparticles distributed on electrode supports. However, interpretation of results obtained from single nanoparticle immobilization studies can be difficult to interpret since the underlying nanoelectrode platform can contribute to the measured current, or the immobilization technique can adversely affect electron transfer. Here, we immobilized ligand-free gold nanoparticles on relatively electrocatalytically inert nitrogen-doped carbon ultramicroelectrodes that were prepared via a soft nitriding method. Sizes of the particles were estimated by a …

Development Of Bismuth Oxyhalide Photocatalysts For Environmental And Industrial Applications, Robert Arthur

Electronic Theses and Dissertations

Heterogeneous semiconductor photocatalysis, of interest for water splitting and environmental remediation applications, uses light to drive reactions. Metal oxide and sulfide semiconductors have been previously studied but have limitations that include large band gap energies and high rates of recombination. Bismuth oxyhalides (BiOX) are an emerging class of photocatalysts with tunable band gaps and low rates of recombination due to their unique crystal structures. Studies of BiOX photocatalytic activity have largely focused on removal of azo dyes from aqueous solutions, with little attention paid to degradation byproducts. Furthermore, these catalysts have not been explored as a means to conduct organic …

Development Of Granulated Adsorbent For Clean-Up Of Water Contaminated By Cesium, Esther Alorkpa

Electronic Theses and Dissertations

A study was conducted on sol-gel synthesis of an adsorbent (phosphotungstic acid embedded in silica gel, H-PTA/SiO­₂) of radioactive cesium. A novelty of this work is covalent bonding of PTA to the surface of solid support that prevents leaching from the surface of the material. The sample was granulated with a binder, aluminium oxide (γ-Al₂O₃). Solid-state NMR and FT-IR spectroscopy were used to confirm the presence of Keggin units of PTA in the bound materials. Thermal analysis of H-PTA/SiO­₂ - γ-Al₂O₃ (50 %) showed that the water content in the …

Use Of Anodic Stripping Voltammetry To Study The Size-Selective Electrophoretic Deposition And Aggregation-Dependent Oxidation Of Metal Nanoparticles., Stacy L. Allen

Electronic Theses and Dissertations

This dissertation describes how anodic stripping voltammetry (ASV) was used to study size-controlled electrophoretic deposition (EPD) and the aggregation-dependent oxidation properties of citrate-stabilized Au nanoparticles (NPs). EPD of citrate-coated Au NPs occurs in the presence of hydroquinone (HQ) onto indium-tin-oxide-coated glass electrodes (glass/ITO) at potentials positive of the HQ oxidation potential. HQ oxidation produces protons at the electrode surface, which serve to neutralize the citrate molecules that electrostatically stabilize the Au NPs. Neutralization leads to the loss of stabilization and deposition onto the electrode. EPD in the presence of ferrocyanide, a non-proton-producing molecule, at oxidation potentials resulted in no deposition …

Evaluating Green Solvents And Techniques In Extraction Methods, Shanmugapriya Dharmarajan

Electronic Theses and Dissertations

Of all analytical techniques, extraction is a huge solvent-consuming process that could adversely impact the environment. Use of petroleum-based solvents for extraction of oilseeds is still a common practice, despite the potential fire hazard and the toxic water pollution. The rising awareness of chemical activities created immense need for sustainable development schemes and strategies that should address the environmental impact without compromising the yield. In the course of developing green extraction techniques, automation, alternative solvents, and selective extractions are the growing trend. This dissertation aligns with that progress by surveying green solvents, comparing their performance during oil extraction, examining a …

Investigating Anions And Hydrophobicity Of Deep Eutectic Solvents By Experiment And Computational Simulation, Amos Kwabena Dwamena

Electronic Theses and Dissertations

Deep eutectic solvents are a new generation of ionic liquid-like solvents formed by combining hydrogen bond acceptor with hydrogen bond donor which result in the depression of the melting point of the solvent. Like ionic liquids, anions play a critical role in tuning the polarity, physicochemical properties, and thermodynamic behavior of deep eutectic solvent (DES). Choline chloride is the most widely used quaternary ammonium salt (QAS) in the literature and has remarkable advantages from reduced cost to low toxicity and volatility. Choline bromide and choline iodide are other QAS that have not been used often for DES synthesis and applications, …

Mass Spectrometry-Based Quantitative Proteomic Analysis Of Biological Fluids, Patience Akosua Afedi

Electronic Theses and Dissertations

Proteomics is a high-throughput approach to study protein expression, structure, function, interaction, post-translational modifications, and localization in a cell or tissue. Proteomic shotgun approach was used to analyze changes in proteins in bovine follicular fluid (FF) and plasma (PL) from cows with high estradiol (HE2) or low E2 (LE2) during the preovulatory period. FF creates a unique microenvironment in follicles necessary for follicle growth and oocyte maturation, and pre-ovulatory concentrations of E2 have been reported to impact several processes involved with fertility. Initial steps in the analysis involved development of an immunodepletion protocol for high abundant proteins (HAPs) in bovine …

Advanced Analysis Of Compounds Of Toxicological Importance By Ice Concentration Linked With Extractive Stirrer (Icecles) Gc-Ms And Rp-Hplc-Esi-Ms-Ms, Joseph K. Dzisam

Electronic Theses and Dissertations

Cyanide and nitrosoamines (NAs) are ubiquitous compounds, found in our food and water, either by natural process or through man-made activities. The toxicity of cyanide is exerted by its ability to inhibit metalloenzymes such as cytochrome c oxidase, causing concomitant cascades of biochemical effects such as lactic acidosis, inhibition of ATP production, respiratory seizure, and potential death. Nitrosoamines, on the other hand, undergo biotransformation (metabolic activation in cytochrome P450) in the body to produce unstable intermediates that alkylate DNA, causing mutations, and leading to carcinogenesis. In order to further the advancement of a promising cyanide, cobinamide (Cbi), an LC-MS-MS method …

Application Of Analytical Techniques In Food Product Development, Sonali R. Pandey

Electronic Theses and Dissertations

Products are analyzed in major sectors of food industry to meet regulatory standards, food safety, quality control, and research and development. Analytical and extraction techniques have been applied for simultaneous investigation of multiple product characteristics. Food analysis faces critical challenges due to the complex composition of food, leading to matrix effects that result in loss of accuracy and reliability. The analytical techniques require an efficient sample preparation to avoid or minimize matrix effects. Solid-phase extraction has been widely used to address this issue. In this dissertation, the aim is to apply analytical techniques in food product development. To accomplish this, …

Physical And Chemical Trace Evidence From 3d-Printed Firearms, And Use Of A Quadcopter For Targeted Sampling Of Gaseous Mercury In The Atmosphere, Oscar Beauchamp Black

Electronic Theses and Dissertations

My forensic research resulted in the first peer-reviepaper to address the forensic challenges presented by 3D-printed polymer firearms. The work involved a systematic approach to the analysis of evidence stemming from 3D-printed firearms filling a critical void in current forensic knowledge. We used DART-MS to characterize the polymer evidence left behind by 3D-printed firearms as well as an evaluation of pre-existing firearm and toolmark techniques and fingerprint analysis. We demonstrated that 3D-printed firearms leave behind characteristic polymer residue on cartridge cases bullets and the receiving surface which can be identified using DART-MS. The culmination of the work includes a database …